TW202124378A - Condensed heterocyclic compound and noxious organism control agent capable of effectively eliminating insects or mites - Google Patents

Abstract

Provided is a novel noxious organism control agent, particularly an insecticide or a miticide, which is a condensed heterocyclic compound represented by formula (1), or a salt of the condensed heterocyclic compound or an N-oxide of the condensed heterocyclic compound and the salt. In formula (1), D substituted by -S(O)nR1 represents a ring represented by D1, D2 or D3; Q represents a ring represented by Q1, Q2, Q3 or Q4; G1, G2, G3, G4, G5, A2, A3, A4, A5 and A8 each represent a nitrogen atom, etc.; T1 and A1 each represent an oxygen atom, etc.; R1 represents C1-C6 alkyl, C1-C6 haloalkyl, etc.; R2, R3, R6, R7 and Y6 each represent a hydrogen atom, a halogen atom, C1-C6 alkyl, etc.; n represents an integer of 0, 1 or 2.

Description

Condensed heterocyclic compounds and pest control agents

The present invention relates to novel condensed heterocyclic compounds and their salts, and pest control agents characterized by containing the compounds as effective ingredients.

For example, although Patent Document 1 to Patent Document 31 disclose condensed heterocyclic compounds, there is no disclosure regarding the condensed heterocyclic compounds of the present invention. Furthermore, its pest control agents, especially as insecticides. The usefulness of acaricides and internal or external parasite control agents for mammals or birds is completely unknown.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2016/005263

[Patent Document 2] International Publication No. 2015/198859

[Patent Document 3] International Publication No. 2015/133603

[Patent Document 4] International Publication No. 2015/121136

[Patent Document 5] International Publication No. 2015/091945

[Patent Document 6] International Publication No. 2015/087458

[Patent Document 7] International Publication No. 2015/071180

[Patent Document 8] International Publication No. 2015/059088

[Patent Document 9] International Publication No. 2015/002211

[Patent Document 10] International Publication No. 2015/000715

[Patent Document 11] International Publication No. 2014/157600

[Patent Document 12] International Publication No. 2014/148451

[Patent Document 13] International Publication No. 2014/142292

[Patent Document 14] International Publication No. 2014/132972

[Patent Document 15] International Publication No. 2014/132971

[Patent Document 16] International Publication No. 2014/123206

[Patent Document 17] International Publication No. 2014/123205

[Patent Document 18] International Publication No. 2014/104407

[Patent Document 19] International Publication No. 2013/180194

[Patent Document 20] International Publication No. 2013/180193

[Patent Document 21] International Publication No. 2013/191113

[Patent Document 22] International Publication No. 2013/191189

[Patent Document 23] International Publication No. 2013/191112

[Patent Document 24] International Publication No. 2013/191188

[Patent Document 25] International Publication No. 2013/018928

[Patent Document 26] International Publication No. 2012/086848

[Patent Document 27] International Publication No. 2012/074135

[Patent Document 28] International Publication No. 2011/162364

[Patent Document 29] International Publication No. 2011/043404

[Patent Document 30] International Publication No. 2010/125985

[Patent Document 31] International Publication No. 2009/131237

The development of pest control agents for the prevention and control of various diseases and pests such as agricultural and horticultural pests, forest pests, or sanitary pests, etc., and a wide variety of pesticides are now available for practical use.

However, through long-term use of these chemicals, disease and pests have gained resistance to chemicals in recent years, making it more and more difficult to prevent and control with existing insecticides or fungicides used in the past. In addition, some of the existing pest control agents are highly toxic, or the problem of disturbing the ecosystem by leaving something in the environment for a long period of time has also been realized. Under such circumstances, it is always desired to develop novel pest control agents that not only have a high degree of pest control activity, but also have low toxicity and low residue.

The object of the present invention is to provide a novel pest control agent with low toxicity and low residue that exhibits excellent pest control activity, has almost no adverse effects on non-standard organisms such as mammals, fish, and beneficial insects.

The inventors of the present invention aim to solve the above-mentioned problems as a result of repeated diligent research, and found that the novel fused heterocyclic compound represented by the following formula (I) related to the present invention exhibits excellent pest control activity, especially insecticidal activity. It has acaricidal activity and has almost no adverse effects on non-standard organisms such as mammals, fish and beneficial insects. It is an extremely useful compound, and the present invention has been completed.

That is, the present invention relates to the following [1] to [171].

A condensed heterocyclic compound represented by formula (1) or its salt or the N-oxide,

[In the formula, _{D substituted with -S(O) n} R ¹ represents a ring represented by any one of D1, D2 or D3,

Q represents a ring represented by any of Q1, Q2, Q3 or Q4,

G ₁ represents a nitrogen atom or C(Y1),

G ₂ represents a nitrogen atom or C(Y2),

G ₃ represents a nitrogen atom or C(Y3),

G ₄ represents a nitrogen atom or C(Y4),

G ₅ represents a nitrogen atom or C(Y5),

T ₁ represents N (T _1a ), oxygen atom or sulfur atom,

A ¹ represents N (A ^1a ), oxygen atom or sulfur atom,

A ² represents a nitrogen atom or C(R ² ),

A ³ represents a nitrogen atom or C(R ³ ),

A ⁴ represents a nitrogen atom or C(R ⁴ ),

A ⁵ represents a nitrogen atom or C(R ⁵ ),

A ⁸ represents a nitrogen atom or C(R ⁸ ),

R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, (C ₁ -C ₆ )alkyl ^{optionally substituted by R 1a} _{, C 2} -C ₆ alkenyl, C ₂ -C ₆ Haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ )alkyl, C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ )alkyl or hydroxy (C ₁ -C ₆ )alkyl,

R ^1a represents C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio , C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl or cyano base,

R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ Haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, -C(O)R ^20a , -C(O)OH, hydroxyl, -NH _2. -NHR ^20g , -N(R ^20h )R ^20g , mercapto, cyano or nitro,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ haloalkenyl group, a C ₂ -C ₆ haloalkynyl group, a C ₁ -C ₈ alkane Oxy, C ₁ -C ₈ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio , R ^3a are substituted with any of (C ₁ -C ₆₎ alkylthio, C ₁ -C ₆ alkylsulfinyl acyl, C ₁ -C ₆ alkylsulfinyl acyl halides, C ₁ -C ₆ alkyl Sulfonyl, C ₁ -C ₆ haloalkylsulfonyl, -C(O)R ^30a , -C(O)OH, hydroxyl, -OC(O)R ^30e , -OS(O) ₂ R ^30f , -NH ₂ , -NHR ^30g , -N(R ^30h )R ^30g , mercapto, -SC(O)R ³⁰ⁱ , -SF ₅ , cyano, nitro, phenyl, phenyl optionally substituted ^{by R 3b} , Heterocyclic group or heterocyclic group optionally substituted ^{by R 3b,}

R ^3a represents a C ₁ -C ₈ alkoxycarbonyl group,

R ^3b represents a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a cyano group or a nitro group,

R ⁴ represents hydrogen atom, halogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ haloalkynyl, C ₁ -C ₈ alkane Oxy, C ₁ -C ₈ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio , R ^4a is substituted with any of the (C ₁ -C ₆₎ alkylthio, C ₁ -C ₆ alkylsulfinyl acyl, C ₁ -C ₆ alkylsulfinyl acyl halides, C ₁ -C ₆ alkyl Sulfonyl, C ₁ -C ₆ haloalkylsulfonyl, -C(O)R ^40a , -C(O)OH, hydroxyl, -OC(O)R ^40e , -OS(O) ₂ R ^40f , -NH ₂ , -NHR ^40g , -N(R ^40h )R ^40g , mercapto, -SC(O)R ⁴⁰ⁱ , -SF ₅ , cyano, nitro, phenyl, phenyl optionally substituted ^{by R 4b} , Heterocyclic group or heterocyclic group optionally substituted ^{by R 4b,}

R ^4a represents a C ₁ -C ₈ alkoxycarbonyl group,

R ^4b represents a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a cyano group or a nitro group,

R ⁵ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ Haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, -C(O)R ^50a , -C(O)OH, hydroxyl, -NH _2. -NHR ^50g , -N(R ^50h )R ^50g , mercapto, cyano or nitro,

R ⁶ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ Haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, -C(O)R ^60a , -C(O)OH, hydroxyl, -NH _2. -NHR ^60g , -N(R ^60h )R ^60g , mercapto, cyano or nitro,

R ⁷ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfonyl, mercapto, -SF ₅ , cyano or nitro,

R ⁸ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group or a cyano group,

A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, ^{A 1a-a} is substituted with any of the (C ₁ -C ₆₎ alkyl, ^{A 1a-a} arbitrarily substituted The (C ₁ -C ₆ ) haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkane Group, C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl Group, C ₁ -C ₆ haloalkylsulfinyl group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ haloalkylsulfinyl group, C(O)R ^10a , hydroxyl or cyano group,

A ^1a-a represents C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ haloalkoxycarbonyl, C ₁ -C ₆ Alkylcarbonyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ A haloalkylsulfinyl group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ haloalkylsulfinyl group, a hydroxyl group or a cyano group,

T _1a represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ Cycloalkyl (C ₁ -C ₆ )alkyl or C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ )alkyl,

Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, ^a (C ₁ -C ₆ )alkyl group optionally substituted by Y a, are the optionally substituted (C ₁ -C ₆₎ haloalkyl Y ^a, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, optionally substituted by Y ^a are the (C ₂ -C ₆₎ alkenyl Group, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, (C ₂ -C ₆ )alkynyl ^{optionally substituted by Y b} _{, C 1} -C ₈ alkoxy, C ₁ -C ₈ Haloalkoxy, (C ₁ -C ₈ )alkoxy ^{optionally substituted by Y a} _{, C 2} -C ₆ alkenyloxy, C ₂ -C ₆ haloalkenyloxy, optionally substituted ^{by Y a} (C ₂ -C ₆ )alkenyloxy, C ₂ -C ₆ alkynyloxy, C ₂ -C ₆ haloalkynyloxy, (C ₂ -C ₆ )alkynyl ^{optionally substituted by Y a} Oxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ halocycloalkyl ( C ₁ -C ₆ )alkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 2} -C ₆ alkenylthio, C ₂ -C ₆ haloalkenyl group, C ₂ -C ₆ alkynyl group, C ₂ -C ₆ haloalkynyl group, C ₁ -C ₆ alkylsulfinyl acyl, C ₁ -C ₆ haloalkylsulfinyl, (C ₁ -C ₆ )alkylsulfinyl ^{optionally substituted by Y a} _{, C 2} -C ₆ alkenylsulfinyl, C ₂ -C ₆ haloalkenyl Sulfinyl, C ₂ -C ₆ alkynylsulfinyl, C ₂ -C ₆ haloalkynylsulfinyl, C ₁ -C ₆ alkyl sulfinyl, C ₁ -C ₆ haloalkylsulfonyl Alkyl, (C ₁ -C ₆ )alkylsulfonyl optionally substituted by Y ^a _{, C 2} -C ₆ alkenylsulfonyl, C ₂ -C ₆ haloalkenylsulfonyl, C ₂ -C ₆ alkynyl sulfonyl, C ₂ -C ₆ haloalkynyl sulfonyl, -C(O)R ^90a , -C(O)NHR ^90b , -C(O)N(R ^90c )R ^90b , -C (O)OH, -C(=NOR ^90d )R ^90a , -C(O)NH ₂ , hydroxyl, -OC(O)R ^90e , -OS(O) ₂ R ^90f , -NH ₂ , -NHR ^90g , -N(R ^90h )R ^90g , sulfhydryl, -SC(O)R ⁹⁰ⁱ , -S(O) ₂ NHR ^90j , -S(O) ₂ N(R ^90k )R ^90j , _{-SF 5} , cyano, nitro Group, phenyl group, phenyl group ^{optionally substituted by Y c} , heterocyclic group Or a heterocyclic group optionally substituted ^{by Y c,}

Y5 and Y6 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl Aceto, C ₁ -C ₆ haloalkylsulfonyl, mercapto, -SF ₅ , cyano, nitro, phenyl or phenyl optionally substituted ^{by Y c,}

Y ^a represents C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ haloalkoxycarbonyl, C ₁ -C ₆ alkyl Carbonyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkane A sulfinyl group, a C ₁ -C ₆ alkyl sulfinyl group, a C ₁ -C ₆ haloalkyl sulfinyl group, a hydroxyl group or a cyano group,

Y ^b represents C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, trimethylsilyl, C ₁ -C ₈ alkoxy, phenyl or phenyl optionally substituted ^{by Y b2,}

Y ^b2 represents C ₁ -C ₆ haloalkyl,

Y ^c represents a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a cyano group or a nitro group,

R ^10a , R ^20a , R ^30a , R ^30e , R ^40a , R ^40e , R ^50a , R ^60a and R ^90a each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ haloalkoxy,

R ^20g , R ^20h , R ^30f , R ^30g , R ^30h , R ³⁰ⁱ , R ^40f , R ^40g , R ^40h , R ⁴⁰ⁱ , R ^50g , R ^50h , R ^60g , R ^60h , R ^90b , R ^90c , R ⁹⁰ⁱ , R ^90j and R ^90k each independently represent a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

R ^90d represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

R ^90e represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₆ alkylamine Group, C ₁ -C ₆ haloalkylamino group, di(C ₁ -C ₆ )alkylamino group or di(C ₁ -C ₆ )haloalkylamino group,

R ^90f represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkylamino, C ₁ -C ₆ haloalkylamino, di (C ₁ -C ₆ ) alkane Amino group or di(C ₁ -C ₆ )haloalkylamino group,

R ^90g and R ^90h each independently represent C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₈ alkane Oxycarbonyl, C ₁ -C ₈ haloalkoxycarbonyl, C ₁ -C ₆ alkylaminocarbonyl, C ₁ -C ₆ haloalkylaminocarbonyl, C ₁ -C ₆ alkylaminothiocarbonyl, C ₁ -C ₆ haloalkylaminothiocarbonyl, phenylcarbonyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylaminosulfonyl Acyl or di(C ₁ -C ₆ )alkylaminosulfonyl,

n represents an integer of 0, 1, or 2].

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

D substituted by -S(O) _n R ¹ represents a ring represented by D1,

G ₁ means C(Y1),

G ₂ means C(Y2),

G ₃ means C(Y3),

G ₄ means C(Y4),

A ² means C(R ² ),

A ³ means C(R ³ ),

R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ Haloalkynyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkyl or C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ ) alkyl,

R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

R ⁵ , R ⁶ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

R ⁷ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ )alkyl ^{optionally substituted by A 1a-a} _{, C 2} -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₈ alkoxy, C ₃ -C ₆ cycloalkyl or C(O)R ^10a ,

A ^1a-a represents a C ₁ -C ₈ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfinyl group or a cyano group,

R ^10a represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₈ alkoxy group,

Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, a (C ₂ -C ₆ )alkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ halo substituted by Y ^b Alkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C _1- C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, -C(O)R ^90a , -C(O)NHR ^90b , -C(O)N(R ^90c )R ^90b ,- C(O)OH, hydroxyl, -OC(O)R ^90e , -OS(O) ₂ R ^90f , -NH ₂ , -NHR ^90g , -N(R ^90h )R ^90g , sulfhydryl, -SC(O)R ⁹⁰ⁱ , -S(O) ₂ NHR ^90j , -S(O) ₂ N(R ^90k )R ^90j , _{-SF 5} , cyano, nitro, phenyl, phenyl optionally substituted ^{by Y c, heterocycle} Group or heterocyclic group optionally substituted ^{by Y c,}

Y ^a represents a C ₁ -C ₈ alkoxycarbonyl group.

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

D substituted by -S(O) _n R ¹ represents a ring represented by D2,

Q represents the ring represented by Q1,

A ¹ means N(A ^1a ),

A ² means C(R ² ),

A ³ means C(R ³ ),

A ⁴ means C(R ⁴ ),

A ⁵ represents a nitrogen atom,

R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ Haloalkynyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkyl or C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ ) alkyl,

R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ )alkyl ^{optionally substituted by A 1a-a} _{, C 2} -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₈ alkoxy, C ₃ -C ₆ cycloalkyl or C(O)R ^10a ,

A ^1a-a represents a C ₁ -C ₈ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfinyl group or a cyano group,

R ^10a represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₈ alkoxy group,

Y5 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

Y6 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, a phenyl group, or a phenyl group optionally substituted ^{by Y c.}

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

D substituted by -S(O) _n R ¹ represents a ring represented by D3,

Q represents the ring represented by Q1,

G ₁ means C(Y1),

G ₂ means C(Y2),

G ₃ means C(Y3),

G ₄ means C(Y4),

T ₁ represents N (T _1a ) or sulfur atom,

A ¹ means N(A ^1a ),

A ² means C(R ² ),

A ³ means C(R ³ ),

A ⁴ means C(R ⁴ ),

A ⁵ represents a nitrogen atom,

R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ Haloalkynyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkyl or C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ ) alkyl,

R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ )alkyl ^{optionally substituted by A 1a-a} _{, C 2} -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₈ alkoxy, C ₃ -C ₆ cycloalkyl or C(O)R ^10a ,

A ^1a-a represents a C ₁ -C ₈ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfinyl group or a cyano group,

R ^10a represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₈ alkoxy group,

T _1a represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy Group, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, cyano or nitro.

The fused heterocyclic compound or its salt or the N-oxide described in [2] above, wherein

Q represents the ring represented by Q1,

A ¹ means N(A ^1a ),

R ¹ represents a C ₁ -C ₆ alkyl group,

R ³ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

R ⁴ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

A ^1a represents a hydrogen atom or a C ₁ -C ₆ alkyl group.

The fused heterocyclic compound or its salt or the N-oxide described in [5] above, wherein

A ⁴ means C(R ⁴ ),

A ⁵ represents a nitrogen atom.

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [5] or [6], wherein,

A ⁴ means C(R ⁴ ),

A ⁵ represents a nitrogen atom,

R ² represents a hydrogen atom,

R ⁴ represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

Y1 represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

Y2 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a (C ₂ -C ₆ )alkynyl group ^{optionally substituted by Y b,} C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, -NH ₂ , -NHR ^90g , nitro, cyano, phenyl, phenyl ^{optionally substituted by Y c} , thiophene-2- Yl, pyridin-3-yl or pyridin-4-yl,

Y3 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a (C ₂ -C ₆ )alkynyl group ^{optionally substituted by Y b,} C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, -C(O)R ^90a , -C(O)N(R ^90c )R ^90b , -C(O)OH, cyano or nitro,

Y4 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkyl group Sulfonyl, -N(R ^90h )R ^90g or cyano,

Y ^a represents a C ₁ -C ₈ alkoxycarbonyl group,

Y ^b represents C ₃ -C ₆ cycloalkyl, trimethylsilyl, C ₁ -C ₈ alkoxy or phenyl optionally substituted ^{by Y b2,}

Y ^c represents a halogen atom or a C ₁ -C ₆ haloalkyl group,

R ^90a represents C ₁ -C ₆ alkyl or C ₁ -C ₈ alkoxy,

R ^90b and R ^90c each independently represent a C ₁ -C ₆ alkyl group,

R ^90g represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₈ alkoxycarbonyl or phenylcarbonyl,

R ^90h represents a C ₁ -C ₆ alkyl group.

The fused heterocyclic compound or its salt or the N-oxide described in [5] above, wherein

A ⁴ represents a nitrogen atom,

A ⁵ represents C(R ⁵ ).

The fused heterocyclic compound or its salt or the above-mentioned one of [5] or [8] And other N-oxides, of which,

A ⁴ represents a nitrogen atom,

A ⁵ means C(R ⁵ ),

R ² represents a hydrogen atom,

R ³ represents C ₁ -C ₆ haloalkyl,

R ⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

Y1 represents a hydrogen atom,

Y2 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

Y3 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group or a cyano group,

Y4 represents a hydrogen atom, a halogen atom, or a C ₁ -C ₈ alkoxy group.

[10]

The fused heterocyclic compound or its salt or the N-oxide described in [2] above, wherein

Q represents the ring represented by Q2,

A ⁴ represents a nitrogen atom or C(R ⁴ ),

A ⁵ represents a nitrogen atom or C(R ⁵ ), (except that A ⁴ and A ⁵ represent a nitrogen atom together)

R ¹ represents a C ₁ -C ₆ alkyl group,

R ² represents a hydrogen atom,

R ³ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

R ⁴ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl.

[11]

The fused heterocyclic compound or its salt or the N-oxide described in [10] above, wherein,

A ⁴ means C(R ⁴ ),

A ⁵ represents C(R ⁵ ).

[12]

The fused heterocyclic compound or its salt or the N-oxide described in [10] above, wherein,

A ⁴ means C(R ⁴ ),

A ⁵ represents a nitrogen atom.

[13]

The fused heterocyclic compound or its salt or the N-oxide described in [10] above, wherein,

A ⁴ represents a nitrogen atom,

A ⁵ represents C(R ⁵ ).

[14]

The fused heterocyclic compound or its salt as in any one of [10] or [13] above or These N-oxides, of which,

A ⁴ represents a nitrogen atom,

A ⁵ means C(R ⁵ ),

R ³ represents C ₁ -C ₆ haloalkyl,

R ⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

R ⁶ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,

Y1 and Y4 represent hydrogen atoms,

Y2 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

Y3 represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group.

[15]

The fused heterocyclic compound or its salt or the N-oxide described in [2] above, wherein

Q represents the ring represented by Q3,

A ⁴ represents a nitrogen atom or C(R ⁴ ),

A ⁵ represents a nitrogen atom or C(R ⁵ ), (except that A ⁴ and A ⁵ represent a nitrogen atom together)

R ¹ represents a C ₁ -C ₆ alkyl group,

R ² represents a hydrogen atom,

R ³ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl,

R ⁴ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl.

[16]

The fused heterocyclic compound or its salt or the N-oxide described in [15] above, wherein,

A ⁴ means C(R ⁴ ),

A ⁵ represents C(R ⁵ ).

[17]

The fused heterocyclic compound or its salt or the N-oxide described in [15] above, wherein,

A ⁴ means C(R ⁴ ),

A ⁵ represents a nitrogen atom.

[18]

The fused heterocyclic compound or its salt or the N-oxide described in [15] above, wherein,

A ⁴ represents a nitrogen atom,

A ⁵ represents C(R ⁵ ).

[19]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [15] or [18], wherein,

A ⁴ represents a nitrogen atom,

A ⁵ means C(R ⁵ ),

R ³ represents C ₁ -C ₆ haloalkyl,

R ⁵ represents a hydrogen atom,

R ⁶ represents a hydrogen atom,

Y1 represents a hydrogen atom,

Y2 and Y3 each independently represent a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

Y4 represents a hydrogen atom or a halogen atom.

[20]

The fused heterocyclic compound or its salt or the N-oxide described in [2] above, wherein

Q represents the ring represented by Q4.

[twenty one]

The fused heterocyclic compound or its salt or the N-oxide described in [20] above, wherein,

A ⁸ represents a nitrogen atom.

[twenty two]

The fused heterocyclic compound or its salt or the N-oxide described in [20] above, wherein,

A ⁸ represents C(R ⁸ ).

[twenty three]

The fused heterocyclic compound or its salt or the N-oxide of any one of [20], [21] or [22] above, wherein,

R ¹ represents a C ₁ -C ₆ alkyl group,

R ⁶ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

R ⁷ represents C ₁ -C ₆ haloalkyl,

R ⁸ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

Y1 and Y4 represent hydrogen atoms,

Y2 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

Y3 represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group.

[twenty four]

The fused heterocyclic compound or its salt or the N-oxide described in [3] above, wherein

R ¹ represents a C ₁ -C ₆ alkyl group,

R ² represents a hydrogen atom,

R ³ represents C ₁ -C ₆ haloalkyl,

R ⁴ represents a hydrogen atom,

A ^1a represents a C ₁ -C ₆ alkyl group,

Y5 represents a hydrogen atom,

Y6 represents a halogen atom, a C ₁ -C ₆ haloalkyl group or a phenyl group optionally substituted ^{by Y c,}

Y ^c represents C ₁ -C ₆ haloalkyl.

[25]

The fused heterocyclic compound or its salt or the N-oxide described in [4] above, wherein,

R ¹ represents a C ₁ -C ₆ alkyl group,

R ² represents a hydrogen atom,

R ³ represents C ₁ -C ₆ haloalkyl,

R ⁴ represents a hydrogen atom,

A ^1a represents a C ₁ -C ₆ alkyl group,

T _1a represents a C ₁ -C ₆ alkyl group,

Y1, Y3 and Y4 represent hydrogen atoms,

Y2 represents C ₁ -C ₆ haloalkyl.

[26]

The fused heterocyclic compound or its salt or the N-oxide described in [2] above, wherein

A ¹ represents N (A ^1a ) or oxygen atom,

R ² represents a hydrogen atom,

R ³ represents a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfinyl group,

R ⁴ represents a hydrogen atom,

R ⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

R ⁶ represents a hydrogen atom,

A ^1a represents a C ₁ -C ₆ alkyl group,

Y1 and Y4 represent hydrogen atoms,

Y2 and Y3 each independently represent a hydrogen atom or a C ₁ -C ₆ haloalkyl group.

[27]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1] or [2], wherein,

The aforementioned formula (1) is based on the following formula (1-A-A1), formula (1-A-B1), formula (1-A-C1), formula (1-A-D1), formula (1-A- E1), formula (1-A-F1), formula (1-A-G1), formula (1-A-H1), formula (1-A-I1), formula (1-A-J1), formula ( Compounds represented by 1-A-K1), formula (1-A-L1), formula (1-A-M1) or formula (1-A-N1),

[28]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1] or [3], wherein,

The aforementioned formula (1) is a compound represented by formula (1-B-A1),

[29]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1] or [4], wherein,

The aforementioned formula (1) is a compound represented by formula (1-C-A1),

[30]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

The aforementioned formula (1) is a compound represented by formula (1-d-A1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

A ^1a represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ alkynyl group,

R ² , R ⁴ , Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[31]

The fused heterocyclic compound or its salt or the N-oxide described in [30] above, wherein

R ¹ and A ^1a each independently represent a C ₁ -C ₆ alkyl group,

R ³ and Y3 each independently represent a C ₁ -C ₆ haloalkyl group,

R ² , R ⁴ , Y2 and Y4 represent a hydrogen atom.

[32]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

The aforementioned formula (1) is a compound represented by formula (1-e-A1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

A ^1a represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ alkynyl group,

R ² , R ⁴ , Y1, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[33]

The fused heterocyclic compound or its salt or the N-oxide described in [32] above, wherein,

R ¹ and A ^1a each independently represent a C ₁ -C ₆ alkyl group,

R ³ and Y3 each independently represent a C ₁ -C ₆ haloalkyl group,

R ² , R ⁴ , Y1 and Y4 represent a hydrogen atom.

[34]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

The aforementioned formula (1) is a compound represented by formula (1-f-A1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

A ^1a represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ alkynyl group,

R ² , R ⁴ , Y1 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

Y2 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, a phenyl group or a phenyl group optionally substituted ^{by Y c.}

[35]

The fused heterocyclic compound or its salt or the N-oxide described in [34] above, wherein,

R ¹ and A ^1a each independently represent a C ₁ -C ₆ alkyl group,

R ³ represents C ₁ -C ₆ haloalkyl,

R ² , R ⁴ , Y1 and Y4 represent a hydrogen atom,

Y2 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group or a phenyl group optionally substituted ^{by Y c,}

Y ^c represents C ₁ -C ₆ haloalkyl.

[36]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

The aforementioned formula (1) is a compound represented by formula (1-g-A1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

A ^1a represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ alkynyl group,

R ² , R ⁴ , Y1, Y2 and Y3 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[37]

The fused heterocyclic compound or its salt or the N-oxide described in [36] above, wherein,

R ¹ and A ^1a each independently represent a C ₁ -C ₆ alkyl group,

R ³ represents C ₁ -C ₆ haloalkyl,

R ² , R ⁴ , Y1 and Y3 represent a hydrogen atom,

Y2 represents a halogen atom or a C ₁ -C ₆ haloalkyl group.

[38]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-G1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

A ^1a represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ alkynyl group,

R ⁴ , R ⁵ , Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[39]

The fused heterocyclic compound or its salt or the N-oxide described in [38] above, wherein,

R ¹ and A ^1a each independently represent a C ₁ -C ₆ alkyl group,

R ³ and Y3 each independently represent a C ₁ -C ₆ haloalkyl group,

R ⁴ , R ⁵ , Y1, Y2, and Y4 represent a hydrogen atom.

[40]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-I1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

A ^1a represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ alkynyl group,

R ² , R ⁵ , Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[41]

The fused heterocyclic compound or its salt or the N-oxide described in [40] above, wherein,

R ¹ and A ^1a each independently represent a C ₁ -C ₆ alkyl group,

R ⁴ represents C ₁ -C ₆ haloalkyl,

Y2 represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

Y3 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

R ² , R ⁵ , Y1 and Y4 represent a hydrogen atom.

[42]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-F1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

R ² , R ⁵ , R ⁶ , Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[43]

The fused heterocyclic compound or its salt or the N-oxide described in [42] above, wherein,

R ¹ represents a C ₁ -C ₆ alkyl group,

R ⁴ represents C ₁ -C ₆ haloalkyl,

Y2 and Y3 each independently represent a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

R ² , R ⁵ , R ⁶ , Y1 and Y4 represent a hydrogen atom.

[44]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-O1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

R ³ , R ⁵ , R ⁶ , Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, or a C ₁ -C ₆ haloalkyl group.

[45]

The fused heterocyclic compound or its salt or the N-oxide described in [44] above, wherein,

R ¹ represents a C ₁ -C ₆ alkyl group,

R ⁴ represents C ₁ -C ₆ haloalkyl,

R ⁶ and Y2 each independently represent a halogen atom,

R ³ , R ⁵ , Y1, Y3, and Y4 represent a hydrogen atom.

[46]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1] or [2], wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-b1),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkane Sulfonyl or C ₁ -C ₆ haloalkylsulfonyl,

R ² , R ⁵ , Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[47]

The fused heterocyclic compound or its salt or the N-oxide described in [46] above, wherein,

R ¹ represents a C ₁ -C ₆ alkyl group,

R ³ represents a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfinyl group,

Y2 and Y3 each independently represent a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

R ² , R ⁴ , R ⁵ , Y1 and Y4 represent a hydrogen atom.

[48]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1] or [2], wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-b2),

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkane Sulfonyl or C ₁ -C ₆ haloalkylsulfonyl,

R ² , Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[49]

The fused heterocyclic compound or its salt or the N-oxide described in [48] above, wherein R ¹ represents a C ₁ -C ₆ alkyl group,

R ³ and Y3 each independently represent a C ₁ -C ₆ haloalkyl group,

R ² , R ⁴ , Y1, Y2, and Y4 represent a hydrogen atom.

[50]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1] or [2], wherein the aforementioned formula (1) is represented by the formula (1-a-m2) Compound,

In the formula, R ¹ represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl,

R ² , R ⁴ , Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[51]

The fused heterocyclic compound or its salt or the N-oxide described in [50] above, wherein,

R ¹ represents a C ₁ -C ₆ alkyl group,

R ³ and Y3 each independently represent a C ₁ -C ₆ haloalkyl group,

R ² , R ⁴ , Y1, Y2, and Y4 represent a hydrogen atom.

[52]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1], [2] or [5], wherein the aforementioned formula (1) is the formula (1-a-p1) ) Represents the compound,

In the formula, R ¹ represents a C ₁ -C ₆ alkyl group,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfonyl group Ji Ji,

R ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

A ^1a represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

R ² , R ⁵ , Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[53]

The fused heterocyclic compound or its salt or the N-oxide described in [52] above, wherein,

R ² and R ⁵ each independently represent a hydrogen atom or a halogen atom,

R ³ represents a hydrogen atom, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfinyl group,

R ⁴ represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

Y2 and Y3 each independently represent a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

Y1 and Y4 represent hydrogen atoms.

[54]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1], [2] or [5], wherein the aforementioned formula (1) is based on the formula (1-a-q1 ) Represents the compound,

In the formula, R ¹ represents a C ₁ -C ₆ alkyl group,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfonyl group Ji Ji,

A ^1a represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

R ² , Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[55]

The fused heterocyclic compound or its salt or the N-oxide described in [54] above, wherein R ³ and Y 2 each independently represent a C ₁ -C ₆ haloalkyl group,

A ^1a represents a C ₁ -C ₆ alkyl group,

R ² , Y1, Y3, and Y4 represent a hydrogen atom.

[56]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1], [2], [10] or [11], wherein the aforementioned formula (1) is based on the formula (1) -a-E1) represents the compound,

In the formula, R ¹ represents a C ₁ -C ₆ alkyl group,

R ² represents a hydrogen atom,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfonyl group Ji Ji,

R ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

R ⁵ , R ⁶ , Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[57]

The fused heterocyclic compound or its salt or the N-oxide described in [56] above, wherein,

R ³ , R ⁴ , Y2 and Y3 each independently represent a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

R ⁵ , R ⁶ , Y1 and Y4 represent a hydrogen atom.

[58]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1], [2], [10] or [12], wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-D1),

In the formula, R ¹ represents a C ₁ -C ₆ alkyl group,

R ² represents a hydrogen atom,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfonyl group Ji Ji,

R ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

R ⁶ , Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[59]

The fused heterocyclic compound or its salt or the N-oxide described in [58] above, wherein,

R ³ represents C ₁ -C ₆ haloalkyl,

Y2 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

Y3 represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

R ⁴ , R ⁶ , Y1 and Y4 represent a hydrogen atom.

[60]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1], [2], [15] or [16], wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-j1),

In the formula, R ¹ represents a C ₁ -C ₆ alkyl group,

R ² represents a hydrogen atom,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfonyl group Ji Ji,

R ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

R ⁵ , R ⁶ , Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[61]

The fused heterocyclic compound or its salt or the N-oxide described in [60] above, wherein,

R ³ and Y3 each independently represent a C ₁ -C ₆ haloalkyl group,

R ⁴ , R ⁵ , R ⁶ , Y1, Y2, and Y4 represent a hydrogen atom.

[62]

The fused heterocyclic compound or its salt or the N-oxide of any one of the above [1], [2], [15] or [17], wherein,

The aforementioned formula (1) is a compound represented by formula (1-a-j2),

In the formula, R ¹ represents a C ₁ -C ₆ alkyl group,

R ² represents a hydrogen atom,

R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfonyl group Ji Ji,

R ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group,

R ⁶ , Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group.

[63]

The fused heterocyclic compound or its salt or the N-oxide described in [62] above, wherein,

R ³ represents C ₁ -C ₆ haloalkyl or C ₁ -C ₆ haloalkylthio,

Y2 represents a hydrogen atom or a halogen atom,

Y3 represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

R ⁴ , R ⁶ , Y1 and Y4 represent a hydrogen atom.

[64]

The fused heterocyclic compound or its salt or the N-oxide described in [1] above, wherein,

D substituted by -S(O) _n R ¹ represents a ring represented by either D1 or D2,

Q represents the ring represented by either Q1 or Q2,

R ^1a represents a C ₁ -C ₈ alkoxycarbonyl group,

R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group or a C ₁ -C ₈ haloalkoxy group,

R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkane Sulfonyl, C ₁ -C ₆ haloalkylsulfonyl, mercapto, cyano or nitro,

R ⁵ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,

R ⁶ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,

A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkyl or C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ ) alkyl,

Y1, Y2, Y3, Y4, Y5, and Y6 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, and a C ₁ -C ₈ Haloalkoxy, cyano or nitro.

[65]

The fused heterocyclic compound or its salt or the N-oxide described in [2] above, wherein

D substituted by -S(O) _n R ¹ represents a ring represented by D1,

G ₁ means C(Y1),

G ₂ means C(Y2),

G ₃ means C(Y3),

G ₄ means C(Y4),

A ¹ represents N (A ^1a ) or oxygen atom,

A ² means C(R ² ),

A ³ means C(R ³ ),

R ¹ and A ^1a each independently represent a C ₁ -C ₆ alkyl group,

R ³ represents a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfinyl group,

R ⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,

Y2 and Y3 each independently represent a hydrogen atom or a C ₁ -C ₆ haloalkyl group,

R ² , R ⁴ , R ⁶ , Y1 and Y4 represent a hydrogen atom.

[66]

The fused heterocyclic compound or its salt or the N-oxide described in [3] above, wherein

D substituted by -S(O) _n R ¹ represents a ring represented by D2,

Q represents the ring represented by Q1,

G ₅ means C(Y5),

A ¹ means N(A ^1a ),

A ² means C(R ² ),

A ³ means C(R ³ ),

A ⁴ means C(R ⁴ ),

A ⁵ represents a nitrogen atom,

R ¹ and A ^1a each independently represent a C ₁ -C ₆ alkyl group,

R ² , R ⁴ and Y5 represent a hydrogen atom,

R ³ and Y6 each independently represent a C ₁ -C ₆ haloalkyl group.

[67]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [66] above, wherein R ¹ represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkane Group, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) Alkyl group or C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ )alkyl group.

[68]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [66] above, wherein R ¹ represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkane Group or C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkyl.

[69]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [66] above, wherein R ¹ represents a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkane base.

[70]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [66] above, wherein R ¹ represents a C ₁ -C ₆ alkyl group.

[71]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [66] above, wherein R ¹ represents a C ₁ -C ₆ haloalkyl group.

[72]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [71] above, wherein R ^1a represents C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkane Oxycarbonyl or cyano.

[73]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [71] above, wherein R ^1a represents a C ₁ -C ₈ alkoxycarbonyl group.

[74]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [73] above, wherein R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or C ₁ -C ₆ haloalkyl.

[75]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [73] above, wherein R ² represents a hydrogen atom.

[76]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [75] above, wherein R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, substituted by R ^3a Optionally substituted (C ₁ -C ₆ )alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl.

[77]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [75] above, wherein R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ alkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ haloalkylthio, C ₁ -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl.

[78]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [75] above, wherein R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl.

[79]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [75] above, wherein R ³ represents a C ₁ -C ₆ haloalkylthio group, C ₁ -C ₆ Haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl.

[80]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [75] above, wherein R ³ represents a halogen atom.

[81]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [75] above, wherein R ³ represents a C ₁ -C ₆ haloalkyl group.

[82]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [75] above, wherein R ³ represents a C ₁ -C ₆ haloalkylthio group.

[83]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [75] above, wherein R ³ represents a C ₁ -C ₆ haloalkylsulfinyl group.

[84]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [75] above, wherein R ³ represents a C ₁ -C ₆ haloalkylsulfonyl group.

[85]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [84] above, wherein R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, substituted by R ^4a Optionally substituted (C ₁ -C ₆ )alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl.

[86]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [84] above, wherein R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ alkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ haloalkylthio, C ₁ -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfonyl.

[87]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [84] above, wherein R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl.

[88]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [84] above, wherein R ⁴ represents a hydrogen atom.

[89]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [84] above, wherein R ⁴ represents a halogen atom.

[90]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [84] above, wherein R ⁴ represents a C ₁ -C ₆ haloalkylthio group, C ₁ -C ₆ Haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl.

[91]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [84] above, wherein R ⁴ represents a C ₁ -C ₆ haloalkyl group.

[92]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [91] above, wherein R ⁵ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or C ₁ -C ₆ haloalkyl.

[93]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [91] above, wherein R ⁵ represents a halogen atom.

[94]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [91] above, wherein R ⁵ represents a hydrogen atom.

[95]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [91] above, wherein R ⁵ represents a C ₁ -C ₆ alkyl group.

[96]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [95] above, wherein R ⁶ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or C ₁ -C ₆ haloalkyl.

[97]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [95] above, wherein R ⁶ represents a hydrogen atom.

[98]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [95] above, wherein R ⁶ represents a halogen atom.

[99]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [95] above, wherein R ⁶ represents a C ₁ -C ₆ alkyl group.

[100]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [99] above, wherein R ⁷ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group.

[101]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [99] above, wherein R ⁷ represents a C ₁ -C ₆ haloalkyl group.

[102]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [101] above, wherein R ⁸ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or C ₁ -C ₆ haloalkyl.

[103]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [101] above, wherein R ⁸ represents a C ₁ -C ₆ alkyl group.

[104]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [103] above, wherein A ^1a represents a hydrogen atom, a C ₁ -C ₆ alkyl group, and A ^{1a- a} optionally substituted (C ₁ -C ₆ )alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₈ alkoxy, C ₃ -C ₆ cycloalkyl or C (O)R ^10a .

[105]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [103] above, wherein A ^1a represents a hydrogen atom, a C ₁ -C ₆ alkyl group, and a C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl.

[106]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [103] above, wherein A ^1a represents a hydrogen atom.

[107]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [103] above, wherein A ^1a represents a C ₁ -C ₆ alkyl group.

[108]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [107] above, wherein Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, and C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, (C ₂ -C ₆ )alkynyl ^{optionally substituted by Y b} _{, C 1} -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, optionally substituted ^{by Y a} _{(C 1} -C ₆ ) Alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl , -C(O)R ^90a , -C(O)NHR ^90b , -C(O)N(R ^90c )R ^90b , -C(O)OH, hydroxyl, -OC(O)R ^90e , -OS (O) ₂ R ^90f , -NH ₂ , -NHR ^90g , -N(R ^90h )R ^90g , sulfhydryl, -SC(O)R ⁹⁰ⁱ , -S(O) ₂ NHR ^90j , -S(O) ₂ N (R ^90k ) R ^90j , _{-SF 5} , cyano, nitro, phenyl, phenyl ^{optionally substituted by Y c} , heterocyclic group or heterocyclic group optionally substituted ^{by Y c.}

[109]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [107] above, wherein Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, and C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, (C ₂ -C ₆ )alkynyl ^{optionally substituted by Y b} _{, C 1} -C ₈ alkoxy, C _1- C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, -C(O)R ^90a , -C(O)N(R ^90c )R ^90b , -C(O)OH, -NH ₂ , -NHR ^90g , -N(R ^90h ) R ^90g , mercapto, cyano, nitro, phenyl, phenyl ^{optionally substituted by Y c} , heterocyclic group or heterocyclic group optionally substituted ^{by Y c.}

[110]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [109] above, wherein Y1 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl.

[111]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [109] above, wherein Y1 represents a hydrogen atom.

[112]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [109] above, wherein Y1 represents a halogen atom.

[113]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [109] above, wherein Y1 represents a C ₁ -C ₆ alkyl group.

[114]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [109] above, wherein Y1 represents a C ₁ -C ₆ haloalkyl group.

[115]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [114] above, wherein Y2 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, (C ₂ -C ₆ )alkynyl ^{optionally substituted by Y b} _{, C 1} -C ₈ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl , -NH ₂ , -NHR ^90g , nitro, phenyl, phenyl or heterocyclic group optionally substituted ^{by Y c.}

[116]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [114] above, wherein Y2 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl.

[117]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [114] above, wherein Y2 represents a hydrogen atom.

[118]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [114] above, wherein Y2 represents a halogen atom.

[119]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [114] above, wherein Y2 represents a C ₁ -C ₆ alkyl group.

[120]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [114] above, wherein Y2 represents a C ₁ -C ₆ haloalkyl group.

[121]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [120] above, wherein Y3 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, and C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkyl Sulfinyl, C ₁ -C ₆ alkylsulfonyl, -C(O)R ^90a , -C(O)N(R ^90c )R ^90b , -C(O)OH, cyano or nitro.

[122]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [120] above, wherein Y3 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl.

[123]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [120] above, wherein Y3 represents a hydrogen atom.

[124]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [120] above, wherein Y3 represents a halogen atom.

[125]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [120] above, wherein Y3 represents a C ₁ -C ₆ alkyl group.

[126]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [120] above, wherein Y3 represents a C ₁ -C ₆ haloalkyl group.

[127]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [126] above, wherein Y4 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, and C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfonyl, -N(R ^90h )R ^90g or cyano.

[128]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [126] above, wherein Y4 represents C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkyl sulfide Group, C ₁ -C ₆ alkylsulfonyl group, -N(R ^90h )R ^90g or cyano group.

[129]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [126] above, wherein Y4 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl.

[130]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [126] above, wherein Y4 represents a hydrogen atom.

[131]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [126] above, wherein Y4 represents a halogen atom.

[132]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [126] above, wherein Y4 represents a C ₁ -C ₆ alkyl group.

[133]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [126] above, wherein Y4 represents a C ₁ -C ₆ haloalkyl group.

[134]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [133] above, wherein Y ^a represents a C ₁ -C ₈ alkoxycarbonyl group or C ₁ -C ₆ Alkylcarbonyl.

[135]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [133] above, wherein Y ^a represents a C ₁ -C ₈ alkoxycarbonyl group.

[136]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [135] above, wherein Y ^b represents C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkane Group, trimethylsilyl group, C ₁ -C ₈ alkoxy group, phenyl group or phenyl group optionally substituted ^{by Y b2.}

[137]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [135] above, wherein Y ^b represents a C ₃ -C ₆ cycloalkyl group or a trimethylsilyl group.

[138]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [135] above, wherein Y ^b represents a C ₃ -C ₆ cycloalkyl group.

[139]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [135] above, wherein Y ^b represents a trimethylsilyl group.

[140]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [139] above, wherein Y ^b2 represents a C ₁ -C ₆ haloalkyl group.

[141]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [140] above, wherein Y ^c represents a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, cyano or nitro.

[142]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [140] above, wherein Y ^c represents a halogen atom or a C ₁ -C ₆ haloalkyl group.

[143]

The fused heterocyclic compound or its salt or the N-oxide thereof according to any one of [1] to [140] above, wherein Y ^c represents a halogen atom.

[144]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [140] above, wherein Y ^c represents a C ₁ -C ₆ haloalkyl group.

[145]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [144] above, wherein R ^10a , R ^20a , R ^30a , R ^30e , R ^40a , R ^40e , R ^50a , R ^60a and R ^90a each independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, or a C ₁ -C ₈ haloalkoxy group.

[146]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [144] above, wherein R ^10a , R ^20a , R ^30a , R ^30e , R ^40a , R ^40e , R ^50a , R ^60a and R ^90a each independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₈ alkoxy group.

[147]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [144] above, wherein R ^10a , R ^20a , R ^30a , R ^30e , R ^40a , R ^40e , R ^50a , R ^60a and R ^90a represent a hydrogen atom.

[148]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [144] above, wherein R ^10a , R ^20a , R ^30a , R ^30e , R ^40a , R ^40e , R ^50a , R ^60a and R ^90a each independently represent a C ₁ -C ₆ alkyl group.

[149]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [144] above, wherein R ^10a , R ^20a , R ^30a , R ^30e , R ^40a , R ^40e , R ^50a , R ^60a and R ^90a each independently represent a C ₁ -C ₈ alkoxy group.

[150]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [149] above, wherein R ^20g , R ^20h , R ^30f , R ^30g , R ^30h , R ³⁰ⁱ , R ^40f , R ^40g , R ^40h , R ⁴⁰ⁱ , R ^50g , R ^50h , R ^60g , R ^60h , R ^90b , R ^90c , R ⁹⁰ⁱ , R ^90j and R ^90k each independently represent a C ₁ -C ₆ alkyl group or C ₁ -C ₆ haloalkyl.

[151]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [149] above, wherein R ^20g , R ^20h , R ^30f , R ^30g , R ^30h , R ³⁰ⁱ , R ^40f , R ^40g , R ^40h , R ⁴⁰ⁱ , R ^50g , R ^50h , R ^60g , R ^60h , R ^90b , R ^90c , R ⁹⁰ⁱ , R ^90j and R ^90k each independently represent a C ₁ -C ₆ alkyl group.

[152]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [151] above, wherein R ^90g and R ^90h each independently represent a C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ haloalkoxycarbonyl, C _1- C ₆ alkylaminocarbonyl, C ₁ -C ₆ haloalkylaminocarbonyl, C ₁ -C ₆ alkylaminothiocarbonyl, C ₁ -C ₆ haloalkylaminothiocarbonyl, phenylcarbonyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylaminosulfonyl or di(C ₁ -C ₆ )alkylaminosulfonyl .

[153]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [152] above, wherein R ^90g represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkane Carbonyl, C ₁ -C ₈ alkoxycarbonyl or phenylcarbonyl.

[154]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [152] above, wherein R ^90g represents a C ₁ -C ₆ alkyl group.

[155]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [152] above, wherein R ^90g represents a C ₁ -C ₆ haloalkylcarbonyl group.

[156]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [152] above, wherein R ^90g represents a C ₁ -C ₈ alkoxycarbonyl group.

[157]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [152] above, wherein R ^90g represents a phenylcarbonyl group.

[158]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [157] above, wherein R ^90h represents a C ₁ -C ₆ alkyl group.

[159]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [158] above, wherein T ₁ represents a sulfur atom.

[160]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [158] above, wherein T ₁ represents N(T _1a ).

[161]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [160] above, wherein T _1a represents a hydrogen atom.

[162]

The fused heterocyclic compound or its salt or the N-oxide of any one of [1] to [160] above, wherein T _1a represents a C ₁ -C ₆ alkyl group.

[163]

A pest control agent which contains one or more of the fused heterocyclic compounds selected from any one of the above [1] to [162] and their salts as active ingredients.

[164]

A pesticide containing one or more of the fused heterocyclic compounds and their salts selected from any one of [1] to [162] above as an active ingredient.

[165]

A control agent for internal or external parasites of mammals or birds, which contains one or more of the fused heterocyclic compounds selected from any one of the above [1] to [162] and their salts as Active ingredients.

[166]

Such as the control agent of [165] above, wherein the external parasites are Siphonaptera or ticks.

[167]

An insecticide or acaricide containing one or more of the fused heterocyclic compounds selected from any one of the above [1] to [162] and their salts as active ingredients.

[168]

A seed treatment agent containing one or more of the fused heterocyclic compounds selected from any one of the above [1] to [162] and their salts as an active ingredient.

[169]

The seed treatment agent of the above-mentioned [168], wherein the seed treatment is performed by dipping.

[170]

A soil treatment agent, which will contain selected from the above-mentioned [1] ~ [162] One or two or more of the fused heterocyclic compounds and their salts in any one of them are used as active ingredients.

[171]

The soil treatment agent of the above-mentioned [170], wherein the soil treatment is performed by soil irrigation treatment.

The compound of the present invention is excellent in killing most agricultural pests, spider mites, internal or external parasites of mammals or birds. The acaricidal activity exerts a sufficient control effect even for pests that have acquired resistance to existing chemicals. Furthermore, it has almost no adverse effects on mammals, fish and beneficial insects, has low residue and has a light load on the environment. Accordingly, the present invention can provide a useful novel pest control agent.

Although the compounds included in the present invention may have geometric isomers of E-forms and Z-forms depending on the type of substituents, the present invention includes these E-forms, Z-forms or E-forms. A mixture of body and Z-body contained in any ratio.

In addition, although the compounds included in the present invention have optically active forms resulting from the presence of one or more uneven carbon atoms or uneven sulfur atoms, the present invention includes all optically active forms or racemates.

In addition, the compounds included in the present invention may vary depending on the type of substituent While there are cases of tautomers, the present invention includes all tautomers or a mixture of tautomers contained in any ratio.

Among the compounds included in the present invention, those that can be converted into salts according to ordinary methods, for example, can be converted into salts of hydrogen halides such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid, nitric acid, sulfuric acid, phosphoric acid, chloric acid, and perchloric acid. Salts of inorganic acids such as chloric acid, salts of methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc., formic acid, acetic acid, propionic acid, trifluoroacetic acid , Fumaric acid, tartaric acid, oxalic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, lactic acid, gluconic acid, citric acid and other carboxylic acid salts, glutamine acid, aspartic acid, etc. Salts of amino acids, salts of alkali metals such as lithium, sodium, and potassium, salts of alkaline earth metals such as calcium, barium, and magnesium, salts of aluminum, tetramethylammonium salt, tetrabutylammonium salt, and benzyl Quaternary ammonium salt such as trimethylammonium salt.

In the compound of the present invention, the so-called N-oxide is a compound that oxidizes the nitrogen atom forming the ring on the heterocyclic group. Examples of the heterocyclic group that can form an N-oxide include a condensed ring containing a pyridine ring, a condensed ring containing a pyrazine ring, a condensed ring containing a pyridazine ring, or a condensed ring containing a pyrimidine ring.

Next, specific examples of each substituent shown in this specification are shown below. Here, n- means positive, i- means different, s- means second, and tert- means third.

As the "halogen atom" in this specification, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are exemplified. In addition, the symbol of "halogen" in this specification also refers to these halogen atoms.

In this specification, _{the label of "C a} ~C _b alkyl" refers to a linear or branched hydrocarbon group with carbon number from a to b. Examples include methyl, ethyl, n -Propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert-butyl, n-pentyl, 1,1-dimethylpropyl, n-hexyl, etc. as specific For example, select the range of the number of carbon atoms specified by each.

In this specification, _{the label of "C a} ~C _b haloalkyl" means that the hydrogen atom bonded to the carbon atom is arbitrarily replaced by a halogen atom. The number of carbon atoms is a straight chain or When the branched hydrocarbon group is substituted by two or more halogen atoms, the halogen atoms may be the same as each other 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 Group, 3-bromo-3,3-difluoropropyl, 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)ethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3, 4,4,4-heptafluorobutyl, nonafluorobutyl, etc., as specific examples, are selected in the range of the number of carbon atoms designated by each.

In this specification, _{the label "C a} ~C _b alkenyl" means that the number of carbon atoms is a straight chain or branched chain formed from a to b, and the molecule has one or more double The unsaturated hydrocarbon group of the bond, for example, vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 2-butenyl, 2-methyl-2-propenyl, 3-methyl- 2-butenyl, 1,1-dimethyl-2-propenyl, etc. are selected as specific examples in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b haloalkenyl" means that the hydrogen atom bonded to the carbon atom is arbitrarily replaced by a halogen atom. The number of carbon atoms is a straight chain or An unsaturated hydrocarbon group that is branched and has one or more double bonds in the molecule. At this time, when it is substituted by two or more halogen atoms, these halogen atoms may be the same as each other, or may be different from each other. For example, 2,2-dichlorovinyl, 2-fluoro-2-propenyl, 2-chloro-2-propenyl, 3-chloro-2-propenyl, 2-bromo-2-propenyl, 3, 3-difluoro-2-propenyl, 2,3-dichloro-2-propenyl, 3,3-dichloro-2-propenyl, 2,3,3-trifluoro-2-propenyl, 2, 3,3-Trichloro-2-propenyl, 1-(trifluoromethyl)vinyl, 4,4-difluoro-3-butenyl, 3,4,4-trifluoro-3-butenyl , 3-chloro-4,4,4-trifluoro-2-butenyl, etc., as specific examples, are selected in the range of the number of carbon atoms each designated.

In this specification, _{the label of "C a} ~C _b alkynyl" means that the number of carbon atoms is a straight chain or branched chain formed from a to b, and it has 1 or 2 or more triads in the molecule. The unsaturated hydrocarbon group of the bond, for example, ethynyl, propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-hexynyl, 4,4,4-trifluoro-2 -Butynyl and the like are selected as specific examples in the range of the number of carbon atoms designated by each.

In this specification, _{the label "C a} ~C _b haloalkynyl" means that the hydrogen atom bonded to the carbon atom is arbitrarily substituted by a halogen atom. The number of carbon atoms is a straight chain or An unsaturated hydrocarbon group that is branched and has one or more triple bonds in the molecule. At this time, when it is substituted by two or more halogen atoms, these halogen atoms may be the same as each other, or may be different from each other. Examples include 2-chloroethynyl, 2-bromoethynyl, 2-iodoethynyl, 3-chloro-2-propynyl, 3-bromo-2-propynyl, 3-iodo-2-propynyl As a specific example, it is selected in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b cycloalkyl" means a cyclic hydrocarbon group with a number of carbon atoms from a to b, which can form a monocyclic ring from a 3-membered ring to a 6-membered ring or Compound ring structure. In addition, 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, etc. can be cited as specific examples. The range of the number of carbon atoms specified by each is selected.

In this specification, _{the label of "C a} ~C _b halocycloalkyl" refers to a cyclic hydrocarbon group in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted by a halogen atom and the number of carbon atoms is a to b. , Can form a single ring or compound ring structure from 3-membered ring to 6-membered ring. In addition, each ring can be optionally substituted by an alkyl group within the range of the specified number of carbon atoms, and the substitution of halogen atoms can be a ring structure part, a side chain part, or both of these, and further by 2 or more When halogen atoms are substituted, these halogen atoms may be the same or different from each other. Examples include 2,2-difluorocyclopropyl, 2,2-dichlorocyclopropyl, 2,2-dibromocyclopropyl, 2,2-difluoro-1-methylcyclopropyl, 2, 2-Dichloro-1-methylcyclopropyl, 2,2-dibromo-1-methylcyclopropyl, 2,2,3,3-tetrafluorocyclobutyl, etc. are taken as specific examples. Selection of the range of the number of carbon atoms.

In this specification, _{the label of "C a} ~C _b alkoxy" means an alkyl-O- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, methoxy, ethyl Oxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, tert-butoxy, 2-ethylhexyloxy, etc. as specific examples , Select from the range of the number of carbon atoms specified by each.

In this specification, _{the label of "C a} ~C _b haloalkoxy" refers to a haloalkyl-O- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, difluoromethyl Oxy, 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-hexafluoropropoxy, etc. as specific For example, select the range of the number of carbon atoms specified by each.

In this specification, _{the label of "C a} ~C _b alkenyloxy" means an alkenyl-O- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, 2-propenyloxy , 2-butenyloxy, 2-methyl-2-propenyloxy, 3-methyl-2-butenyloxy, etc., as specific examples, are selected in the range of the number of carbon atoms each designated.

In this specification, _{the label of "C a} ~C _b haloalkenyloxy" means a haloalkenyl-O- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, 3,3 -Difluoroallyloxy, 3,3-dichloroallyloxy, etc., as specific examples, are selected in the range of the number of carbon atoms each designated.

In this specification, _{the label of "C a} ~C _b alkynyloxy" means an alkynyl-O- group with the aforementioned meaning formed by the number of carbon atoms from a to b. Examples include ethynyloxy and propionyl. An alkynyloxy group, a 2-butynyloxy group, a 1-pentynyloxy group, a 1-hexynyloxy group, etc. are selected as specific examples in the range of the number of carbon atoms designated by each.

In this specification, _{the label "C a} ~C _b haloalkynyloxy" refers to a haloalkynyl-O- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, 3-chloro 2-propynyloxy, 3-bromo-2-propynyloxy, 3-iodo-2-propynyloxy, etc. are specific examples, and are selected in the range of the number of carbon atoms each designated.

In this specification, _{the label of "C a} ~C _b alkylthio" means an alkyl-S- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, methylthio, ethyl Sulfuryl, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, tert-butylthio, etc. are specific examples, with the number of carbon atoms each designated The range of choices.

In this specification, _{the label of "C a} ~C _b haloalkylthio" means a haloalkyl-S- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, difluoromethyl Sulfuryl, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2 -Chloro-1,1,2-trifluoroethylthio, pentafluoroethylthio, 1,1,2,3,3,3-hexafluoropropylthio, heptafluoropropylthio, 1,2,2 , 2-Tetrafluoro-1-(trifluoromethyl)ethylthio, nonafluorobutylthio and the like are specific examples, and are selected in the range of the number of carbon atoms each designated.

In this specification, _{the label of "C a} ~C _b alkenylthio" means an alkenyl-S- group with the aforementioned meaning formed by the number of carbon atoms from a to b. For example, 2-propenylthio is mentioned. , 2-butenylthio, 2-methyl-2-propenylthio, 3-methyl-2-butenylthio, etc., as specific examples, are selected within the range of the number of carbon atoms designated by each.

In this specification, _{the label "C a} ~C _b haloalkenylthio" means a haloalkenyl-S- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, 2-fluoro -2-propenylthio, 2-chloro-2-propenylthio, 3,3-difluoro-2-propenylthio, 3,3-dichloro-2-propenylthio, 2,3,3-tri Fluoro-2-propenylthio, 4,4-difluoro-3-butenylthio, 3,4,4-trifluoro-3-butenylthio, etc. as specific examples, with the number of carbon atoms each designated Range selection.

In this specification, _{the label of "C a} ~C _b alkynylthio" means an alkynyl-S- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, propynylthio, As specific examples, butynylthio, pentynylthio, hexynylthio, etc., are selected within the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b haloalkynylthio" means a haloalkynyl-S- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, 3-chloro 2-propynylthio, 3-bromo-2-propynylthio, 3-iodo-2-propynylthio, etc. are specific examples, and are selected in the range of the number of carbon atoms each designated.

In this specification, _{the label of "C a} ~C _b alkylsulfinyl group" means an alkyl-S(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, List methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, i-propylsulfinyl, n-butylsulfinyl, i-butylsulfinyl , S-butylsulfinyl, tert-butylsulfinyl, etc., as specific examples, are selected in the range of the number of carbon atoms designated by each.

In this specification, _{the mark of "C a} ~C _b haloalkylsulfinyl" refers to a haloalkyl-S(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b, For example, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, 2,2,2-trifluoroethane Sulfinyl group, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethylsulfinyl group, nonafluorobutylsulfinyl group, etc., as specific examples, and each designated carbon The range of atomic number is selected.

In this specification, _{the label of "C a} ~C _b alkenylsulfinyl" means an alkenyl -S(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b. For example, List 2-propenylsulfinyl, 2-butenesulfinyl, 2-methyl-2-propenylsulfinyl, 3-methyl-2-butenesulfinyl, etc. as specific examples , Select from the range of the number of carbon atoms specified by each.

In this specification, _{the mark of "C a} ~C _b haloalkenylsulfinyl" refers to a haloalkenyl -S(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b, For example, 2-fluoro-2-propenylsulfinyl, 2-chloro-2-propenylsulfinyl, 3,3-difluoro-2-propenylsulfinyl, 3,3-bis Chloro-2-propenylsulfinyl, 4,4-difluoro-3-butenylsulfinyl, 3,4,4-trifluoro-3-butenylsulfinyl, etc. as specific examples , Select from the range of the number of carbon atoms specified by each.

In this specification, _{the label of "C a} ~C _b alkynylsulfinyl group" means an alkynyl -S(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b. For example, A 2-propynylsulfinyl group, a 2-butynylsulfinyl group, etc. are given as specific examples, and they are selected within the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b haloalkynylsulfinyl" refers to a haloalkynyl -S(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b, For example, 3-chloro-2-propynylsulfinyl, 3-bromo-2-propynylsulfinyl, 3-iodo-2-propynylsulfinyl, etc. can be cited as specific examples. The range of the number of carbon atoms specified by each is selected.

In this specification, _{the label of "C a} ~C _{b alkylsulfonyl" refers to an alkyl-SO 2} -group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, methyl Sulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl, i-butylsulfonyl, s-butylsulfonyl, As a specific example, tert-butylsulfonyl and the like are selected in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _{b haloalkylsulfonyl" refers to a haloalkyl-SO 2} -group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, Difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethanesulfonyl, bromodifluoromethanesulfonyl, 2,2,2-trifluoroethylsulfonyl, 1, 1,2,2-tetrafluoroethylsulfonyl, 2-chloro-1,1,2-trifluoroethylsulfonyl, etc. are selected as specific examples in the range of the number of carbon atoms designated by each.

In this specification, _{the label "C a} ~C _{b alkenylsulfonyl" refers to an alkenyl -SO 2} -group with the aforementioned meaning formed by the number of carbon atoms from a to b. For example, 2- Propenylsulfonyl, 2-butenylsulfonyl, 2-methyl-2-propenylsulfonyl, 3-methyl-2-butenylsulfonyl, etc. are taken as specific examples. Selection of the range of the number of carbon atoms.

In this specification, _{the label of "C a} ~C _{b haloalkenyl sulfonyl" refers to a haloalkenyl -SO 2} -group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, 2-fluoro-2-propenylsulfonyl, 2-chloro-2-propenylsulfonyl, 3,3-difluoro-2-propenylsulfonyl, 3,3-dichloro-2-propenyl Sulfonyl, 4,4-difluoro-3-butenylsulfonyl, 3,4,4-trifluoro-3-butenylsulfonyl, etc. as specific examples, with the number of carbon atoms each designated Range selection.

In this specification, _{the label of "C a} ~C _{b alkynylsulfonyl" refers to an alkynyl -SO 2} -group having the aforementioned meaning and having the number of carbon atoms from a to b. For example, 2- Propynylsulfonyl, 2-butynylsulfonyl, etc. are selected as specific examples in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _{b haloalkynylsulfonyl" refers to a haloalkynyl -SO 2} -group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, 3-chloro-2-propynylsulfonyl, 3-bromo-2-propynylsulfonyl, 3-iodo-2-propynylsulfonyl, etc., as specific examples, with the number of carbon atoms each designated The range of choices.

In this specification, _{the label of "C a} ~C _b alkylamino group" means that one of the hydrogen atoms is an alkyl substituted amino group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, Methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, tert-butylamino group, etc. are taken as specific examples. The range of the number of carbon atoms specified by each is selected.

In this specification, _{the label of "C a} ~C _b haloalkylamino group" means that one of the hydrogen atoms is a haloalkyl substituted amino group with a carbon atom number from a to b, which has the aforementioned meaning, for example Specific examples include 2,2,2-trifluoroethylamino, 2-chloro-2,2-difluoroethylamino, 3,3,3-trifluoropropylamino, etc., which are designated for each The range of carbon atoms is selected.

In this specification, the label of "two (C _a ~C _b ) alkylamino groups" means that both hydrogen atoms can be the same or different from each other. The number of carbon atoms is composed of a ~ b and has the aforementioned meaning The alkyl substituted amino group, for example, dimethylamino, ethyl (methyl) amino, diethyl amino, n-propyl (methyl) amino, i-propyl (methyl) ) Amino group, di(n-propyl)amino group, di(n-butyl)amino group, etc., as specific examples, are selected in the range of the number of carbon atoms each designated.

In this specification, the label of "two (C _a ~C _b ) haloalkylamino groups" means that both hydrogen atoms can be the same or different from each other. The number of carbon atoms is composed of a ~ b. The meaning of the haloalkyl substituted amino group includes, for example, a bis(2,2,2-trifluoroethyl)amino group as a specific example, and it is selected in the range of the number of carbon atoms each designated.

In this specification, _{the label of "C a} ~C _b alkylcarbonyl" means an alkyl-C(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, acetyl Butanoyl, propyl, butanoyl, isobutanoyl, pentanoyl, isopentanoyl, 2-methylbutanoyl, Pivaloyl, hexanoyl, heptanoyl, etc. as specific examples, each Selection of the range of the specified number of carbon atoms.

In this specification, _{the label of "C a} ~C _b haloalkylcarbonyl" refers to a haloalkyl-C(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, Fluoroacetyl, chloroacetyl, difluoroacetyl, dichloroacetyl, trifluoroacetyl, chlorodifluoroacetyl, bromodifluoroacetyl, trichloroacetyl, pentafluoro Propionyl, heptafluorobutanoyl, 3-chloro-2,2-dimethylpropanoyl, etc. are specific examples, and are selected in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b alkoxycarbonyl group" means an alkyl-OC(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b, for example, methyl Oxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, s-butoxycarbonyl, tert-butoxycarbonyl , 2-ethylhexyloxycarbonyl, etc., as specific examples, are selected in the range of the number of carbon atoms each designated.

In this specification, _{the label of "C a} ~C _b haloalkoxycarbonyl" means a haloalkyl-OC(O)- group with the aforementioned meaning formed by the number of carbon atoms from a to b. For example, Examples include chloromethoxycarbonyl, 2-chloroethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 2,2,2,-trifluoroethoxycarbonyl, 2,2,2,-trichloroethane As a specific example, an oxycarbonyl group etc. are selected in the range of the number of carbon atoms each designated.

_{The label of "C a} ~C _b alkylaminocarbonyl" in this specification means that one of the hydrogen atoms is an alkyl-substituted amine methanoyl group having the aforementioned meaning with the number of carbon atoms from a to b. For example, methylaminomethanoyl, ethylaminomethanoyl, n-propylaminomethanoyl, i-propylaminomethanoyl, n-butylaminomethanoyl, i-butylaminomethanoyl An acyl group, s-butylaminoformyl group, tert-butylaminoformyl group, etc. are selected as specific examples in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b haloalkylaminocarbonyl" means that one of the hydrogen atoms is a haloalkyl substituted amine methyl with the number of carbon atoms from a to b. Group, for example, 2-fluoroethylaminomethanoyl, 2-chloroethylaminomethanoyl, 2,2-difluoroethylaminomethanoyl, 2-trifluoroethylaminomethanoyl and the like can be mentioned as examples A specific example is selected in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b alkylamine thiocarbonyl group" means that one of the hydrogen atoms is an alkylamino group -C(= S)- groups, for example, methylthioamine methionyl, ethylthioamine methionyl, n-propylthioamine methionyl, i-propylthioamine methionyl, n-butylthioamine Methionyl, i-butylthiocarbamate, s-butylthiocarbamate, tert-butylthiocarbamate, etc. are selected as specific examples in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b haloalkylamine thiocarbonyl group" means that one of the hydrogen atoms is a haloalkylamino group -C with the number of carbon atoms from a to b. (=S)-group, for example, 2-fluoroethylthioaminoformyl, 2-chloroethylthioaminoformyl, 2,2-difluoroethylthioaminoformyl, 2-trifluoro As a specific example, ethylthioaminoformyl and the like are selected in the range of the number of carbon atoms designated by each.

In this specification, _{the label of "C a} ~C _b alkylaminosulfonyl" means that one of the hydrogen atoms is an alkyl substituted sulfonamide with the number of carbon atoms from a to b. Group, for example, methylsulfasulfonyl, ethylsulfasulfonyl, n-propylsulfasulfonyl, i-propylsulfasulfonyl, n-butylsulfasulfonyl, i-butyl A sulfamoyl, s-butyl sulfamoyl, tert-butyl sulfamoyl, etc. are taken as specific examples, and selected in the range of the number of carbon atoms designated by each.

In this specification, the label of "two (C _a ~C _b ) alkylaminosulfonyl groups" means that both hydrogen atoms can be the same or different from each other. The number of carbon atoms is composed of a to b. The alkyl-substituted sulfasulfonyl group with the aforementioned significance, for example, N,N-dimethylsulfasulfonyl group, N-ethyl-N-methylsulfasulfonyl group, N,N-diethylamine Sulfonyl, N,N-bis(n-propyl)sulfasulfonyl, N,N-bis(n-butyl)sulfasulfonyl, etc., as specific examples, are selected in the range of the number of carbon atoms each designated .

In the present specification, the label of "heterocyclic group" includes, for example, thiophen-2-yl, thiophen-3-yl, furan-2-yl, furan-3-yl, pyrrol-1-yl, pyridine Pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, iso Oxazol-5-yl, isoxazolin-3-yl, isoxazolin-4-yl, isoxazolin-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5- Yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl , Imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-3-yl, 1,2 ,4-oxadiazole-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazole-5 -Yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,2,3-thiadi Azol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2, 3-triazol-4-yl, 1,2,3,4-tetrazol-1-yl, 1,2,3,4-tetrazol-2-yl, 1,2,3,4-tetrazole- 5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, pyridazine- 3-yl, pyridazin-4-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-Triazine-6-yl, benzothiophen-2-yl, benzothiophen-3-yl, benzothiophen-4-yl, benzothiophen-5-yl, benzothiophene-6 -Yl, benzothiophen-7-yl, benzofuran-2-yl, benzofuran-3-yl, benzofuran-4-yl, benzofuran-5-yl, benzofuran-6-yl , Benzofuran-7-yl, indol-1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl , Indole-7-yl, benzothiazol-2-yl, benzothiazol-4-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzothiazol-7-yl, benzothiazol Imidazol-1-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, benzimidazol-6-yl, benzimidazol-7-yl, benziisoxan Azol-3-yl, benzisoxazol-4-yl, benzisoxazol-5-yl, benzisoxazole-6- Group, benzisothiazol-7-yl, benzisothiazol-3-yl, benzisothiazol-4-yl, benzisothiazol-5-yl, benzisothiazol-6-yl, benzo Isothiazol-7-yl, indazol-1-yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, benzene Oxazol-2-yl, benzoxazol-4-yl, benzoxazol-5-yl, benzoxazol-6-yl, benzoxazol-7-yl, quinolin-2-yl , Quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl , Isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, isoquinolin-8-yl, quino Oxalin-2-yl, quinoxalin-3-yl, quinoxalin-5-yl, quinoxalin-6-yl, quinoxalin-7-yl, quinoxalin-8-yl, phthalazine ( Phthalazine)-1-yl, phthalazin-4-yl, phthalazin-5-yl, phthalazin-6-yl, phthalazin-7-yl, phthalazin-8-yl, phthalazin-3-yl, phthalazin-3-yl Lin-4-yl, cinnoline-5-yl, cinnoline-6-yl, cinnoline-7-yl, cinnoline-8-yl, quinazolin-2-yl, quinazolin-4-yl, Quinazolin-5-yl, quinazolin-6-yl, quinazolin-7-yl, quinazolin-8-yl, etc. are given as specific examples.

In this specification, "C _a ~C _b cycloalkyl (C _d ~C _e ) alkyl", "C _a ~C _b halocycloalkyl (C _d ~C _e ) alkyl" or "hydroxy (C _d) ~C _{e )Alkyl" and the like refer to a} hydrogen atom bonded to a carbon atom by any of the aforementioned meanings of C _a ~C _b cycloalkyl, C a ~C _{b halocycloalkyl, or hydroxyl group.} The number of arbitrarily substituted carbon atoms is an alkyl group having the aforementioned meaning formed from d to e, and is selected in the range of the number of carbon atoms designated by each.

In this description are the optionally substituted (C _a ~ C _b) alkyl groups R ^{1a, A 1a-a} is substituted with any of the (C ₁ -C ₆₎ alkyl, substituted by any of Y ^a (C ₁ -C ₆₎ alkyl, etc. numerals Department expressed by any of R ^{1a, A 1a-a} or Y ^a, the number of carbon atoms and hydrogen atoms bonded to carbon atoms of the optionally substituted by one from a ~ b The alkyl groups having the aforementioned meanings are selected in the range of the number of carbon atoms designated respectively. At this time, the individual (C _a ~ C _b) alkyl substituent on the group R ^1a, or when ^{A 1a-a} Y ^a presence of two or more, individual R ^{1a, A 1a-a} Y ^a may be identical to each other or also Can be different from each other.

In the present specification, ^{A 1a-a} is substituted with any of the (C _a ~ C _b) haloalkyl, it being optionally substituted (C _a ~ C _b) Y ^a haloalkyl and the like the marker of any system expressed by A ^1a-a or Y ^a , the hydrogen atom or halogen atom bonded to the carbon atom is arbitrarily substituted by the number of carbon atoms is a haloalkyl group with the aforementioned meaning, with the respective designated carbon atoms Selection of the range of numbers. At this time, the individual (C _a ~ C _b) on the haloalkyl substituent group ^{A 1a-a} Y ^a or the presence of two or more, individual ^{A 1a-a} Y ^a may be the same or different from each other can each other.

In this specification, the labels of (C _a ~C _b ^{) alkenyl groups arbitrarily substituted by Y a} refer to the number of carbon atoms in which the hydrogen atom bonded to the carbon atom is arbitrarily substituted ^{by any Y a} The alkenyl groups with the aforementioned meanings are formed from a to b, which are selected in the range of the number of carbon atoms designated by each. At this time, when there are two or more ^{substituents Y a} _{on the individual (C a} -C _b ) alkenyl groups ^{, the individual Y a} may be the same or different from each other.

In this specification, the labels of (C _a ~C _b ^{)alkynyl groups optionally substituted by Y b} refer to the number of carbon atoms in which the hydrogen atom bonded to the carbon atom is arbitrarily substituted ^{by any Y b} The alkynyl groups with the aforementioned meanings are formed from a to b, and are selected in the range of the number of carbon atoms designated by each. At this time, when there are two or more ^{substituents Y b} _{on the individual (C a} -C _b ) alkynyl groups ^{, the individual Y b} may be the same or different from each other.

In this specification, the labels of (C _a ~C _b ^{) alkoxy groups optionally substituted by Y a} indicate that by any Y ^a , the number of carbon atoms in which the hydrogen atom bonded to the carbon atom is arbitrarily substituted is The alkoxy group with the aforementioned meaning formed from a to b is selected in the range of the number of carbon atoms designated by each. At this time, when there are two or more ^{substituents Y a} _{on the individual (C a} -C _b ) alkoxy groups ^{, the individual Y a} may be the same or different from each other.

In this specification, the labels of (C _a ~C _b ^{)alkenyloxy groups optionally substituted by Y a} indicate that by any Y ^a , the number of carbon atoms in which the hydrogen atom bonded to the carbon atom is arbitrarily substituted is The alkenyloxy group having the aforementioned meaning formed from a to b is selected in the range of the number of carbon atoms designated by each. At this time, the group Y ^a substituent is present on two or more individual (C _a ~ C _b) alkenyl group, Y ^a may be the same individual can also be different from each other to each other.

In this specification, the labels of (C _a ~C _b ^{)alkynyloxy group optionally substituted by Y a} indicate that by any Y ^a , the number of carbon atoms in which the hydrogen atom bonded to the carbon atom is arbitrarily substituted is The alkynyloxy group having the aforementioned meaning formed from a to b is selected in the range of the number of carbon atoms designated by each. At this time, the group Y ^a substituent is present on two or more individual (C _a ~ C _b) alkynyl group, Y ^a may be the same individual can also be different from each other to each other.

R ^3a is in this description of the optionally substituted (C _a ~ C _b) alkylthio, R ^4a is substituted by any of (C _a ~ C _b) thioalkyl, any of the substituents Y ^a (C _a ~C _b ) The label of alkylthio group, etc., means that the number of carbon atoms of the hydrogen atom bonded to the carbon atom ^{by any of R 3a} , R ^4a or Y ^{a is composed of a to b.} The alkylthio group having the aforementioned meaning is selected in the range of the number of carbon atoms designated respectively. At this time, the individual (C _a ~ C _b) the substituents on the alkylthio group R ^3a, R ^4a when two or more Y ^a or the presence of individual R ^3a, R ^4a or Y ^a may be identical or another relative to each other different.

In this specification, the labels of (C _a ~C _b ^{)alkylsulfinyl groups arbitrarily substituted by Y a} indicate that the hydrogen atom bonded to the carbon atom is arbitrarily substituted ^{by any Y a.} The number of atoms is an alkylsulfinyl group having the aforementioned meaning formed from a to b, and is selected in the range of the number of carbon atoms designated by each. At this time, the individual (C _a ~ C _b) alkylsulfinyl the acyl group Y ^a time when two or more substituents exist, individual Y ^a may be identical to one another also different from each other.

In this specification, the labels of (C _a ~C _b ^{)alkylsulfonyl groups arbitrarily substituted by Y a} indicate that the hydrogen atom bonded to the carbon atom is arbitrarily substituted ^{by any Y a.} The number is an alkylsulfonyl group with the aforementioned meaning formed from a to b, and is selected in the range of the number of carbon atoms designated by each. At this time, the individual (C _a ~ C _b) alkylsulfonyl group on the group Y ^a time when two or more substituents exist, individual Y ^a may be identical to one another also different from each other.

In this specification, ^{the phenyl optionally substituted by R 3b} , the phenyl optionally substituted by R ^4b , or the phenyl optionally substituted by Y ^c , etc., means that by any of R ^3b , R ^4b or Y ^c , the phenyl group in which the hydrogen atom bonded to the carbon atom is arbitrarily substituted. At this time, when there are two or more ^{substituents R 3b} , R ^4b or Y ^c on the individual phenyl group ^{, the individual R 3b} , R ^4b or Y ^c may be the same or different from each other.

In this specification ^{, the labels of a heterocyclic ring optionally substituted by R 3b} , a heterocyclic ring optionally substituted by R ^4b , or a heterocyclic ring optionally substituted by Y ^c , etc., mean that by any of R ^3b , R ^4b or Y ^c , a heterocyclic group in which a hydrogen atom bonded to a carbon atom or a nitrogen atom is optionally substituted. At this time, when there are two or more ^{substituents R 3b} , R ^4b or Y ^c on the individual heterocyclic group ^{, the individual R 3b} , R ^4b or Y ^c may be the same or different from each other.

Next, the method for producing the compound of the present invention represented by the aforementioned formula (1) will be described below. The compound of the present invention can be produced by the following production method 1 to production method 17, for example.

Manufacturing method 1

By combining the compound represented by the formula (2Q1-a) (wherein A ^1a , A ² , A ³ , A ⁴ and A ^{5 have the} same meaning as the foregoing), and the compound represented by the formula (3D-a) (wherein, R ¹ , D and n represent the same meaning as the aforementioned compound) in a solvent or without a solvent, if necessary in the presence of a dehydrating condensing agent, if necessary in the presence of a catalyst, the reaction can be prepared by formula (4- a) A compound represented by (in the formula, R ¹ , A ^1a , A ² , A ³ , A ⁴ , A ⁵ , D, and n have the same meaning as described above). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a dehydrating condensing agent. As the dehydrating condensing agent that can be used, for example, 1H-benzotriazol-1-yloxyginseng (dimethylamino)phosphonium hexafluorophosphate, N,N'-dicyclohexylcarbodiimide , 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 2-chloro-1-methylpyridine iodide. As the equivalent of the dehydrating condensing agent, it can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (2Q1-a), preferably in the range of 1 to 20 equivalents.

This reaction can be carried out in the presence of a catalyst. Examples of catalysts that can be used include 1-hydroxybenzotriazole and 4-(dimethylamino)pyridine. As the equivalent of the catalyst, it can be used in the range of 0.005 to 20 equivalents relative to the compound represented by the formula (2Q1-a), preferably in the range of 0.1 to 5 equivalents.

The reaction temperature can be set from -80℃ to the reflux temperature of the reaction mixture The arbitrary temperature up to this is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (3D-a) can be used in the range of 0.5 to 50 equivalents relative to the compound (2Q1-a), preferably in the range of 1 to 20 equivalents.

In addition, the compound represented by the formula (4-a) can be obtained by combining the compound represented by the formula (2Q1-a) with the formula (3D-b) (in the formula, R ¹ , D, and n have the same meaning as described above) The indicated compound can be prepared by reacting in a solvent or without a solvent, if necessary, in the presence of a base. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a base. Examples of usable bases include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-( Dimethylamino)pyridine Pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or 1,5-bis Azabicyclo[4.3.0]-5-nonane (DBN) and other organic bases, sodium hydroxide, potassium hydroxide, sodium hydride, sodium bicarbonate, potassium carbonate, cesium carbonate and other inorganic bases. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (2Q1-a), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (3D-b) can be used in the range of 0.5 to 50 equivalents relative to the compound (2Q1-a), preferably in the range of 1 to 20 equivalents.

Secondly, by putting the compound represented by the formula (4-a) in a solvent or without a solvent, if necessary in the presence of an acid, and if necessary in the presence of a dehydrating agent, dehydration and condensation can be prepared by the formula (1-a) ) (In the formula, R ¹ , A ^1a , A ² , A ³ , A ⁴ , A ⁵ , D, and n represent the same meaning as described above). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of an acid. Examples of usable acids include p-toluenesulfonic acid, polyphosphoric acid, acetic acid, and propionic acid. The acid equivalent can be used in the range of 0.1 to 1000 equivalents relative to the compound represented by the formula (4-a), preferably in the range of 1 to 500 equivalents.

This reaction can be carried out in the presence of a dehydrating agent. Examples of the dehydrating agent that can be used include phosphorus oxychloride and acetic anhydride. As the equivalent of the dehydrating agent, it can be used in the range of 0.5 to 50 equivalents relative to the compound represented by the formula (4-a), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

Some of the compounds represented by the general formula (2Q1-a) are well-known compounds, and some of them are available as commercial products. In addition, others can also be synthesized in accordance with Reaction Formula 4 described below, for example.

The compound represented by the formula (3D-a) can be synthesized in accordance with the following reaction formula 1 and reaction formula 2, for example.

The compound represented by the formula (3D-b) can be synthesized in accordance with the reaction formula 1 described below, for example.

Manufacturing method 2

By combining the compound represented by the formula (1-f) (wherein R ¹ , A ² , A ³ , A ⁴ , A ⁵ , D, and n have the same meaning as described above), and the compound represented by the formula (16) [formula Where A ^1aa represents a C ₁ -C ₆ alkyl group, X ₁ represents a halogen atom, a C ₁ -C ₄ alkyl sulfonate group (such as a methanesulfonyloxy group, etc.), a C ₁ -C ₄ haloalkyl sulfonate A compound represented by an ester group (e.g., trifluoromethanesulfonyloxy group, etc.) or an arylsulfonate group (e.g., benzenesulfonyloxy group, p-toluenesulfonyloxy group, etc.) , In a solvent or no solvent, if necessary, in the presence of a base, the reaction can be made into formula (1-g) (where R ¹ , A ^1aa , A ² , A ³ , A ⁴ , A ⁵ , D And n represents the compound represented by the same meaning as above). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a base. Examples of usable bases include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-( Dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) Or 1,5-diazabicyclo[4.3.0]-5-nonane (DBN) and other organic bases, sodium hydroxide, potassium hydroxide, sodium hydride, sodium bicarbonate, potassium carbonate, cesium carbonate, etc. Inorganic bases. As the equivalent of the base, it can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (1-f), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (16) can be used in the range of 0.5 to 50 equivalents relative to the compound (1-f), preferably in the range of 1 to 20 equivalents.

The compound represented by the general formula (1-f) can be synthesized in accordance with the production method 1.

Some of the compounds represented by formula (16) are well-known Part of the compound can be obtained as a commercially available product.

Manufacturing method 3

By combining the compound represented by the formula (2Q1-a) and the compound represented by the formula (17-a) (wherein G ₁ , G ₂ , G ₃ and G ₄ represent the same meaning as described above), according to the manufacturing method The reaction described in step [A] of step 1 can produce formula (18-a) (where A ^1a , A ² , A ³ , A ⁴ , A ⁵ , G ₁ , G ₂ , G ₃ and G ₄ represents the compound represented by the same meaning as above).

In addition, the compound represented by the formula (18-a) can be obtained by combining the compound represented by the formula (2Q1-a) with the formula (17-b) (in the formula, G ₁ , G ₂ , G ₃ and G _{4 are} represented by The compound represented by the same meaning as above) is prepared by reacting according to the method described in step [A] of manufacturing method 1.

Next, by subjecting the compound represented by the formula (18-a) to dehydration and condensation according to the method described in the step [B] of the manufacturing method 1, the formula (19-a) can be prepared (where A ^1a , A ² , A ³ , A ⁴ , A ⁵ , G ₁ , G ₂ , G ₃ and G ₄ represent the compounds represented by the aforementioned).

Next, by reacting the compound represented by the formula (19-a) in a solvent or without a solvent, with the compound represented by the formula (9) (in the formula, R ¹ represents the same meaning as described above) and a halogenating agent, It can be expressed by the formula (1-h) (where R ¹ , A ^1a , A ² , A ³ , A ⁴ , A ⁵ , G ₁ , G ₂ , G ₃ and G _{4 have the} same meaning as above) Compound. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

Examples of the halogenating agent include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethyl Hydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo- 5,5-Dimethylhydantoin, etc. The equivalent of the halogenating agent can be used in the range of 0.5 to 50 equivalents relative to the compound represented by formula (19-a), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (9) can be used in the range of 0.5 to 50 equivalents relative to the compound (19-a), preferably in the range of 1 to 20 equivalents.

Furthermore, by reacting the compound represented by the formula (19-a) with a halogenating agent in a solvent or without a solvent, the formula (23-a) can be prepared (where A ^1a , A ² , A ³ , A ⁴ , A ⁵ , G ₁ , G ₂ , G ₃ and G ₄ represent the same meanings as described above, and X ₁₀ represents a compound represented by a chlorine atom, a bromine atom, or an iodine atom. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

Examples of the halogenating agent include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethyl Hydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, etc. The equivalent of the halogenating agent can be used in the range of 0.5 to 50 equivalents relative to the compound represented by formula (19-a), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

Secondly, by putting the compound represented by formula (23-a) and the compound represented by formula (24) (in the formula, R ¹ has the same meaning as above) in a solvent or without a solvent, if necessary, the presence of a base The following reaction can produce formula (1-h) (where R ¹ , A ^1a , A ² , A ³ , A ⁴ , A ⁵ , G ₁ , G ₂ , G ₃ and G ₄ represent the same as the above Meaning) represents the compound. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a base. Examples of usable bases include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-( Dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) Or 1,5-diazabicyclo[4.3.0]-5-nonane (DBN) and other organic bases, sodium hydroxide, potassium hydroxide, sodium hydride, sodium bicarbonate, potassium carbonate, cesium carbonate, etc. Inorganic bases. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (23-a), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (24) can be used in the range of 0.5 to 50 equivalents relative to the compound (23-a), preferably in the range of 1 to 20 equivalents.

In addition, the compound represented by the formula (1-h) can be obtained by combining the compound represented by the formula (23-a) and the compound represented by the formula (9) in a solvent or insoluble The agent is prepared by reacting in the presence of a base if necessary, a palladium catalyst if necessary, and a ligand if necessary. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidinone and other amides, dimethyl sulfide and other sulfenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a base. Examples of usable bases include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-( Dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) Or 1,5-diazabicyclo[4.3.0]-5-nonane (DBN) and other organic bases, sodium hydroxide, potassium hydroxide, sodium hydride, sodium bicarbonate, potassium carbonate, cesium carbonate, etc. Inorganic bases. As the equivalent of the base, it can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (23-a), preferably in the range of 1 to 20 equivalents.

This reaction can be carried out in the presence of a palladium catalyst. As the palladium catalyst that can be used, for example, palladium-carbon, palladium(II) chloride, palladium(II) acetate, bis(triphenylphosphine)palladium(II) dichloride, tetrakis(triphenylphosphine) Palladium(0), bis(dibenzylideneacetone)palladium(0), ginseng(dibenzylideneacetone)dipalladium(0), etc. Palladium as a catalyst The equivalent weight can be used in the range of 0.005 to 20 equivalents relative to the compound (23-a), preferably in the range of 0.01 to 5 equivalents.

The reaction can be carried out in the presence of ligands. Examples of ligands that can be used include 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene, 1,10-phenanthroline, and the like. As the equivalent of the ligand, it can be used in the range of 0.005 to 20 equivalents relative to the compound (23-a), preferably in the range of 0.01 to 5 equivalents.

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

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (9) can be used in the range of 0.5 to 50 equivalents relative to the compound (23-a), preferably in the range of 1 to 20 equivalents.

Some of the compounds represented by formula (17-a) are well-known compounds, and some of them are available as commercially available products.

Some of the compounds represented by the formula (17-b) are well-known compounds, and some of them are available as commercially available products.

Some of the compounds represented by the formula (9) are well-known compounds, and some of them are available as commercially available products.

Some of the compounds represented by formula (24) are well-known compounds, and some of them are available as commercially available products.

Manufacturing method 4

By combining the compound represented by the formula (2Q1-a) with the compound represented by the formula (20-a) (wherein, T ₁ , G ₁ , G ₂ , G ₃ and G ₄ represent the same meaning as described above), according to The reaction method described in step [A] of manufacturing method 1 can produce formula (21-a) (where A ^1a , A ² , A ³ , A ⁴ , A ⁵ , T ₁ , G ₁ , G _2. G ₃ and G ₄ represent the compounds represented by the same meaning as above).

In addition, the compound represented by the formula (21-a) can be obtained by combining the compound represented by the formula (2Q1-a) with the formula (20-b) (in the formula, T ₁ , G ₁ , G ₂ , G ₃ and G ₄ represents the compound represented by the same meaning as above), which is prepared by reacting according to the method described in step [A] of manufacturing method 1.

Next, by subjecting the compound represented by formula (21-a) to dehydration and condensation in accordance with the method described in step [B] of manufacturing method 1, formula (22-a) (wherein A ^1a , A ^2. A ³ , A ⁴ , A ⁵ , T ₁ , G ₁ , G ₂ , G ₃ and G ₄ represent the compounds represented by the same meaning as above).

Next, the compound represented by formula (22-a) is reacted in accordance with the method described in step [C] of manufacturing method 3, or the method described in step [D] and step [E] of manufacturing method 3 , Can be made into formula (1-i) (where R ¹ , A ^1a , A ² , A ³ , A ⁴ , A ⁵ , T ₁ , G ₁ , G ₂ , G ₃ and G ₄ represent the same as the above Meaning) represents the compound.

Some of the compounds represented by the formula (20-a) are well-known compounds, and some of them are available as commercially available products.

Some of the compounds represented by the formula (20-b) are well-known compounds, and some of them are available as commercially available products.

Manufacturing method 5

A compound represented by the formula (2Q1-b) (wherein A ² , A ³ , A ⁴ and A ⁵ represent the same meanings as described above, and A ^1b represents an oxygen atom or a sulfur atom). The compound represented by the formula (3D- The compound represented by a) is reacted according to the method described in step [A] of manufacturing method 1, and can be prepared by formula (4-b) (wherein, A ^1b , R ¹ , A ² , A ³ , A ⁴ , A ⁵ , D and n represent the compound represented by the same meaning as above).

In addition, the compound represented by the formula (4-b) can also be obtained by combining the compound represented by the formula (2Q1-b) and the compound represented by the formula (3D-b) in accordance with the step [A] of the manufacturing method 1 Prepared by the method described in the reaction.

Secondly, by reacting the compound represented by the formula (4-b) in a solvent or without a solvent, if necessary in the presence of an acid, and if necessary in the presence of a dehydrating condensing agent, the formula (1-b) ) (In the formula, A ^1b , R ¹ , A ² , A ³ , A ⁴ , A ⁵ , D, and n represent the same meanings as described above). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of an acid. Examples of usable acids include p-toluenesulfonic acid, polyphosphoric acid, acetic acid, and propionic acid. The acid equivalent can be used in the range of 0.1 to 1000 equivalents relative to the compound represented by the formula (4-b), preferably in the range of 1 to 500 equivalents.

This reaction can be carried out in the presence of a dehydrating condensing agent. As a dehydrating condensing agent that can be used, for example, a mixture of triphenylphosphine and azodicarboxylic acid bis(2-methoxyethyl) can be cited.

As the equivalent of triphenylphosphine, it can be used in the range of 0.5 to 50 equivalents relative to the compound represented by the formula (4-b), preferably in the range of 1 to 20 equivalents.

As the equivalent of azodicarboxylic acid bis(2-methoxyethyl), relative to The compound represented by the formula (4-b) can be used in the range of 0.5 to 50 equivalents, 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

Some of the compounds represented by the formula (2Q1-b) are well-known compounds, and some of them are available as commercially available products.

Manufacturing method 6

By combining the compound represented by the formula (2Q2-a) (wherein A ² , A ³ , A ⁴ and A ⁵ represent the same meaning as described above), and the compound represented by the formula (3D-c) (where R ¹ , R ⁶ , D and n have the same meanings as before, and X ₂ represents a chlorine atom, a bromine atom or an iodine atom) in a solvent or without a solvent. If necessary, the reaction can be carried out in the presence of a base to obtain the formula (1 -c) (wherein R ¹ , R ⁶ , A ² , A ³ , A ⁴ , A ⁵ , D, and n represent the same meaning as described above). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a base. Examples of usable bases include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-( Dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) Or 1,5-diazabicyclo[4.3.0]-5-nonane (DBN) and other organic bases, sodium hydroxide, potassium hydroxide, sodium hydride, sodium bicarbonate, potassium carbonate, cesium carbonate, etc. Inorganic bases. As the equivalent of the base, it can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (2Q2-a), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

Some of the compounds represented by the formula (2Q2-a) are well-known compounds, and some of them are available as commercially available products. In addition, others can also be synthesized in accordance with Reaction Formula 5 described below, for example.

The compound represented by the formula (3D-c) can be synthesized in accordance with the reaction formula 1 described below, for example.

Manufacturing method 7

By combining a compound represented by formula (1-j) (wherein, R ¹ , A ² , A ³ , A ⁴ , A ⁵ , D, and n have the same meaning as described above), and a halogenating agent in a solvent or The reaction without solvent can produce formula (1-k) (wherein, R ¹ , A ² , A ³ , A ⁴ , A ⁵ , D and n have the same meanings as above, and X ₄ represents a chlorine atom or a bromine atom Or iodine atom). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

Examples of the halogenating agent include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethyl Hydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, etc. The equivalent of the halogenating agent can be used in the range of 0.5 to 50 equivalents relative to the compound represented by the formula (1-j), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

The compound represented by the formula (1-j) can be synthesized according to the method described in Production Method 6.

Manufacturing method 8

By combining a compound represented by the formula (2Q3-a) (wherein R ² , R ³ , A ⁴ and A ⁵ represent the same meaning as described above), and the compound represented by the formula (3D-d) (where R ¹ , D and n represent the same meaning as the compound represented above), in a solvent or without a solvent, if necessary, in the presence of an acid, the reaction can be prepared by formula (40) (where R ¹ , R ² , R ³ , A ⁴ , A ⁵ , D and n represent the compounds represented by the same meaning as above). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of an acid. Examples of usable acids include acetic acid, formic acid, and p-toluenesulfonic acid. As an acid equivalent, relative to the compound represented by formula (2Q3-a), it can be used in the range of 0.1 to 100 equivalents It is preferably used 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (3D-d) can be used in the range of 0.5 to 50 equivalents relative to the compound (2Q3-a), preferably in the range of 1 to 20 equivalents.

Secondly, by reacting the compound represented by formula (40) with phosphite in a solvent or no solvent, formula (1-1) can be prepared (where R ¹ , R ² , R ³ , A ^4. A ⁵ , D and n represent the compounds represented by the same meaning as above). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

Examples of phosphites include trimethyl phosphite and triethyl phosphite Wait. As the equivalent of phosphite, it can be used in the range of 0.5 to 50 equivalents relative to the compound represented by formula (40), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

Some of the compounds represented by the formula (2Q3-a) are well-known compounds, and some of them are available as commercially available products. In addition, other methods may be used in accordance with well-known methods described in the literature, for example, in accordance with the reaction conditions described in [J.Med.Chem.] 2008, Vol. 50, page 2468, International Publication No. 2011/075628, etc. Compound synthesis.

Some of the compounds represented by the formula (3D-d) are well-known compounds, and some of them are available as commercially available products. In addition, others can also be synthesized in accordance with Reaction Formula 6 described below, for example.

Manufacturing method 9

By taking the compound represented by the formula (2Q3-b) (in the formula, R ² , R ³ , A ⁴ and A ⁵ represent the same meaning as described above, and X ₃ represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), By reacting with sodium azide in a solvent or without a solvent, a compound represented by the formula (2Q3-c) (wherein R ² , R ³ , A ⁴ and A ⁵ represent the same meaning as described above) can be prepared. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

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

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, sodium azide can be used in the range of 0.5 to 50 equivalents relative to the compound (2Q3-b), preferably in the range of 1 to 20 equivalents.

Secondly, by combining the compound represented by formula (2Q3-c) and the compound represented by formula (3D-d) in a solvent or no solvent, if necessary in the presence of a base, if necessary in the presence of a catalyst By carrying out the reaction, a compound represented by formula (41) (wherein R ¹ , R ² , R ³ , A ⁴ , A ⁵ , D, and n have the same meaning as described above) can be prepared. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidinone and other amines, dimethyl sulfenite and other sulfenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a base. Examples of usable bases include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-( Dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) Or 1,5-diazabicyclo[4.3.0]-5-nonane (DBN) and other organic bases, sodium hydroxide, potassium hydroxide, sodium hydride, sodium bicarbonate, potassium carbonate, cesium carbonate, etc. Inorganic bases. As the equivalent of the base, it can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (2Q3-c), preferably in the range of 1 to 20 equivalents.

This reaction can be carried out in the presence of a catalyst. As the catalyst that can be used, for example, titanium tetrachloride can be cited. As the equivalent of the catalyst, it can be used in the range of 0.005 to 20 equivalents relative to the compound represented by the formula (2Q3-c), preferably in the range of 0.1 to 5 equivalents.

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

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (3D-d) can be used in the range of 0.5 to 50 equivalents relative to the compound (2Q3-c), preferably 1 to 20 equivalents Range.

Secondly, by cyclizing the compound represented by formula (41) in solvent or without solvent, formula (1-m) can be prepared (wherein, R ¹ , R ² , R ³ , A ⁴ , A ⁵ , D and n represent the compound represented by the same meaning as above).

In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidinone and other amides, dimethyl sulfide and other sulfenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

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

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

Some of the compounds represented by the general formula (2Q3-b) are well-known compounds, and some of them are available as commercially available products. In addition, others can also be synthesized in accordance with Reaction Formula 7 described below, for example.

Manufacturing method 10

By reacting a compound represented by formula (2Q4-a) (wherein, R ⁷ and A ^{8 have the} same meaning as described above) with a compound represented by formula (3D-c) according to the method described in Production Method 6, Compounds represented by formula (1-n) (wherein R ¹ , R ⁶ , R ⁷ , A ⁸ , D and n have the same meaning as described above) can be prepared.

Some of the compounds represented by the formula (2Q4-a) are well-known compounds, and some of them are available as commercially available products. In addition, others may be synthesized from known compounds in accordance with well-known methods described in the literature, for example, in accordance with the reaction conditions described in Journal of Fluorine Chemistry 2012, Volume 133, Section 115, CN101768135, CN101885708, etc.

Manufacturing method 11

By combining a compound represented by formula (1-d) (wherein, R ¹ , Q and D have the same meaning as described above), and an oxidizing agent, in a solvent or without a solvent, the reaction is carried out in the presence of a catalyst if necessary , A compound represented by formula (1-e) (wherein, R ¹ , Q and D represent the same meaning as described above, and n'represents an integer of 1 or 2) can be prepared. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other sulfites, pyridine, quinoline and other nitrogen-containing aromatic compounds, acetic acid or Such mixed solvents, etc.

As the oxidizing agent, for example, m-chloroperbenzoic acid, peracetic acid, etc. Peracid, hydrogen peroxide, potassium peroxymonosulfate (registered trademarks of OXONE, EI DuPont; potassium peroxosulfate content). As the equivalent of the oxidizing agent, it can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (1-d), preferably in the range of 1 to 20 equivalents.

This reaction can be carried out in the presence of a catalyst. Examples of catalysts that can be used include sodium tungstate. As the equivalent of the catalyst, it can be used in the range of 0.005 to 20 equivalents relative to the compound represented by the formula (1-d), preferably in the range of 0.1 to 5 equivalents.

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

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

The compound represented by the formula (1-d) can be synthesized according to the methods described in Manufacturing Methods 1 to 10 or the following Manufacturing Methods 14 to 17.

Manufacturing method 12

The compound represented by the formula (1-o) (wherein R ¹ , R ² , R ³ , R ⁴ , A ¹ , D, and n have the same meaning as above) is combined with an oxidizing agent in accordance with the method described in Manufacturing Method 11 The reaction is carried out to produce a compound represented by formula (1-p) (wherein, R ¹ , R ² , R ³ , R ⁴ , A ¹ and D have the same meaning as described above).

The compound represented by formula (1-o) can be synthesized in accordance with the methods described in manufacturing methods 1 to 5.

Manufacturing method 13

By formulating (1-q) (wherein, R ¹ , A ¹ , A ² , A ⁴ , A ⁵ , D, and n represent the same meaning as described above, and X ₉ represents a chlorine atom, a bromine atom, or an iodine atom) The compound represented, for example, in accordance with the method described in [Organic Lett.] 2007, Volume 9, Page 3687, [Tetrahedron] 1998, Volume 44, Page 1187, International Publication No. 2011/159839, etc., and 3-mercaptopropane The thiolation agent of 2-ethylhexyl acid, sodium hydrogen sulfide, sodium sulfide, etc. can be reacted to produce formula (1-r) (where R ¹ , A ¹ , A ² , A ⁴ , A ⁵ , D and n represent the compound represented by the same meaning as above).

Secondly, by combining the compound represented by the formula (1-r), for example, in accordance with the methods described in International Publication No. 2013/043962, International Publication No. 2013/040863, International Publication No. 2012/082566, etc., and Umemoto test Trifluoromethyl reagent (5-(Trifluoromethyl)dibenzothiophenium trifluoromethanesulfonate), Togni reagent (1-Trifluoromethyl-3,3-dimethyl-1,2-benziodoxole) and other trifluoromethylating agents can be reacted with the formula (1-s ) (In the formula, R ¹ , A ¹ , A ² , A ⁴ , A ⁵ , D, and n represent the same meaning as described above).

Next, the compound represented by the formula (1-s) is reacted with an oxidizing agent according to the method described in the production method 11 to produce the formula (1-t) (where R ¹ , A ¹ , A ² , A ⁴ , A ⁵ , D and n represent the same meaning as the above, and n" represents an integer of 1 or 2).

The compound represented by the formula (1-q) can be synthesized according to the method described in Manufacturing Methods 1 to 5.

Manufacturing method 14

A compound represented by the formula (2Q1-c) (in the formula, A ^1a , A ⁴ , A ⁵ , R ² and R ^{3 have the} same meanings as described above, and X ₁₁ represents a chlorine atom, a bromine atom, or an iodine atom) , And the compound represented by the formula (3D-e) (wherein R ¹ , D and n have the same meaning as above), in a solvent or without a solvent, if necessary in the presence of a copper catalyst, if necessary in the presence of a copper catalyst It is prepared by reacting in the presence of a base and if necessary in the presence of a ligand. In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a copper catalyst. Examples of copper catalysts that can be used include copper iodide (I). The equivalent of copper as a catalyst can be used in the range of 0.005 to 20 equivalents relative to the compound (2Q1-c), preferably in the range of 0.01 to 5 equivalents.

This reaction can be carried out in the presence of a base. Examples of usable bases include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-( Dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) Or organic bases such as 1,5-diazabicyclo[4.3.0]-5-nonane (DBN), sodium hydroxide, potassium hydroxide, sodium hydride, Inorganic bases such as sodium bicarbonate, potassium carbonate, cesium carbonate, and potassium phosphate. As the equivalent of the base, it can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (2Q1-c), preferably in the range of 1 to 20 equivalents.

The reaction can be carried out in the presence of ligands. As the ligand that can be used, for example, 1,10-phenanthroline, 1,2-diaminoethane, N,N'-dimethylethylenediamine, and the like can be cited. As the equivalent of the ligand, it can be used in the range of 0.005 to 20 equivalents relative to the compound (2Q1-c), preferably in the range of 0.01 to 5 equivalents.

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

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (3D-e) can be used in the range of 0.5 to 50 equivalents relative to the compound (2Q1-c), preferably in the range of 1 to 20 equivalents.

Next, by subjecting the compound represented by the formula (4-c) to dehydration and condensation according to the method described in the step [B] of the manufacturing method 1, the formula (1-u) can be prepared (where A ^1a , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , D and n represent the compounds represented by the same meaning as above).

Some of the compounds represented by the general formula (2Q1-c) are well-known compounds, and some of them are available as commercial products. In addition, others can also be synthesized in accordance with Reaction Formula 4 described below, for example.

The compound represented by the formula (3D-e) can be synthesized in accordance with the reaction formula 8 described below, for example.

Manufacturing method 15

By formulating a compound represented by formula (50) (wherein R ² , R ³ , A ^1a , A ⁴ and A ⁵ represent the same meaning as described above, and X ₁₂ represents a chlorine atom, a bromine atom, or an iodine atom), and The compound represented by the formula (5-a) (wherein G ₁ , G ₂ , G ₃ and G ₄ represent the same meaning as described above) is reacted according to the method described in Production Method 6, and the formula (51) ( In the formula, R ² , R ³ , A ^1a , A ⁴ , A ⁵ , G ₁ , G ₂ , G ₃ and G ₄ represent the compounds represented by the same meaning as described above).

Next, by reacting the compound represented by the formula (51) and the compound represented by the formula (9) in accordance with the method described in the step [C] of the manufacturing method 3, the formula (1-v)( In the formula, R ¹ , R ² , R ³ , A ^1a , A ⁴ , A ⁵ , G ₁ , G ₂ , G ₃ and G ₄ represent the compounds represented by the same meaning as described above).

Furthermore, by reacting the compound represented by the formula (51) with a halogenating agent in accordance with the method described in the step [D] of the manufacturing method 3, the formula (52) (where R ² , R ^3. A ^1a , A ⁴ , A ⁵ , G ₁ , G ₂ , G ₃ , G ₄ and X ₁₀ represent the compounds represented by the same meaning as above).

Next, by reacting the compound represented by the formula (52) and the compound represented by the formula (24) in accordance with the method described in the step [E] of the manufacturing method 3, the compound represented by the formula (1-v) can be prepared The compound.

In addition, the compound represented by the formula (1-v) can be prepared by reacting the compound represented by the formula (52) with the compound represented by the formula (9) in accordance with the method described in the step [E] of the manufacturing method 3. have to.

The compound represented by the formula (50) can be synthesized in accordance with the reaction formula 9 described below, for example.

Some of the compounds represented by the formula (5-a) are well-known compounds, and some of them are available as commercially available products.

Manufacturing method 16

By reacting the compound represented by the formula (50) and the compound represented by the formula (9) in a solvent or without a solvent, if necessary in the presence of a base, the formula (53) can be prepared (where R ^1. R ² , R ³ , A ^1a , A ⁴ and A ⁵ represent the compounds represented by the same meaning as above). In the case of using a solvent, the solvent used may be inert to the reaction, for example, water, methanol, ethanol and other lower alcohols, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane and other aliphatic hydrocarbons, two Halogenated hydrocarbons such as methyl chloride, chloroform, 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, N,N'-dimethylimidazolidone and other amides, dimethyl sulfenite and other arsenites, pyridine, quinoline and other nitrogen-containing aromatic compounds or the like The mixed solvent and so on.

This reaction can be carried out in the presence of a base. As the base that can be used, for example Examples include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-(dimethylamino)pyridine , 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or 1,5-diaza Heterobicyclo[4.3.0]-5-nonane (DBN) and other organic bases, sodium hydroxide, potassium hydroxide, sodium hydride, sodium bicarbonate, potassium carbonate, cesium carbonate and other inorganic bases. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to the compound (50), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

As the equivalent of the substrate, the compound (9) can be used in the range of 0.5 to 50 equivalents relative to the compound (50), preferably in the range of 1 to 20 equivalents.

Secondly, by combining the compound represented by formula (53) and the halogenating agent in a solvent or without solvent, if necessary in the presence of a silylation agent, if necessary in the presence of a base, and if necessary in the presence of an acid By reaction, formula (54) can be obtained (wherein R ¹ , R ² , R ³ , A ^1a , A ⁴ and A ^{5 have the} same meaning as above, and X ₁₃ represents a chlorine atom, a bromine atom or an iodine atom). The compound. When a solvent is used, the solvent used may be inert to the reaction. Examples include fatty acids such as water and acetic acid, lower alcohols such as methanol and ethanol, diethyl ether, tetrahydrofuran, and 1,4 -Dioxane, 1,2-dimethoxyethane and other ethers, benzene, chlorobenzene, bromobenzene, xylene, toluene and other aromatic hydrocarbons, pentane, hexane, cyclohexane, etc. Aliphatic hydrocarbons, dichloromethane, chloroform, 1,2-dichloroethane and other halogenated hydrocarbons, acetonitrile, propionitrile and other nitriles, N,N-dimethylformamide, N,N- Dimethylacetamide, N-methylpyrrolidone, N,N'-dimethylimidazolidinone and other amides, dimethyl sulfinium and other sulfides, pyridine, quinoline and other nitrogen-containing aromatics Group compounds or these mixed solvents, etc.

Examples of the halogenating agent include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethyl Hydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, trimethylphenyltris Ammonium bromide and so on. The equivalent of the halogenating agent can be used in the range of 0.5 to 50 equivalents relative to the compound represented by formula (53), preferably in the range of 1 to 20 equivalents.

The reaction can be carried out in the presence of a silylation agent. Examples of usable silylation agents include trimethylsilyl trifluoromethanesulfonate and the like. As the equivalent of the silylation agent, it can be used in the range of 0.005 to 20 equivalents relative to the compound represented by formula (53), preferably in the range of 0.01 to 5 equivalents.

This reaction can be carried out in the presence of a base. Examples of usable bases include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4-( Dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) Or organic bases such as 1,5-diazabicyclo[4.3.0]-5-nonane (DBN), sodium hydroxide, potassium hydroxide, sodium hydride, Inorganic bases such as sodium bicarbonate, potassium carbonate, cesium carbonate, and potassium phosphate. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to the compound represented by the formula (53), preferably in the range of 1 to 20 equivalents.

This reaction can be carried out in the presence of an acid. Examples of usable acids include hydrobromic acid and hydrogen bromide in acetic acid. The acid equivalent can be used in the range of 0.1 to 100 equivalents relative to the compound represented by formula (53), 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 is preferably a range from 0°C to the reflux temperature of the reaction mixture.

Although the reaction time varies with the concentration of the reaction substrate and the reaction temperature, it can usually be set arbitrarily in the range from 5 minutes to 100 hours, and preferably in the range from 1 hour to 48 hours.

Next, by reacting the compound represented by formula (54) with the compound represented by formula (5-a) in accordance with the method described in Production Method 6, the compound represented by formula (1-v) can be produced.

Manufacturing method 17

Will be represented by the formula (54) compound with the formula (5-b) (wherein, G ₅ and Y6 represent the same meaning as aforementioned) of the compound represented by the reaction in accordance with the method described in the production method 6, A compound represented by formula (1-w) (wherein R ¹ , R ² , R ³ , A ^1a , A ⁴ , A ⁵ , G ₅ and Y6 represent the same meaning as described above) was prepared.

In the reaction of manufacturing method 1 to manufacturing method 17, the reaction mixture after the reaction is directly concentrated and dissolved in an organic solvent, washed with water, concentrated and poured into ice water, and subjected to the usual post-processing such as organic solvent extraction and concentration, etc., to achieve the goal Invention compound. In addition, if necessary, separation and purification can be performed by any purification method such as recrystallization, column chromatography, thin layer chromatography, liquid chromatography fractionation, and the like. Moreover, it is also possible to proceed to the next step without isolation and purification. If necessary, in manufacturing method 1 step [A], manufacturing method 3 step [A], manufacturing method 4 step [A], manufacturing method 5 step [A], and manufacturing method 14 step [A], By carrying out the dehydration condensation reaction in the next step, each step [B] can also be omitted.

Among the compounds represented by formula (3D-a) and formula (3D-b) used in manufacturing method 1, manufacturing method 5, the formula (3D-a1) and formula (3D-b1) where n is an integer of 0 The compound represented and the compound represented by the formula (3D-c) used in the manufacturing method 6, the manufacturing method 10, the formula (3D-c1) where n is an integer of 1 or 2, and the formula (3D-c1) where n is an integer of 0 The compound represented by the formula (3D-c2) can be produced in accordance with the production method described in the following reaction formula 1, for example.

Reaction formula 1

The compound represented by the formula (5-a) can be prepared by reacting with the compound represented by the formula (6) (where Ra represents a C ₁ -C ₆ alkyl group) according to the method described in Manufacturing Method 6 Formula (7-a) (wherein, G ₁ , G ₂ , G ₃ and G ₄ represent the same meaning as described above, and Ra represents a C ₁ -C ₆ alkyl group).

Next, the compound represented by the formula (7-a) is reacted with a halogenating agent in accordance with the method described in the production method 7 to produce the formula (8-a) (where G ₁ , G ₂ , G ₃ and G ₄ represent the same meanings as described above, Ra represents a C ₁ -C ₆ alkyl group, and X ₅ represents a compound represented by a chlorine atom, a bromine atom, or an iodine atom.

Next, the compound represented by formula (8-a) is carried out with the compound represented by formula (9) (in the formula, R ¹ represents the same meaning as described above) by the method described in step [E] of manufacturing method 3 The reaction can produce a compound represented by formula (10-a) (wherein, G ₁ , G ₂ , G ₃ , G ₄ and R ^{1 have the} same meaning as described above, and Ra represents a C ₁ -C ₆ alkyl group).

Secondly, by subjecting the compound represented by the formula (10-a) to a hydrolysis reaction according to a well-known method in the literature, the formula (3D-a1) (where G ₁ , G ₂ , G ₃ , G ₄ and R ¹ represent the compound represented by the same meaning as above).

Secondly, by reacting the compound represented by the formula (3D-a1) with a chlorinating agent according to a well-known method in the literature, the formula (3D-b1) can be prepared (where G ₁ , G ₂ , G _3. G ₄ and R ¹ represent the compound represented by the same meaning as above).

Secondly, by reacting the compound represented by the formula (3D-b1) with the N,O-dimethylhydroxylamine represented by the formula (11) or its hydrochloride in the presence of a base if necessary, A compound represented by formula (12) (wherein G ₁ , G ₂ , G ₃ , G ₄ and R ¹ represent the same meaning as described above) was prepared.

Secondly, by combining the compound represented by formula (12) with the ^{Grignard reactant represented by formula (13) (where R 6} represents the same meaning as described above, and X ₇ represents a chlorine atom, a bromine atom, or an iodine atom) According to the well-known method in the literature, the compound represented by formula (14) (wherein, G ¹ , G ² , G ³ , G ⁴ , R ¹ and R ⁶ represent the same meaning as above) can be prepared.

Next, by reacting the compound represented by the formula (14) with an oxidizing agent in accordance with the method described in the production method 11, the formula (15) can be prepared (where G ₁ , G ₂ , G ₃ , G ₄ , R ¹ , R ⁶ and n'represent the same meaning as the aforementioned compound).

Next, by reacting the compound represented by the formula (15) with a halogenating agent according to the method described in step [B] of the manufacturing method 16, the formula (3D-c1) (where G ₁ , G ₂ , G ₃ , G ₄ , R ¹ , R ⁶ , X ₂ and n'represent the compounds represented by the same meaning as described above).

Furthermore, by reacting the compound represented by the formula (14) with a halogenating agent according to the method described in step [B] of the manufacturing method 16, the formula (3D-c2) (where G ₁ , G ₂ , G ₃ , G ₄ , R ¹ , R ⁶ and X ₂ represent the compounds represented by the above).

Some of the compounds represented by the formula (5-a) are well-known compounds, and some of them are available as commercially available products.

Some of the compounds represented by formula (6) are well-known compounds, and some of them are available as commercially available products.

Some of the compounds represented by the formula (13) are well-known compounds, and some of them are available as commercially available products.

Among the compounds represented by the formula (3D-a) used in the production method 1, the compound represented by the formula (3D-a2) in which n is an integer of 0 can be, for example, in accordance with the production method described in the following reaction formula 2 manufacture.

Reaction formula 2

The compound represented by the formula (5-b) is reacted with the compound represented by the formula (6) in accordance with the method described in the production method 6 to produce the formula (7-b) (where G ₅ , Y6 And Ra represents the compound represented by the same meaning as above).

Next, the compound represented by the formula (7-b) can be prepared by reacting with the halogenating agent according to the method described in the production method 7 to obtain the formula (8-b) (where G ₅ , Y6 and Ra are represented by The same meaning as the foregoing, X ₆ represents a compound represented by a chlorine atom, a bromine atom or an iodine atom).

Next, the compound represented by the formula (8-b) is reacted with the compound represented by the formula (9) according to the method described in the step [E] of the manufacturing method 3 to produce the formula (10-b)( In the formula, G ₅ , Y6, R ¹ and Ra represent the compound represented by the same meaning as above).

Secondly, by subjecting the compound represented by formula (10-b) to a hydrolysis reaction according to well-known methods in the literature, formula (3D-a2) can be prepared (where G ₅ , Y6 and R ¹ represent the same as the aforementioned The same meaning) means the compound.

Some of the compounds represented by the formula (5-b) are well-known compounds, and some of them are available as commercially available products.

The compound represented by the formula (10-a) used in the reaction formula 1 can be produced, for example, in accordance with the production method described in the following reaction formula 3.

Reaction formula 3

The compound represented by the formula (7-a) is reacted with the compound represented by the formula (9) and a halogenating agent according to the method described in the step [C] of the manufacturing method 3 to produce the formula (10-a) ) Represents the compound.

Among the compounds represented by the formula (2Q1-a) used in the production method 1, the compound represented by the formula (2Q1-a-1) can be produced in accordance with the production method described in the following reaction formula 4, for example.

Reaction formula 4

By combining a compound represented by formula (25) (in the formula, R ² , R ³ and A ^{5 have the} same meaning as described above), for example, in accordance with the method described in International Publication No. 2007/093901, and N-bromosuccinate The bromination agent such as imidine reacts to produce a compound represented by formula (26) (wherein, R ² , R ³ and A ^{5 have the} same meaning as described above).

Next, by reacting the compound represented by the formula (26) with the compound represented by the formula (16) in accordance with the method described in the production method 2, the formula (27) can be prepared (where R ² , R ³ , A ^1aa and A ⁵ represent the compounds represented by the same meaning as above).

Secondly, by reacting the compound represented by formula (27) with an aminating agent such as ammonia, ammonia or lithium amide according to the method described in International Publication No. 2012/086848, etc., the formula (2Q1-a-1) (In the formula, R ² , R ³ , A ^1aa and A ⁵ represent the same meanings as described above).

Some of the compounds represented by formula (25) are well-known compounds, and some of them are available as commercially available products.

Among the compounds represented by the formula (2Q2-a) used in the production method 6, the compound represented by the formula (2Q2-a-1) can be produced in accordance with the production method described in the following reaction formula 5, for example.

Reaction formula 5

By formulating a compound represented by formula (28) (wherein R ² and R ³ represent the same meaning as described above, and Rb represents a C ₁ -C ₆ alkyl group), for example, according to [J.Fluorine.Chem.] 1989, Volume 44, 361 pages, [J.Heterocyclic Chem.] 1993, Volume 30, 49 pages, [Synthesis] 2000, page 1078, etc. The method described in formula (29) [where Rc represents C ₁ -C ₆ alkyl group, X ₈ represents a halogen atom, a C ₁ -C ₄ alkyl sulfonate group (such as methanesulfonyloxy group, etc.), a C ₁ -C ₄ haloalkyl sulfonate group (such as trifluoro Methanesulfonyloxy group, etc.) or arylsulfonate group (such as benzenesulfonyloxy group, p-toluenesulfonyloxy group, etc.) and other compounds represented by the reaction, can be prepared Formula (30) (wherein, R ² , R ³ , Rb, and Rc represent the same meaning as described above).

Secondly, by comparing the compound represented by formula (30), for example, according to the method described in [Bioorganic & Med. Chem. Lett.] 2011, volume 21, page 1601, etc., and formula (31) R ⁵ represents the same meaning as above) by reacting the compound represented by formula (32) (wherein, R ² , R ³ and R ⁵ represent the same meaning as above).

Secondly, by combining the compound represented by formula (32), for example, in accordance with the methods described in International Publication No. 2012/061337, International Publication No. 2005/033084, etc., with phosphorous oxychloride, Thionyl chloride (Thionyl chloride) ) Or a chlorinating agent such as ethanedichloride to produce a compound represented by formula (33) (wherein, R ² , R ³ and R ^{5 have the} same meaning as described above).

Secondly, by reacting the compound represented by formula (33) with ammonia water according to the methods described in International Publication No. 2012/061337, International Publication No. 2005/033084, etc., the formula (2Q2-a -1) The compound represented.

Some of the compounds represented by the formula (28) are well-known compounds, and some of them are available as commercially available products.

Some of the compounds represented by formula (29) are well-known compounds, and some of them are available as commercially available products.

Some of the compounds represented by formula (31) are well-known Part of the compound can be obtained as a commercially available product.

The compound represented by the formula (3D-d) used in the production method 8 can be produced in accordance with the production method described in the following reaction formula 6, for example.

Reaction formula 6

By combining the compound represented by the formula (3D-a) with diphenylphosphoryl azide (diphenylphosphoryl azide) ( DPPA) and the compound represented by formula (34) (where Rd represents C ₁ -C ₆ alkyl) can be reacted to produce formula (3D-d-1) (where R ¹ , Rd, D and n represents the compound represented by the same meaning as above).

Next, by reacting the compound represented by the formula (3D-d-1) with an acid according to the methods described in International Publication No. 2012/174312, International Publication No. 2003/018021, etc., the formula (3D-d) represents the compound.

Among the compounds represented by the formula (2Q3-b) used in the production method 9, the compound represented by the formula (2Q3-b-1) can be produced in accordance with the production method described in the following reaction formula 7, for example.

Reaction formula 7

By using the compound represented by formula (35) (wherein R ² , R ³ and R ⁵ represent the same meaning as described above), for example, according to International Publication No. 2013/064460, International Publication No. 2013/064461, etc. The method uses a halogenating agent for halogenation to prepare a compound represented by formula (36) (wherein, R ² , R ³ , R ⁵ and X _{3 have the} same meaning as described above).

Next, by reducing the compound represented by formula (36), for example, in accordance with the methods described in International Publication No. 2013/064460, International Publication No. 2013/064461, etc., the formula (37) can be prepared (where , R ² , R ³ , R ⁵ and X ₃ represent the compound represented by the same meaning as above).

Secondly, by oxidizing the compound represented by formula (37), for example, in accordance with the methods described in International Publication No. 2013/064460, International Publication No. 2013/064461, etc., the formula (2Q3-b-1 ) (In the formula, R ² , R ³ , R ⁵ and X ₃ represent the same meaning as described above).

Some of the compounds represented by the formula (35) are well-known compounds, and some of them are available as commercially available products. Also, other than that, you can also rely on According to the well-known method described in the literature, for example, it is synthesized from the well-known compound in accordance with the reaction conditions described in International Publication No. 2000/039094 and the like.

Among the compounds represented by the formula (3D-e) used in the production method 14, the compound represented by the formula (3D-e1) in which n is an integer of 0 can be, for example, in accordance with the production method described in the following reaction formula 8 manufacture.

Reaction formula 8

By reacting the compound represented by the formula (3D-b1) with ammonia water according to the method described in Japanese Patent Application Publication No. 2009/108046, etc., the formula (3D-e1) (where R ¹ , G ₁ , G ₂ , G ₃ and G ₄ represent the compounds represented by the same meaning as above).

The compound represented by the formula (50) used in the production method 15 and the production method 16 can be produced in accordance with the production method described in the following reaction formula 9, for example.

Reaction formula 9

The compound represented by the formula (2Q1-d) is reacted with the compound represented by the formula (55) according to the method described in the step [A] of the manufacturing method 1 to produce the formula (56) (where R ^2. R ³ , A ^1a , A ⁴ and A ⁵ represent the compounds represented by the same meaning as above).

Next, by deacetylating the compound represented by formula (56), for example, according to the method described in [Synthesis] 1991, page 465, etc., formula (57) (where R ² , R ³ , A ^1a , A ⁴ and A ⁵ represent the compounds represented by the same meaning as above).

Next, by subjecting the compound represented by formula (57) to dehydration and condensation in accordance with the method described in step [B] of manufacturing method 1, formula (58) (wherein, R ² , R ³ , A ^1a, A ⁴ and A ⁵ represents a compound represented by the aforementioned same meaning).

Secondly, by reacting the compound represented by the formula (58) with an oxidizing agent, for example, according to the method described in [J.Med.Chem.] 1998, volume 31, page 545, the formula (59) can be prepared (In the formula, R ² , R ³ , A ^1a , A ⁴ and A ^{5 have the} same meaning as the foregoing).

Next, by combining the compound represented by the formula (59) with the halogenating agent, according to the method described in step [B] of the manufacturing method 16, or for example according to [J.Med.Chem.] 1988, Vol. 31, 656 Page, [J.Med.Chem.] 2005, Volume 48, Page 7658, etc., by reaction, the compound represented by formula (50) can be prepared.

The compound represented by the formula (55) is a well-known compound and can be obtained as a commercially available product. In addition, although the compound represented by the formula (55) has an optically active form due to the presence of one asymmetric carbon, it includes all optically active forms and racemates.

In each of these reactions, after the completion of the reaction, by performing normal post-processing, each production intermediate that becomes the raw material compound of the production method 1 to the production method 17 can be obtained.

Moreover, each manufacturing intermediate produced by this method is not isolated. For purification, you can directly use the reaction in the next step. If necessary, in step [B] of reaction formula 9, step [C] can also be omitted by carrying out the dehydration condensation reaction in the next step.

As the condensed heterocyclic compound represented by formula (1) contained in the present invention which can be produced by the above-mentioned method, the compounds shown in Table 1 to Table 4 below can be cited. However, the compounds shown in the following Tables 1 to 4 are examples, and the compounds included in the present invention are not limited to these.

In the table, the substituent system described as Me represents a methyl group, and in the following, Et represents an ethyl group, ⁿ Pr represents an n-propyl group, and ⁱ Pr represents an isopropyl group.

The so-called pest control agent in the present invention means that it will be used in the field of agriculture and horticulture or livestock production. In the sanitation field (internal parasites of mammals or birds as domestic animals or pet animals, external parasites or sanitary pests for household and business use, unpleasant pests) and other harmful arthropod pest control agents. In addition, the so-called pesticide in the present invention means insecticide in the field of agriculture and horticulture. Acaricides, nematicides, herbicides and fungicides, etc.

As insects, mites, crustaceans, molluscs and nematodes that can be controlled and controlled by the compound of the present invention, specifically, for example, the following can be cited Biology, etc., but the present invention is not limited to these.

Adoxophyes honmai, Adoxophyes orana faciata, Archips breviplicanus, Archips fuscocupreanus, Grapholita molesta, Homona magnanima, Soy Heartworm (Leguminivora glycinivorella), Matsumuraeses phaseoli, Pandemis heparana, Bucculatrix pyrivorella, Lyonetia clerkella, Lyonetia prunifoliella malinella , Caloptilia theivora, Phyllonorycter ringoniella, Phyllocnistis citrella, Acrolepiopsis sapporensis, Acrolepiopsis sapporensis, Acrolepiopsis suzukiella, Plutella xylostella, Persimmon moth (Stathmopoda masinissa), sweet potato wheat moth (Helcystogramma triannulella), cotton pink bollworm (Pectinophora gossypiella), peach fruit moth (Carposina sasakii), codling moth (Cydla pomonella), rice stem borer (Chilo suppressalis) ), Cnaphalocrocis medinalis, Conogethes punctiferalis, Diaphania indica, Etiella zinckenella, Glyphodes pyloalis, Cabbage borer (Hellula undalis), Asian corn borer (Ostrinia furnacalis), purple corn borer (Ostrinia scapulalis), European corn borer (Ostrinia nubilalis), blue grass borer (Parapediasia teterrella), rice butterfly (Parnara guttata), cabbage butterfly (Pieris brassicae, Pieris rapae crucivora, Ascotis selenaria, Pseudoplusia includens, Euproctis pseudoconspersa, Lymantria dispar, Orgyia thyellina, Hyphantria cunea, Lemyra imparilis, Adris tyrannus, Aedia leucomelas, Agrotis ipsilon, Agrotis segetum, Autographa nigrisigna, Ctenoplusia agnata, Helicoverpa armigera, Helicoverpa assulta, Helicoverpa zea, Heliothis virescens ), Mamestra brassicae, Mythimna separata, Naranga aenescens, Spodoptera eridania, Spodoptera exigua, Spodoptera frugiperda , African cotton leaf moth (Spodoptera littoralis), Spodoptera litura, Spodoptera depravata (Spodoptera depravata), Trichoplusia ni, Grape fruit borer (Endopiza viteana), Tomato hawk moth ( Lepidopteran insects such as Manduca quinquemaculata and Manduca sexta.

Flower thrips (Frankliniella intonsa), western flower thrips (Frankliniella occidentalis), greenhouse thrips (Heliothrips haemorrhoidalis), tea yellow thrips (Scirtothrips dorsalis), palm thrips (Thrips palmi), onion thrips (Thrips tabaci), Persimmon Thrips (Ponticulothrips diospyrosi) and other Thysanoptera insects.

Dolycoris baccarum, Eurydema rugosum, Eysarcoris aeneus, Eysarcoris lewisi, Eysarcoris ventralis, Glaucus subpunct Halyomorpha halys, Nezara antennata, Nezara viridula, Piezodorus hybneri, Plautia crossota, Scotinophora lurida, and Scotinophora lurida (Cletus punctiger), Leptocorisa chinensis, Riptortus clavatus, Rhopalus msculatus, Cavelerius saccharivorus, Togo hemipterus, Dysdercus cingulatus, Stephanitis pyrioides, Halticus insularis, Lygus lineolaris, Stenodema sibiricum, Stenotus rubrovittatus, Stenotus rubrovittatus Stink bug (Trigonotylus caelestialium), grape leafhopper (Arboridia apicalis), black-breasted two-chambered leafhopper (Balclutha saltuella), two-pointed large leafhopper (Epiacanthus stramineus), potato small green leafhopper (Empoasca fabae), small green leafhopper (Empoasca nipponica) , Empoasca onukii, Empoasca sakaii, Macrosteles striifrons, Nephotettix cinctinceps, Psuedatomoscelis seriatus, Laodelphax striatellus ( Laodelphax striatella), brown planthopper (Nilaparvata lugens), white-backed planthopper (Sogatella furcifera), orange Diaphorina citri, Psylla pyrisuga, Aleurocanthus spiniferus, Bemisia argentifolii, Bemisia tabaci, Dialeurodes citri, Greenhouse Whitefly (Trialeurodes vaporariorum), grape phylloxera (Viteus vitifolii), cotton aphid (Aphis gossypii), leaf roller aphid (Aphis spiraecola), green peach aphid (Myzus persicae), orange two-pointed aphid (Toxoptera aurantii), grass cover scale (Drosicha corpulenta), Icerya purchasi, Phenacoccus solani, Planococcus citri, Planococcus kuraunhiae, Pseudococcus comstocki, Pseudococcus comstocki Ceroplastes ceriferus, Ceroplastes rubens, Aonidiella aurantii, Comstockaspis perniciosa, Fiorinia theae, Pseudaonidia paeoniae, Mulberry Hemiptera insects such as Pseudaulacaspis pentagona, Pseudaulacaspis prunicola, Unaspis euonymi, Unaspis yanonensis, and Cimex lectularius.

Anomala cuprea, Anomala rufocuprea, Gametis jucunda, Heptophylla picea, Popilia japonica, Lepinotarsa decemlineata), Melanotus fortnumi, Melanotus tamsuyensis, Lasioderma serricorne, Epuraea domina, Epilachna varivestis, Epilachna vigintioctopunctata, Tenebrio molitor, Tribolium castaneum, Anoplophora malasiaca, Monochamus alternatus, Psacothea hilaris , Xylotrechus pyrrhoderus, Callosobruchus chinensis, Aulacophora femoralis, Chaetocnema concinna, Cucumber Beetle (Diabrotica undecimpunctata), Corn Root Firefly (Diabrotica virgifera), Long Diabrotica barberi, Oulema oryzae, Phyllotreta striolata, Psylliodes angusticollis, Rhynchites heros, Cylas formicarius ), Mexican cotton boll weevil (Anthonomus grandis), rice weevil (Echinocnemus squameus), sweet potato weevil (Euscepes postfasciatus), alfalfa weevil (Hypera postica), rice water weevil (Lissohoptrus oryzophilus), black bored weevil Coleopteran insects such as Otiorhynchus sulcatus, Sitophilus granarius, Sitophilus zeamais, Sphenophorus venatus vestitus, Paederus fuscipes, etc.

Soybean gall midge (Asphondylia yushimai), wheat red midge (Sitodiplosis mosellana), melon fruit fly (Bactrocera cucurbitae), orange fruit fly (Bactrocera dorsalis), Mediterranean fruit fly (Ceratitis capitata), rice leaf miner (Hydrellia griseola), Spot-winged fruit fly (Drosophila suzukii), Japanese rice miner (Agromyza oryzae), pea Chromatomyia horticola, Liriomyza bryoniae, Liriomyza chinensis, Liriomyza sativae, Liriomyza trifolii, Liriomyza trifolii, Liriomyza bryoniae (Delia platura), Pegomya cunicularia, Rhagoletis pomonella, Mayetiola destructor, Musca domestica, Sting fly (Stomoxys calcitrans), Melophagus ovinus ), Hypoderma bovis, Hypoderma lineatum, Oestrus ovis, Glossina palpalis (Glossina morsitans), Prosimulium yezoensis, Horsefly (Tabanus trigonus), White spotted moth Gnats (Telmatoscopus albipunctatus), Japanese Culex (Leptoconops nipponensis), Culex pipiens pallens, Aedes aegypti, Aedes albopicutus, Anophelesine hyracanus, etc. Diptera insects.

Apethymus kuri, Athalia rosae, Arge pagana, Neodiprion sertifer, Dryocosmus kuriphilus, Eciton burchelli, Hymenoptera such as Eciton schmitti, Camponotus japonicus, Vespa mandarina, Myrmecia spp., Solenopsis spp., Monomorium pharaonis, etc. insect.

Yellow-brown oil gourd (Teleogryllus emma), oriental mole cricket (Gryllotalpa orientalis), migratory locust (Locusta migratoria), small wings Orthoptera insects such as Oxya yezoensis and Schistocerca gregaria.

Onychiurus folsomi (Onychiurus folsomi), Onychiurus sibiricus, Bourletiella hortensis and other sticky tube insects.

Dictyopteran insects such as Periplaneta fuliginosa, Periplaneta japonica, and Blattella germanica.

Termites such as Coptotermes formosanus, Reticulitermes speratus, and Odontotermes formosanus.

Cat fleas (Ctenocephalidae felis), dog fleas (Ctenocephalides canis), chicken fleas (Echidnophaga gallinacea), itchy fleas (Pulex irritans), rat fleas (Xenopsylla cheopis) and other fleas.

Chicken body lice (Menacanthus stramineus), cattle lice (Bovicola bovis) and other hair-eating insects.

Insects such as Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Solenopotes capillatus, etc.

Dust mites such as Phytonemus pallidus, Polyphagotarsonemus latus and Tarsonemus bilobatus.

Red-headed spider mite (Penthaleus erythrocephalus), Penthaleus major (Penthaleus major) and other walking mites.

Oligonychus shinkajii, Panonychus citri, Panonychus mori, Panonychus ulmi, Tetranychus kanzawai, Tetranychus kanzawai (Tetranychus urticae) and other spider mites.

Aeaphylla theavagrans, Aceria tulipae, Aculops lycopersici, Aculops pelekassi, Aculus schlechtendali, Pseudopear Gall mites such as the rust tick (Eriophyes chibaensis) and the citrus tick (Phyllocoptruta oleivora).

Acaroid mites such as Rhizoglyphus robini, Tyrophagus putrescentiae, and Tyrophagus similis.

Spider mites such as bee crab mites (Varroa jacobsoni).

Boophilus microplus, Rhipicephalus sanguineus, Haemaphysalis longicornis, Haemophysalis flava, Haemophysalis campanulata, Ixodes ovatus), Ixodes persulcatus, Amblyomma spp., Dermacentor spp. and other ticks.

And Red mite (Dermanyssus gallinae), Tropical rat mite (Ornithonyssus bacoti), Northern fowl mite (Ornithonyssus sylviarum), etc. .

Chigger mites (Cheyletiella yasguri), Cheyletiella yasguri (Cheyletiella yasguri) blakei) and other carnivorous mites.

Demodex mites such as Demodex canis and Demodex cati.

Sheep mites such as Psoroptes ovis.

Sarcoptes scabiei, Notoedres cati, Knemidocoptes spp. and other scabies.

Crustaceans such as Armadillidium vulgare.

Pomacea canaliculata, African snail (Achatina fulica), two-line slug (Meghimatium bilineatum), brown beetle slug (Limax Valentiana), Ryukyu snail (Acusta despecta sieboldiana), three-striped snail (Euhadra peliomphala).

Southern root rot nematode (Prathylenchus coffeae), northern root rot nematode (Prathylenchus penetrans), walnut root rot nematode (Prathylenchus vulnus), potato cyst nematode (Globodera rostochiensis), soybean cyst nematode (Heterodera ogyne glycines), northern root rot nematode (Meloidodera ogyne glycines) hapla), Meloidogyne incognita, Aphelenchoides besseyi, Bursaphelenchus xylophilus and other nematodes.

Horned fly or Oriental arm fly (Haematobia irritans), fly or fly (Tabanus spp.), sting fly or Stomoxys calcitrans, gnat or black mosquito (Simulium spp.), blind fly or spot fly (Chrysops spp.) .), tick flies or sheep tick flies (Melophagus ovinus) and tsetse flies or venomous flies (Glossina spp.) and other adult flies.

Goat flies (Oestrus ovis and Cuterebra spp.), blow flies or green flies (Phaenicia spp.), screw flies or new world screw flies (Cochliomyia hominivorax), cattle flies or cow flies (Hypoderma spp.), horses Parasitic fly maggots such as fleeceworm and Gastrophilus.

Mosquitoes such as Culex spp., Anopheles spp. and Aedes spp.

In addition, as internal parasites of domestic animals, poultry, pet animals and the like that can be controlled using the compound of the present invention, specific examples include the following internal parasites, but the present invention is not limited to these.

Haemonchus, Trichostrongylus, Ostertagia, Nematodirus, Cooperia, Ascaris, Ascaris Bunostomun, Oesophagostomum, Chabertia, Trichuris, Stormgylus, Trichonema, Dictyocaulus , Capillaria, Heterakis, Toxocara, Ascaridia, Oxyuris, Ancylostoma, Uncinaria, Nematodes such as Toxascaris and Parascaris.

Silk of Wuchereria, Brugia, Onchoceca, Dirofilaria, Loa, etc. Filariidae line Insects.

Dracunculidae nematodes such as Deacunculus.

Dipylidium caninum, Taenia taeniaeformis, Taenia solium, Taenia saginata, Hymenolepis diminuta, Moniezia Benedeni), Diphyllobothrium latum, Monson's split head (Diphyllobothrium erinacei), Echinococcus granulosus (Echinococcus granulosus), Echinococcus multilocularis, etc.

Liver leeches (Fasciola hepatica, F. gigantica), Paragonimus westermanii (Paragonimus westermanii), Fasciolopsic bruski (Fasciolopsic bruski), Pancreatic fluke (Eurytrema pancreaticum, E. coelomaticum), Liver fluke (Clonorchis) sinensis), Schistosoma japonicum (Schistosoma japonicum), Schistosoma haematobium (Schistosoma haematobium), Schistosoma mansoni (Schistosoma mansoni) and other flukes.

Such as Eimeria tenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima, Nicatex ball Eimeria necatrix, Eimeria bovis, Eimeria ovinoidalis (Eimeria spp.).

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

Furthermore, the compound of the present invention is effective against existing insecticides such as organophosphorus-based compounds, urethane-based compounds, and pyrethrin-based compounds, and is also effective against harmful organisms with developed resistance.

That is, the compound of the present invention is effective against the order of the Mucotubes (Collembola), Dictyoptera (Blachiaria), Orthoptera, Termites, Thysanoptera (Peroptera), Hemiptera (Hemiptera and Homoptera). ), Lepidoptera, Coleoptera, Hymenoptera, Diptera (Flys), Isoptera (Sips), and other insects, mites, gastropods and nematodes and other harmful organisms are effective at low concentrations Prevention.

On the other hand, the compound of the present invention has almost no adverse effects on mammals, fish, crustaceans, and beneficial insects (such as beneficial insects such as bees, bumblebees, or natural enemies of bright bees, oil bees, parasitic curls, agaric bugs, and mites). The impact is extremely useful.

By using the compound of the present invention, it is mixed with a generally appropriate solid carrier or liquid carrier, and further, as desired, surfactant, penetrating agent, spreading agent, viscosity increasing agent, antifreezing agent, binding agent, anti-caking agent, and collapse are added as desired Agents, defoamers, preservatives and anti-decomposition agents, etc., can be practically supplied in liquids (soluble concentrates), emulsions (emulsifiable concentrates), hydrating agents (wettable powder), water solvents (water soluble powder), Water dispersible granule, water soluble granule, suspension concentrate, concentrated emulsion, suspension emulsion, microemulsion, dustable Any dosage form such as powder, granule, tablet and emulsifiable gel. In addition, from the viewpoint of labor saving and safety improvement, it is also possible to provide a water-soluble package such as a water-soluble capsule and a water-soluble film bag enclosed in any of the above-mentioned formulations.

Examples of solid carriers include quartz, calcite, sepiolite, dolomite, chalk, kaolinite, pyrophyllite, sericite, Halloysite, Metahalloysite, Knot clay, and Frog clay. Natural minerals such as, pottery, Zeeklite, volcanic ash, mica, talc, bentonite, activated clay, acid clay, pumice, magnesia bentonite, zeolite and diatomite; burned clay, perlite, volcanic ash hollow Calcined products of natural minerals such as shirasu balloon, vermiculite, attapulgus clay and calcined diatomaceous earth; magnesium carbonate, calcium carbonate, sodium carbonate, sodium bicarbonate, ammonium sulfate, sodium sulfate, Inorganic salts of magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and potassium chloride; sugars such as glucose, fructose, sucrose and lactose; polysaccharides such as starch, powdered cellulose and dextrin; urea, urea derived Organic matter such as benzoic acid and benzoic acid salt; wood flour, cork powder, corn cob, walnut shell and tobacco stems, etc.; fly ash, white carbon (such as hydrated synthetic silica, anhydrous synthetic two Silica and hydrated synthetic silicate, etc.) and fertilizers.

As the liquid carrier, for example, _{aromatic hydrocarbons such as xylene, alkyl (C 9} or C _10, etc.) benzene, phenylxylan ethane, and alkyl (C ₁ or C _3, etc.) naphthalene; motor oil, Aliphatic hydrocarbons such as n-paraffin, isoparaffin and naphthenic hydrocarbons; mixtures of aromatic and aliphatic hydrocarbons such as kerosene; alcohols such as ethanol, isopropanol, cyclohexanol, phenoxyethanol and benzyl alcohol; ethyl Polyols such as glycol, propylene glycol, diethylene glycol, hexylene glycol, polyethylene glycol and polypropylene glycol; propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and propylene glycol monophenyl ether; ketones such as acetophenone, cyclohexanone, γ-butyrolactone, etc.; fatty acid methyl ester, dioxane succinate Esters, dialkyl glutamate, dialkyl adipate and dialkyl phthalate; N-alkyl (C ₁ , C ₈ or C _12, etc.) pyrrolidone and other amides; soybean oil , Linseed oil, rapeseed oil, coconut oil, cottonseed oil, castor oil and other fats; dimethyl sulfide, water, etc.

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

As the surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl (mono or di) phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxyethylene poly Propylene oxide block oligomer, polyoxyethylene fatty acid (mono or di) ester, sorbitol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, castor oil ethylene oxide (Ethylene oxide) adduct, Nonionic interfacial activity of acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylenic alcohol, alkyl glycoside, etc. Agent; Alkyl sulfate, alkylbenzene sulfonate, lignin sulfonate, alkyl sulfosuccinate, naphthalene sulfonate, alkyl naphthalene sulfonate, salt of formaldehyde condensate of naphthalene sulfonic acid , Formaldehyde condensate of alkyl naphthalene sulfonic acid Salt, polyoxyethylene alkyl ether sulfuric acid or phosphate salt, polyoxyethylene (mono or di) alkyl phenyl ether sulfuric acid or phosphate salt, polyoxyethylene (mono, di or tri) styryl phenyl ether Anionic surfactants such as sulfuric acid or phosphate salts, polycarboxylates (such as polyacrylates, polymaleates, and copolymers of maleic acid and olefins, etc.) and polystyrene sulfonates; alkyl amines Cationic surfactants such as salts and alkyl quaternary ammonium salts; amphoteric surfactants of amino acid type and betaine type; silicone-based surfactants and fluorine-based surfactants; etc.

Although the content of these surfactants is not particularly limited, it is usually desired to be in the range of 0.05 to 20 parts by weight relative to 100 parts by weight of the preparation of the present invention. Moreover, these surfactants may be used individually or in combination of 2 or more types.

Although the application amount of the compound of the present invention varies depending on the application scene, application period, application method, cultivated crop, etc., in general, as an effective ingredient amount, about 0.005-50 kg per hectare (ha) is appropriate.

In addition, for the prevention and treatment of external or internal parasites of domestic animals and mammals and birds as pet animals, by using the compound of the present invention, the effective amount of the compound of the present invention can be administered orally together with the additives for preparations; injection; (Intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) and other non-oral administration; dipping, spraying, bathing, washing, pouring-on, spotting-on, dusting, etc. Transdermal administration; nasal administration for administration. The compound of the present invention can be administered by using shaped products such as fine pieces, plates, tapes, colors, earmarks, limbs, and marking devices.

The compound of the present invention can be made into any suitable route of administration by administration Dosage form.

In the case of using the compound of the present invention to repel external or internal parasites, the preferred dosage of the compound of the present invention represented by formula (1) of the active ingredient depends on the type of the parasite to be controlled and the species of the animal to be administered. It may be determined by the method of administration, etc., but it is usually 0.01 to 100 mg/kg, preferably 0.01 to 50 mg/kg, relative to the body weight of the animal to be administered. In particular, the dosage for dogs may vary depending on the type or age of the target dog, or the external parasites to be controlled, and it is usually 1 to 5000 mg/kg per 1 kg of the target dog’s live weight. Preferably it is 1-100 mg/kg.

When the compound of the present invention is administered to eliminate external or internal parasites, although the interval of administration depends on the type of parasite to be controlled, the species of the animal to be administered, or the method of administration, etc., it is usually daily~ The range of once a year is arbitrarily set. It is preferably once a week to once every 6 months, more preferably once a day (24 hours), once a month, once a month, once every two months, or once every three months.

In addition, when the compound of the present invention is used for the control of external parasites in dogs, as the timing of administering the compound of the present invention to dogs, for example, 30 minutes before the start of the bait or 120 minutes after the end of the bait, the timing of administration to the dog For oral administration. In this case, 30 minutes before the start of the food and 120 minutes after the end of the food, the behavior of feeding the dog for the purpose of nutritional intake is used as a standard. For example, when the feeding time for a dog is 20 minutes, the prescribed time is 170 minutes from 30 minutes before the start of the feeding to 120 minutes after the end of the feeding. It is also included in the case where once the food is interrupted in the food, the compound of the present invention is orally administered and then the food is administered. In this specification, the term “bait” refers to the behavior of animals eating bait.

Generally speaking, although the number of times a dog will eat per day varies with breed, age or habits, it is usually 3 to 4 times a day for dogs less than half a year after birth, and dogs less than 1 year after birth. 2 to 3 times a day, for adult dogs between 1 and 5 years old, twice a day, and for older dogs over 6 years old, about 2 to 3 times a day. In the present invention, the so-called bait refers to the feeding behavior for the purpose of taking nutrition, and does not include the behavior of giving the so-called dog training or training to give the bait for the purpose.

The prepared arbitrary dosage forms include solid preparations such as powders, granules, hydration agents, granules, lozenges, colloids, capsules, and shaped products containing active compounds; liquids for injection, liquids for oral administration, etc. Liquid preparations such as liquid preparations used on the skin or in body cavities; solution preparations such as Pour-on agents, Spot-on agents, flow agents, emulsions, etc.; ointments, gels The semi-solid preparation; etc.

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

In addition, as a dosage form for transdermal administration, for example, solid preparations such as powders (Powders); emulsions (Cream), ointments (Salve and Ointment), pastes (Pastes), gels (Gels), etc. Semi-solid preparations; Liquid preparations such as Spray, Aerosols, Solutions and Emulsions, Suspensions, Lotions, etc.; etc.

Furthermore, as a dosage form when the drug is administered by injection, for example, a liquid Liquid preparations such as (Solutions and Emulsions), Suspensions, etc., as dosage forms for nasal administration, for example, liquid preparations such as aerosols (Aerosols), and the like. In addition, as a dosage form for dispersing and processing in the breeding environment of animals such as livestock houses, for example, solid preparations such as Wettable powders, Dusts, Granules, etc.; Emulsions, Flowable Liquid preparations such as Suspension concentrates; etc.

Moreover, the formulations used in the parasite control agent of the present invention are not limited to these formulations.

The solid preparation can be used as direct oral administration, or diluted with water, and dispersed in the feeding environment of animals such as transdermal drug administration and livestock houses.

The solid preparation used for oral administration can be prepared by mixing the compound represented by formula (1) or its salt, with one or more excipients and binding agents suitable for oral administration, and then if necessary Physiologically acceptable additives such as lubricants, disintegrants, dyes, pigments, etc., are prepared in a desired shape.

Excipients and binding agents include, for example, sugars or sugar derivatives such as lactose, sucrose, mannitol, and sorbitol; starches such as corn starch, wheat starch, rice starch, and potato starch; methylcellulose, Cellulose or cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose; proteins or protein derivatives such as zein and gelatin; honey, arabic Paste, polyvinyl alcohol, polyvinylpyrrolidone and other synthetic polymer compounds; etc.

As the lubricant, for example, magnesium stearate and the like can be cited, and as the disintegrant, For example, cellulose, agar, alginic acid, cross-linked polyvinylpyrrolidone (Pyrrolidinone), carbonate, etc. can be mentioned.

Furthermore, among the solid preparations used for oral administration, especially in the case of solid preparations such as chewables, although additives that impart taste, mouthfeel, and flavor to the administered animal can also be used, the parasite of the present invention The carrier and additives used in the solid preparation of the control agent composition are not limited to these.

Liquid preparations can be administered directly transdermally or by injection, or mixed in feed, and can be used as oral administration, diluted with water for transdermal administration, and dispersed in animal breeding environments such as livestock houses.

Liquid for injection can be administered intravenously, intramuscularly and subcutaneously. Liquids for injection are prepared by dissolving the active compound in a suitable solvent, and if necessary, it can be prepared by adding solubilizers, acids, bases, buffer salts, antioxidants, protective agents, and other additives.

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

Examples of the solubilizer include polyvinylpyrrolidone, polyoxyethylated castor oil, polyoxyethylated sorbitol ester, and the like.

As the protective agent, benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid ester, n-butanol, etc. may be mentioned.

Oral liquids can be administered directly or diluted. It can be prepared in the same way as the liquid for injection.

Flow agents, emulsions, etc. can be directly or diluted and administered in transdermal, Or environmental treatment.

The liquid used on the skin can be administered by coating, and the coating is performed by titration, diffusion, imprinting, spraying, spreading, or immersion (dipping, bathing, or washing). These liquids can be prepared in the same way as the liquids for injection.

Pour-on agents and spot-on agents are titrated on the skin at a limited place or sprayed, so that the active compound can be impregnated in the skin to make it act systemically. The titrant and the spot agent can be prepared by dissolving the active ingredient in a suitable skin-compatible solvent or solvent mixture, or suspending or emulsifying it. If necessary, auxiliary agents such as surfactants, colorants, absorption promoting substances, antioxidants, light stabilizers, and adhesives can 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 oils, DMF (N,N-dimethylformamide ), mobile paraffin, light mobile paraffin, silicone, dimethylacetamide, N-methylpyrrolidone or 2,2-dimethyl-4-oxy-methylene-1,3-dioxurea .

Examples of absorption promoting substances include DMSO (dimethyl sulfide), isopropyl myristate, dipropylene glycol pelargonate, silicone oil, fatty esters, triglycerides, or fatty alcohols.

Among the antioxidants, sulfites, metasulfites, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, or vitamin E can be cited.

Emulsions can be administered orally, transdermally, or injected. Emulsion series Dissolve the active ingredients in the hydrophobic phase or the hydrophilic phase. Use appropriate emulsifiers and, if necessary, use coloring agents, absorption promoting substances, protective agents, antioxidants, sunscreens, and viscosity-increasing substances, etc. The auxiliary agent is homogenized with other phase solvents to prepare.

Examples of the hydrophobic phase (oil) include paraffin oil, silicone oil, sesame oil, almond oil, castor oil, synthetic triglycerides, ethyl stearate, di-n-butyryl adipate, and hexamethylene laurate. Ester, dipropylene glycol pelargonate, esters of branched short-chain fatty acids and saturated fatty acids with chain lengths of C16~C18, isopropyl myristate, isopropyl palmitate, and saturated fatty alcohols with chain lengths of C12~C18 Caprylic acid/capric acid ester, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid ester, dibutyl phthalate, diiso adipate Propyl ester, isotridecanol, 2-octyldodecanol, cetearyl alcohol, oleyl alcohol, etc.

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

Examples of emulsifiers include polyoxyethylated castor oil, polyoxyethylated monoolefin sorbitol, sorbitol monostearate, glycerol monostearate, and polyoxyethylene stearate. Nonionic surfactants such as esters, alkylphenol polyglycol ethers, etc.; Amphoteric surfactants such as disodium N-lauryl-β-iminodipropionate, lecithin, etc.; Sodium lauryl sulfate, fatty alcohol Anionic surfactants such as sulfuric acid ether, monoethanolamine salt of mono/dialkyl polyglycol orthophosphate, etc.; cationic surfactants such as cetyltrimethylammonium chloride, etc.

As other auxiliary agents, carboxymethyl cellulose and methyl cellulose can be cited Vegetarian, polyacrylate, alginate, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, methyl vinyl ether, copolymer of maleic anhydride, polyethylene glycol, wax, colloidal silica, etc.

The semi-solid preparation can be administered by spreading it on the skin, or spreading it, or introducing it into a body cavity. Gel is a solution prepared as described above for injection liquid. In order to produce a transparent substance with ointment-like viscosity, it can be prepared by adding sufficient thickener.

Next, examples of formulations when using the compound of the present invention are shown. However, the cooperation examples of the present invention are not limited to these. In addition, the "parts" in the following compounding examples refer to parts by weight.

[Hydrating Agent]

As others, for example, an anti-caking agent, an anti-decomposition agent, etc. can be cited.

[Emulsion]

As other examples, a spreading agent, an anti-decomposition agent, etc. can be cited.

[Suspending agent]

As other examples, antifreeze agents, thickeners, and the like can be cited.

[Particle hydrating agent]

As others, for example, a binding agent, an anti-decomposition agent, etc. can be cited.

[Liquid]

As other examples, an antifreeze agent, a spreading agent, etc. can be cited.

[Granules]

Other 0~10 copies

As others, for example, a binding agent, an anti-decomposition agent, etc. can be cited.

[powder]

Other examples include anti-drift agents, anti-decomposition agents, and the like.

Next, although an example of a preparation using the compound of the present invention as an active ingredient is shown more specifically, the present invention is not limited to these.

In addition, in the following mixing examples, "parts" means parts by weight.

[Combination example 1] Hydrating agent

(Trade name, mixture of nonionic surfactant and anionic surfactant: manufactured by Toho Chemical Industry Co., Ltd.).

CARPLEX#80D 2 copies

(Trade name, synthetic hydrous silicic acid: manufactured by Shiono Yoshihide Pharmaceutical Co., Ltd.).

The above is uniformly mixed and pulverized to become a hydrating agent.

[Combination example 2] Emulsion

5 parts of Compound No.1-1-001a of the present invention

(Trade name, mixture of nonionic surfactant and anionic surfactant: manufactured by Toho Chemical Industry Co., Ltd.).

The above is uniformly mixed to form an emulsion.

[Combination example 3] Suspending agent

After the above is uniformly mixed, wet pulverization is performed to form a suspension.

[Combination example 4] Granular hydrating agent

(Trade name, anionic surfactant: manufactured by Nippon Paper Co., Ltd.).

CARPLEX#80D 10 copies

(Trade name, synthetic hydrous silicic acid: manufactured by Shiono Yoshihide Pharmaceutical Co., Ltd.).

After the above is uniformly mixed and pulverized, a small amount of water is added for stirring and mixing, and granulated by an extrusion granulator, and dried to become a granular hydrating agent.

[Combination Example 5] Granules

After the above is uniformly mixed and pulverized, a small amount of water is added, stirred and mixed, and granulated by an extrusion granulator, and dried to form granules.

[Combination example 6] Powder

The above is uniformly mixed and pulverized to become a powder.

When in use, the above formulation is diluted with water to 1 to 10000 times, or directly dispersed without dilution.

[Combination example 7] Hydrating agent preparation

[Combination example 8] Water-soluble thickener preparation

[Combination example 9] Liquid for spray

[Combination example 10] Liquid for transdermal administration

[Combination example 11] Liquid for transdermal administration

[Combination example 12] Liquid for transdermal administration (titration)

[Combination example 13] Liquid for transdermal administration (titration)

In addition, when the compound of the present invention is used as a pesticide, if necessary, it can be combined with other herbicides, various insecticides, acaricides, nematicides, fungicides, plant growth regulators, synergists, fertilizers, and soil. When a modifier or the like is mixed and applied to the formulation or when it is dispersed.

Especially by mixing with other pesticides or plant hormones, it can be It is expected that the reduction in the amount of pesticides will reduce the cost of prevention and control, and the synergistic effect of the mixture will expand the insecticidal spectrum or have a higher pest control effect. In this case, it may also be a combination with plural well-known pesticides at the same time.

As the types of pesticides to be mixed with the compound of the present invention, for example, compounds described in (The Pesticide Manual) 15th edition, 2009, and the like can be cited. Specifically, the general name is as described below if it is exemplified, but it is not limited to these.

Fungicides: acibenzolar-S-methyl, acylaminobenzamide, acypetacs, aldimorph, ametoctradin, aminopyrifen, Amisulbrom, amobam, ampropyfos, anilazine, azaconazole, azithiram, azoxystrobin ), barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, benzoxyl Bentaluron, Benthiavalicarb-isopropyl, Benthiazole, Benzamacril, Benzafur, Benzovindiflupyr, Bethoxazine ), binapacryl, biphenyl, bitertanol, blasticidin-S, bixafen, bordeaux mixture, white gram Boscalid, bromuconazole, bupirimate, buthiobate, lime sulfur mixture (calcium polysulfide, calcium polysulfide, captafol, captan, carpropamid, carbamorph, carbendazim, rustling (carboxin), carvone, cheshunt mixture, chinomethionat, chlobenthiazone, chloraniformethane, chloranil , Chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlozolinate, climbazole ), fluconazole (clotrimazole), copper acetate (copper acetate), basic copper carbonate (basic), copper hydroxide (copper hydroxide), copper naphthenate (copper naphthenate), copper oleate (copper oleate) ), copper oxychloride (copper oxychloride), copper sulfate (copper sulfate), alkaline copper sulfate (basic), copper zinc chromate (copper zinc chromate), zinc manganese (cufraneb), syringomycin ( coumoxystrobin, cuprobam, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cyazofamid (cypendazole), cyproconazol, cyprodinil, cyprofuram, dazomet, debacarb, decafentin, dehydroacetic acid acid), dichlobentiazox, dichlofluanid, dichloronaphthoquinone (dichlone), dichlorophen, dichlozoline, diclobutrazol, diclobutrazol, diclocymet, diclomedine, dicloran, etc. .

Fungicides (following): diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, dinazole Alcohol (diniconazole), Dakley (diniconazole-M), dinobuton, dinocap, dinocap-4, dinocap-6, ortho Dinocton, dithiopine (dinosulfon), nitrobutyl ester (dinoterbon), diphenylamine (diphenylamine), dipymetitrone (dipymetitrone), dipyrithione (dipyrithione), prednisone ( ditalimfos), dithianon, dodemorph-acetate, dodine, drazoxolon, edifenphos, enestrobin, Enoxastrobin, epoxiconazole, etaconazole, ethaboxam, etem, ethirimol, ethoxyquin ), etridiazole, famoxadone, fenarimol, fenbuconazole, fenamidone, fenaminosulf, fenoxadone ( fenaminstrobin, fenapanil, fendazosulam, fenfuram, fenhexamid, fenitropan, Fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpyrazamine, fenpropimorph, fentin, thiram ferbam), ferimzone, fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, flumetover, flumorph, fluorine Fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole ), flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, folpet fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cis , Furmecyclox, furphanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, Fickley ( hexaconazole, hexylthiofos, 8-hydroxyquinoline sulfate, hymexazol, imazalil, imibenconazole, biguanidine octamine benzenesulfon (Iminoctadine-albesilate), iminoctadine-triacetate, inpyrfluxam, ipconazole, Ipfentrifluconazole, iprobenfos, Epton (iprodione), iprovalicarb, isofetamid, isoflucypram, isoprothiolane, isopyrazam, isotianil, isovaglitadione (isovaledione) and so on.

Fungicide (following): kasugamycin, kresoxim-methyl, laminarin, mancopper, mancozeb, mandestrobin ), mandipropamid, maneb, mebenil, mecarbinzid, mefentrifluconazole, mepanipyrim, meptyldinocap, mepronil ), metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, furfur Methfuroxam, methyl isothiocyanate, metiram, metominostrobin, metrafenone, metsulfovax, metiram milneb), myclobutanil, myclozolin, nabam, natamycin, nickel bis(dimethyl dithiocarbamate) (nickel bis( dimethyldithiocarbamate), nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, orysastrobin ), oxathiapiprolin, oxadixyl, oxine copper), oxycarboxin, oxpoconazole fumarate, pefurzoate, penconazole, penflufen, pencycuron, picroc Penthiopyrad, o-phenylphenol, phosdiphen, phthalide, picarbutrazox, picoxystrobin, piperazine Piperalin, polycarbamate, polyoxins, polyoxorim, potassium azide, potassium hydrogen carbonate, Proquinazid, probenazole, prochloraz, procymidone, propamocarb hydrochloride, propiconazole, propineb, amine Prothiocarb, prothioconazole, pydiflumetofen, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyraziflumid, pyrazophos ), pyribencarb-methyl, pyridinitril, pyrifenox, pyrimethanil, pyriminostrobin, pyrimorph, Pyriofenone, pyrisoxazole, pyroquilon, pyroxychlor, pyroxyfur, quinomethionate, quinofumelin, quinofin (quinoxyfen), quintozene, quinolone. sulfuric acid Salt (quinacetol-sulfate), quinone hydrazone (quinazamid), quinconazole, rabenzazole and Bacillus subtilis (Strain: D747, FZB24, GBO3, HAI0404, MBI600, QST713, Y1336, etc.), etc. .

Fungicides (following): Syngenta (sedaxane), sodium azide, sodium hydrogen carbonate, sodium hypochlorite, sulfur, spirodiclofen (spiroxamine), salicylanilide, silthiofam, simeconazole, tebuconazole, tebufloquin, tecnazene , Tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiochlorfenphim ), thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid , Tolclofos-methyl, tolprocarb, tolylfluanid, triadimefon, toriadimenol, triamiphos, azoxystrobin (triarimol), triazoxide, triazbutil, tributyltin oxide, tricholamide, tricyclazole, triidemorph, Trifloxystrobin, triflumizole, triforine, triclopyricarb, tricloconazole (triticonazole), validamycin, valifenalate, vinclozolin, zarilamide, zinc sulfate, zinc sulfate, zineb, ziram, zoxanil (zoxamide), mushroom mycelium extract, mushroom fruit body extract, ZF-9646 (test name), NF-180 (test name), MIF-1002 (test name), S-2399 (test name), AKD -5195 (test name) and NNF-0721 (test name), etc.

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

Nematicides: aldoxycarb, benclothiaz, cadusafos, DBCP, dichlofenthion, DSP, ethoprophos, fenamiphos, Fensulfothion, fluazaindolizine, fluensulfone, fosthiazate, fosthietan, imicyafos, isamidofos , Isazofos, oxamyl, thiaxazafen, thionazin, tioxazafen, BYI-1921 (test name) and MAI-08015 (test name), etc.

Acaricides: acequinocyl, acrinathrin, acynonapyr, amidoflumet, amitraz, azocyclotin, BCI-033 (test name), cylonac (benzoximate), bifenazate, bromopropylate, chinomethionat, chlorobezilate, clofentezine, cyenopyrafen, bromopropylate cyflumetofen, cyhexatine, dicofol, dienochlor, diflovidazin, DNOC, etoxazole, fenazaquin, fenbu Fenbutatin oxide, fenothiocarb, fenpropathrin, fenpyroximate, fluacrypyrim, halfenprox, hexythiazox, milmectin (milbemectin), propargite, pyflubumide, pyridaben, pyrimidifen, S-1870 (test name), spirodiclofen, snail Spyromesifen, CL900167 (test name), tebufenpyrad, NA-89 (test name), etc.

Insecticides: abamectin, acephate, acetamipirid, afidopyropen, afoxolaner, alanycarb, aldione Aldicarb, allethrin, azamethiphos, azinphos-ethyl, azinphos-methyl, bacillus thuringiensis, immune Bendiocarb, benfluthrin, benfuracarb, bensultap, benzpyrimoxan, bifenthrin, bioallethrin, bioresmethrin, double triple Flufenoxuron (bistrifluron), broflanilide, buprofezin, butocarboxim, carbaryl, carbofuran, carbosulfan, cartap ), chlorantraniliprole, chlorethxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, dextro-trans-chloropropane Chloroprallethrin, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyanophos, cyantraniliprole, Cyclaniliprole, cycloprothrin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalodiamide, chlorofluorocyanate Cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, ζ-cypermethrin ( zeta-cypermethrin), cyphenothrin, cyromazine, deltamethrin, diacloden, diafenthiuron, diazinon, diazinon ( dicloromezotiaz), dichlorvos, diflubenzuron, dimefluthrin, dimethylvinphos, dinotefuran, diofenolan, Disulfoton, dimethoate, emamectin-benzoate, empenthrin, anxa Endosulfan, alpha-endosulfan, pine pine (EPN), esfenvalerate, ethiofencarb, ethiprole, etofenprox, Etrimfos, fenitrothion, fenobucarb, fenoxycarb, fenpropathrin, fenthion, fenvalerate, Fipronil, flonicamid, fluazuron, flubendiamide, flucycloxuron, flucythrinate, flufenerim, flufenerim Flufenoxuron, flufenprox, flumethrin, fluralaner, fluvalinate, tau-fluvalinate, dafuse (fonophos), formetanate, formothion, furathiocarb, flufiprole, fluhexafon, flupyradifurone, flometoquin Wait.

Insecticides (following): gamma-cyhalothrin, halofenozide, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid ), improthrin, isofenphos, indoxacarb, indoxacarb-MP, isoprocarb, isoxathion, κ-bifenin ( kappa-bifenthrin), kappa-tefluthrin, lepimectin, lufenlong (lufenuron), marathon (malathion), meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methacrifos ), metalearb, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, ε-mei Epsilon-metofluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, monocrotophos, muscalure , Nitenpyram, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxamyl oxydeprofos), parathion, parathion-methyl, pentachlorophenol (PCP), permethrin, phenothrin, cedarsone ( phenthoate, phoxim, phorate, phosalone, phosmet, phosphamidon, pirimicarb, pirimiphos- methyl), profenofos, profluthrin, prothiofos, propaphos, protrifenbute, pymetrozine, pyraclofos , Pyrethrins, pyridalyl, pyrifluquinazon, pyriprole, pyriprole (pyrafluprole), pyriproxyfen, resmethrin, rotenone, SI-0405 (test name), sulprofos, silafluofen, Schonote spinetoram, spinosad, spiromesifen, spirotetramat, sulfoxaflor, sulfotep, SYJ-159 (test name), defenno (tebfenozide), teflubenzuron, tefluthorin, terbufos, tetrachlorvinphos, tetramethrin, d-tetramethrin, tetrafluoro Tetramethylfluthrin, tetraniliprole, thiacloprid, thiocyclam, thiodicarb, thiamethoxam, thiofanox, thiofanox Thiometon, tolfenpyrad, trolomethrin, transfluthrin, triazamate, trichlorfon, triazuron, triflumezopyrim ), triflumuron, vamidothion, fluxametamide, MIE-1209 (test name), ME5382 (test name), etc.

[Example]

In the following, the synthesis examples and test examples of the compounds of the present invention are described as examples. Although the present invention is further described in detail, the present invention is not limited by these.

The medium-pressure fractionation liquid chromatography described in the synthesis and reference examples uses a medium-pressure fractionation device from Shanshan Co., Ltd.; YFLC-Wprep (a column with a flow rate of 18 ml/min and a silica gel of 40 μm).

In addition, the chemical shift value of proton nuclear magnetic resonance (NMR) in the synthesis example and the reference example was measured at 300 MHz (model: ECX300 or ECP300, manufactured by JEOL) _{using Me 4 Si (tetramethylsilane) as a reference material.}

The symbols in the proton nuclear magnetic resonance chemical shift values indicate the following meanings.

s: singlet, brs: wide singlet, d: doublet, dd: doublet, t: triplet, q: quartet, m: multiplet

In addition, the name of the solvent used in the NMR measurement is in the data of the chemical shift value, which is indicated in parentheses.

Synthesis Example 1: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-7-(trifluoromethyl)imidazole Synthesis of and [1,2-c]pyrimidine (Compound No.1-3-001a of the present invention)

Dissolve 82 mg of 6-(trifluoromethyl)pyrimidin-4-amine in 5 ml of chlorobenzene, and add 2-bromo-1-[3-(ethylsulfonyl)-7-(trifluoromethyl) at room temperature Imidazo[1,2-a]pyridin-2-yl]ethanone 200mg. After the addition, the reaction mixture was stirred under heating and reflux for 9 hours. After the completion of the reaction, 10 ml of 1M sodium hydroxide aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The residue obtained was purified by dissolution medium pressure fractional liquid chromatography in n-hexane-ethyl acetate [100:0~0:100 (the same as the volume ratio) gradient], and a flesh-colored solid was obtained. The target compound is 163.5 mg.

Melting point: 235-237°C

¹ H-NMR(CDCl ₃ ): δ9.38(d,J=7.5Hz,1H),9.19(s,1H),8.63(s,1H),8.12-8.09(m,1H),8.02-8.00( m,1H), 7.28-7.23(m,1H), 3.73(q,J=7.4Hz,2H), 1.34(t,J=7.4Hz,3H).

Synthesis Example 2: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl) Group)-3H-imidazo[4,5-b]pyridine (compound No.1-1-002b of the present invention) and 2-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazole And [1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (the compound No.1-1 of the present invention -002a) synthesis

Step 1: 3-(Ethylthio)-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-7-(trifluoromethyl)imidazo[1 Synthesis of ,2-a]pyridine-2-carboxyamide

Dissolve 856 mg of N ² -methyl-5-(trifluoromethyl)pyridine-2,3-diamine in 20 ml of pyridine, and add 3-(ethylthio)-7-(trifluoromethyl)imidazole at room temperature And [1,2-a]pyridine-2-carboxylic acid 1.00g, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 1.32g and 4-(two Methylamino)pyridine 42mg. After the addition was complete, the reaction mixture was stirred at room temperature for 6 hours. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The resulting organic layer was washed with 1M hydrochloric acid aqueous solution, and then dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain a crude product of 1.40 g of the target product. This material can be used directly in the next step without further purification.

Step 2: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine Synthesis of pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-002b of the present invention)

The crude product obtained in step 1 is 3-(ethylthio)-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-7-(trifluoro 1.40 g of methyl)imidazo[1,2-a]pyridine-2-carboxyamide was dissolved in 15 ml of acetic acid, and the mixture was stirred under heating and reflux for 2 hours. After the stirring, the reaction mixture was stirred at room temperature overnight. After the stirring, the precipitated solid in the reaction mixture was filtered off. The obtained solid was washed with diisopropyl ether to obtain 645 mg of the target white solid.

Melting point: 199-202°C

¹ H-NMR(CDCl ₃ ): δ8.78(d,J=7.2Hz,1H), 8.73(d,J=1.5Hz,1H), 8.40(d,J=2.0Hz,1H), 8.06-8.04 (m,1H),7.21(dd,J=7.2,1.5Hz,1H),4.33(s,3H),3.15(q,J=7.4Hz,2H),1.22(t,J=7.4Hz,3H) .

Step 3: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl) Synthesis of (methyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-002a of the present invention)

To 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)- To a solution of 645 mg of 3H-imidazo[4,5-b]pyridine in 15 ml of chloroform, 961 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 2.5 hours. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. Dry After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 660 mg of the target white solid.

Melting point: 203-205°C

¹ H-NMR(CDCl ₃ ): δ9.42(d,J=7.5Hz,1H), 8.77(s,1H), 8.36(d,J=1.7Hz,1H), 8.16(s,1H), 7.32 (dd,J=7.5,1.7Hz,1H), 4.18(s,3H), 4.11(q,J=7.5Hz,2H), 1.47(t,J=7.5Hz,3H).

Synthesis Example 3: 2-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-[(trifluoromethyl)sulfur] Benzo[d]oxazole (compound No.1-2-003b of the present invention), 2-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a] Pyridin-2-yl]-5-[(trifluoromethyl)sulfinyl]benzo[d]oxazole (compound No.1-2-002a of the present invention) and 2-[3-(ethylsulfonyl) (Trifluoromethyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-[(trifluoromethyl)sulfonyl]benzo[d]oxazole (this Synthesis of Invention Compound No.1-2-001a)

Step 1: 3-(Ethylthio)-N-{2-hydroxy-5-[(trifluoromethyl)thio]phenyl}-6-(trifluoromethyl)imidazo[1,2-a] Synthesis of Pyridine-2-Carboxamide

Dissolve 466 mg of 2-amino-4-[(trifluoromethyl)thio]phenol in 10ml of pyridine, and add 3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2 -a) 356 mg of pyridine-2-carboxylic acid, 471 mg of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and 75 mg of 4-(dimethylamino)pyridine . After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the reaction, the solvent was distilled off under reduced pressure. The obtained residue was purified by liquid chromatography with medium pressure fractionation in n-hexane-ethyl acetate (gradient from 100:0 to 0:100). Then, 100 mg of the target substance was obtained as a black tea-colored solid.

Step 2: 2-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-[(trifluoromethyl)thio]benzene Synthesis of and [d]oxazole (Compound No.1-2-003b of the present invention)

Add 3-(ethylthio)-N-{2-hydroxy-5-[(trifluoromethyl)sulfur]phenyl}-6-(trifluoromethyl)imidazo[1,2-a]pyridine- A solution of 89 mg of 2-carboxyamide in 5 ml of tetrahydrofuran was heated to 50°C, and 65 mg of azodicarboxylic acid bis(2-methoxyethyl) and 73 mg of triphenylphosphine were added.

After the addition, the reaction mixture was stirred at 50°C for 3 hours. After the stirring, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and extraction was carried out with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 85:15 to 0:100) by medium pressure fractionation liquid chromatography to obtain 21 mg of the target product as a light brown solid.

¹ H-NMR(CDCl ₃ ): δ8.96(s,1H), 8.23(s,1H), 8.00-7.45(m,4H), 3.11(q,J=7.4Hz,2H), 1.26(t, J=7.4Hz, 3H).

Step 3: 2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-[(trifluoromethyl)ylidene Sulfonyl]benzo[d]oxazole (compound No.1-2-002a of the present invention) and 2-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazo[1, Synthesis of 2-a]pyridin-2-yl]-5-[(trifluoromethyl)sulfonyl]benzo[d]oxazole (compound No.1-2-001a of the present invention)

In 2-[3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2- A solution of 21 mg of chloroform in 5 ml of chloroform]-5-[(trifluoromethyl)sulfur]benzo[d]oxazole, 67 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) is added at room temperature . After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the stirring, the reaction mixture was stirred under heating and refluxing for 2 hours. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The residue obtained was purified in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) by medium pressure fractionation liquid chromatography to obtain the target 2-[ 3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-[(trifluoromethyl)sulfinyl]benzo [d] Oxazole 5mg and the target 2-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-[ (Trifluoromethyl)sulfonyl]benzo[d]oxazole 13mg.

2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-[(trifluoromethyl)sulfinyl ]Benzo[d]oxazole ¹ H-NMR(CDCl ₃ ): δ9.75(s,1H),8.37(s,1H),8.05-7.35(m,4H),4.09(q,J=7.5 Hz, 2H), 1.48 (t, J=7.5 Hz, 3H).

2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-[(trifluoromethyl)sulfonyl] ¹ H-NMR (CDCl ₃ ) of benzo[d]oxazole: δ9.74(s,1H),8.62(s,1H),8.25-7.40(m,4H),4.07(q,J=7.5Hz) ,2H), 1.50(t,J=7.5Hz,3H).

Synthesis Example 4: 5-(Ethylthio)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2-( Trifluoromethyl)imidazo[2,1-b]thiazole (this Invention compound No.2-1-001b) and 5-(ethylsulfonyl)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine Synthesis of -2-yl]-2-(trifluoromethyl)imidazo[2,1-b]thiazole (compound No.2-1-001a of the present invention)

Step 1: 5-(Ethylthio)-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-2-(trifluoromethyl)imidazo[2 ,1-b] Synthesis of thiazole-6-carboxyamide

Dissolve 242 mg of N ² -methyl-5-(trifluoromethyl)pyridine-2,3-diamine in 10 ml of pyridine, and add 5-(ethylthio)-2-(trifluoromethyl)imidazole at room temperature And [2,1-b]thiazole-6-carboxylic acid 250mg, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 322mg and 4-(dimethylaminopropyl) Amino) pyridine 10 mg. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The obtained organic layer was washed with 1M hydrochloric acid aqueous solution, and then dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain the desired 5-(ethylthio)-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl] A crude product of -2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxyamide. This material can be used directly in the next step without further purification.

Step 2: 5-(Ethylthio)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2-(three Synthesis of fluoromethyl)imidazo[2,1-b]thiazole (compound No.2-1-001b of the present invention)

The crude product obtained in step 1 is 5-(ethylthio)-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-2-(trifluoro (Methyl)imidazo[2,1-b]thiazole-6-carboxyamide was dissolved in 10ml of acetic acid and stirred for 4.5 hours under heating under reflux Time. After the reaction, the solvent was distilled off under reduced pressure. 10ml of 1M hydrochloric acid aqueous solution was added to the obtained residue, and the mixture was extracted with ethyl acetate (10ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The precipitated solids are separated by filtration. The obtained solid was washed with diisopropyl ether to obtain 332 mg of the target white solid.

Melting point: 200-203°C

¹ H-NMR(CDCl ₃ ): δ8.72-8.67(m,1H), 8.37-8.33(m,1H), 8.12-8.08(m,1H), 4.25(s,3H), 3.14(q,J =7.5Hz,2H),1.25(t,J=7.5Hz,3H).

Step 3: 5-(Ethylsulfonyl)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2- Synthesis of (trifluoromethyl)imidazo[2,1-b]thiazole (compound No.2-1-001a of the present invention)

In 5-(ethylthio)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2-(trifluoromethyl Base) imidazo[2,1-b]thiazole 132 mg of chloroform solution in 3 ml, 155 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 1.5 hours. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 110 mg of the target white solid.

Melting point: 249-251°C

¹ H-NMR (CDCl ₃ ): δ8.76-8.71 (m, 1H), 8.71-8.66 (m, 1H), 8.36-8.32 (m, 1H), 4.23 (s, 3H), 4.19 (q, J =7.5Hz,2H),1.45(t,J=7.5Hz,3H).

Synthesis Example 5: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-7-(trifluoromethyl)imidazole Synthesis of and [1,2-b]pyridazine (Compound No.1-4-001a of the present invention)

Dissolve 82 mg of 5-(trifluoromethyl)pyridazine-3-amine in 5 ml of chlorobenzene, and add 2-bromo-1-[3-(ethylsulfonyl)-7-(trifluoromethyl) at room temperature. ) Imidazo[1,2-a]pyridin-2-yl]ethanone 200mg. After the addition, the reaction mixture was stirred under heating and reflux for 3 hours. After the completion of the reaction, 10 ml of 1M sodium hydroxide aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) by medium pressure fractionation liquid chromatography to obtain 142 mg of the target brown solid.

Melting point: 214-218°C

¹ H-NMR(CDCl ₃ ): δ9.40(d,J=7.5Hz,1H), 8.94(s,1H), 8.58(d,J=2.0Hz,1H), 8.34-8.30(m,1H) ,8.11-8.09(m,1H), 7.24(dd,J=7.5,2.0Hz,1H), 3.79(q,J=7.4Hz,2H), 1.36(t,J=7.4Hz,3H).

Synthesis Example 6: 2-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyrazin-2-yl]-3-methyl-6-(trifluoro Methyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-029b of the present invention) and 2-[3-(ethylsulfonyl)-6-(trifluoromethyl) Imidazo[1,2-a]pyrazin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazole Synthesis of and [4,5-b]pyridine (Compound No.1-1-029a of the present invention)

Step 1: 3-(Ethylthio)-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-6-(trifluoromethyl)imidazo[1 ,2-a]Pyrazine-2-Carboxamide Synthesis

Dissolve 271 mg of N ² -methyl-5-(trifluoromethyl)pyridine-2,3-diamine in 10 ml of pyridine, and add 3-(ethylthio)-6-(trifluoromethyl)imidazole at room temperature And [1,2-a]pyrazine-2-carboxylic acid 270mg and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 357mg. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 3-(ethylthio)-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-6- (Trifluoromethyl)imidazo[1,2-a]pyrazine-2-carboxamide crude product. This material can be used directly in the next step without further purification.

Step 2: 2-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyrazin-2-yl]-3-methyl-6-(trifluoromethyl) Yl)-3H-imidazo[4,5-b]pyridine (Compound No.1-1-029b of the present invention)

The crude product obtained in step 1 is 3-(ethylthio)-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-6-(trifluoro (Methyl)imidazo[1,2-a]pyrazine-2-carboxyamide was dissolved in 10 ml of acetic acid, and stirred under heating and reflux for 17 hours. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, The solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 80:20) to obtain 257 mg of the target white solid.

Melting point: 220-222°C

¹ H-NMR(CDCl ₃ ): δ9.24(s,1H), 8.99(s,1H), 8.76(d,J=1.5Hz,1H), 8.42(d,J=1.5Hz,1H), 4.37 (s,3H), 3.26(q,J=7.5Hz,2H),1.25(t,J=7.5Hz,3H).

Step 3: 2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyrazin-2-yl]-3-methyl-6-(trifluoromethyl) Synthesis of fluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-029a of the present invention)

To 2-[3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyrazin-2-yl]-3-methyl-6-(trifluoromethyl) -3H-imidazo[4,5-b]pyridine 232mg chloroform 5ml solution, 65% by mass of m-chloroperbenzoic acid (containing about 30% by mass of water) 326mg was added under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. By adding 10 ml of diisopropyl ether to the obtained solid and filtering, 203 mg of the target white solid was obtained.

Melting point: 234-236°C

¹ H-NMR (CDCl ₃ ): δ 9.63 (s, 1H), 9.39 (s, 1H), 8.81-8.77 (m, 1H), 8.39-8.36 (m, 1H), 4.25 (s, 3H), 4.23(q,J=7.5Hz,2H), 1.49(t,J=7.5Hz,3H).

Synthesis Example 7: 2-[6-Bromo-3-(ethylthio)-7-(trifluoromethyl)imidazo [1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (the present compound No.1-1- 023b) and 2-[6-bromo-3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)-3-methyl-6 Synthesis of -(Trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No.1-1-023a of the present invention)

Step 1: 6-Bromo-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-7-(trifluoromethyl)imidazo[1,2-a ] Synthesis of pyridine-2-carboxamide

Dissolve 1.51 g of N ² -methyl-5-(trifluoromethyl)pyridine-2,3-diamine in 20 ml of pyridine, and add 6-bromo-7-(trifluoromethyl)imidazo[1 ,2-a]pyridine-2-carboxylic acid 2.04g and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 2.53g. After the addition was complete, the reaction mixture was stirred at room temperature for 3 hours. After the completion of the reaction, 20 ml of water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain 2.98 g of the target substance as a flesh-colored solid.

Melting point: 200-205°C

¹ H-NMR (CDCl ₃ ): δ8.77 (brs, 1H), 8.54 (s, 1H), 8.40-8.36 (m, 1H), 8.28 (s, 1H), 8.04 (s, 1H), 7.85 ( d,J=2.0Hz,1H), 5.20(brs,1H), 3.10(d,J=4.8Hz,3H).

Step 2: 2-[6-Bromo-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H- Synthesis of imidazo[4,5-b]pyridine

Make 6-bromo-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine 2.93 g of -2-carboxyamide was dissolved in 15 ml of acetic acid, and stirred for 2 hours under heating under reflux. After the reaction, the solvent was distilled off under reduced pressure. Add 10ml of water to the residue obtained, in chloroform (10ml×2) extraction. The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) by medium pressure fractionation liquid chromatography to obtain 2.82 g of the target product as a light brown solid.

Melting point: 220-225°C

¹ H-NMR(CDCl ₃ ): δ8.71(d,J=1.4Hz,1H), 8.55(s,1H), 8.51(s,1H), 8.27(d,J=1.4Hz,1H), 8.14 (s, 1H), 4.47 (s, 3H).

Step 3: 2-[6-Bromo-3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-( Synthesis of (trifluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-023b of the present invention)

518 mg of N-chlorosuccinimide was dissolved in 5 ml of 1,2-dichloroethane, and 321 mg of ethane mercaptan was added at -40°C. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After the stirring, 2-[6-bromo-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6- (Trifluoromethyl)-3H-imidazo[4,5-b]pyridine 300mg in 1,2-dichloroethane 2ml solution. After the addition, the reaction mixture was stirred under heating and reflux for 3 hours. After the stirring, to the reaction mixture, a solution of 1.04 g of N-chlorosuccinimide and 642 mg of ethane mercaptan in 5 ml of 1,2-dichloroethane prepared in another container was added at room temperature. After the addition, the reaction mixture was stirred under heating and reflux for 3 hours. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. Dissolve the resulting residue in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) Purification was carried out by medium pressure fractionation liquid chromatography to obtain 212 mg of the target product as a white solid.

Melting point: 214-215°C

¹ H-NMR(CDCl ₃ ): δ8.93(s,1H), 8.74(d,J=1.4Hz,1H), 8.40(d,J=1.4Hz,1H), 8.13(s,1H), 4.33 (s,3H), 3.18(q,J=7.4Hz,2H), 1.24(t,J=7.4Hz,3H).

Step 4: 2-[6-Bromo-3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6 Synthesis of -(Trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No.1-1-023a of the present invention)

In 2-[6-bromo-3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl) A solution of 150 mg of (methyl)-3H-imidazo[4,5-b]pyridine in 5 ml of chloroform was added with 175 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 142 mg of the target white solid.

Melting point: 226-228°C

¹ H-NMR(CDCl ₃ ): δ9.60(s,1H), 8.77(d,J=1.4Hz,1H), 8.36(d,J=1.4Hz,1H), 8.23(s,1H), 4.19 (s,3H), 4.15(q,J=7.5Hz,2H), 1.49(t,J=7.5Hz,3H).

Synthesis Example 8: 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a] Pyridin-2-yl]-5-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-031b of the present invention), 2-[3-(ethylthio )-7-(Trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-1-methyl-5-(trifluoromethyl)-1H-imidazo[4,5-b ] Pyridine (compound No. 1-7-001b of the present invention) and 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]- Synthesis of 3-methyl-5-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-030b of the present invention)

Step 1: N-[2-Amino-6-(trifluoromethyl)pyridin-3-yl]-3-ethylthio-7-(trifluoromethyl)imidazo[1,2-a]pyridine Synthesis of -2-Carboxamide

Dissolve 712 mg of 6-(trifluoromethyl)pyridine-2,3-diamine in 10ml of pyridine, and add 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2- a] 972 mg of pyridine-2-carboxylic acid and 1.32 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the reaction was completed, 20 ml of water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain a crude product of 1.20 g of the target product of a black tea-colored solid. This material can be used directly in the next step without further purification.

Step 2: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-(trifluoromethyl)-3H-imidazole Synthesis of and [4,5-b]pyridine (Compound No.1-1-031b of the present invention)

N-[2-amino-6-(trifluoromethyl)pyridin-3-yl]-3-ethylthio-7-(trifluoromethyl)imidazo[ 1.2 g of 1,2-a]pyridine-2-carboxyamide was dissolved in 10 ml of propionic acid, and the mixture was stirred under heating and reflux for 3 hours. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The resulting organic layer was mixed with 1M hydrogen Wash with sodium oxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 1.0 g of the target brown solid. This material can be used directly in the next step without further purification.

¹ H-NMR(CDCl ₃ ): δ8.59(d,J=7.2Hz,1H), 8.03(d,J=7.8Hz,1H), 7.83(s,1H), 7.36(d,J=7.8Hz ,1H),7.04-6.98(m,1H),3.02(q,J=7.4Hz,2H),1.05(t,J=7.4Hz,3H) (the peak of the proton of NH cannot be observed).

Step 3: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-1-methyl-5-(trifluoromethyl )-1H-imidazo[4,5-b]pyridine (compound No.1-7-001b of the present invention) and 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1 ,2-a]pyridin-2-yl]-3-methyl-5-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (the present compound No.1-1-030b) Synthesis

To 63% by mass sodium hydride (dispersed in mineral oil) 66mg of N,N-dimethylformamide 3ml solution, add 2-[3-(ethylthio)-7-(trifluoromethyl) under ice cooling )Imidazo[1,2-a]pyridin-2-yl]-5-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine 500mg N,N-dimethylformamide 7ml solution. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the stirring, 286 mg of methyl trifluoromethanesulfonate was added to the reaction mixture under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 1.5 hours. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and extraction was carried out with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The residue obtained was purified in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) by medium pressure fractionation liquid chromatography to obtain the target product of brown solid. 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-1-methyl-5-(trifluoromethyl)-1H -150 mg of imidazo[4,5-b]pyridine and 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2 as the target product of a white solid -Yl]-3-methyl-5-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine 218 mg.

2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-1-methyl-5-(trifluoromethyl)-1H -Melting point of imidazo[4,5-b]pyridine: 164-166°C

¹ H-NMR(CDCl ₃ ): δ8.81(d,J=7.5Hz,1H), 8.03(s,1H), 7.91(d,J=8.2Hz,1H), 7.70(d,J=8.2Hz ,1H), 7.20(dd,J=7.5,1.7Hz,1H), 4.31(s,3H), 3.35(q,J=7.4Hz,2H), 1.24(t,J=7.4Hz,3H).

2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-5-(trifluoromethyl)-3H -Melting point of imidazo[4,5-b]pyridine: 163-165°C

¹ H-NMR(CDCl ₃ ): δ8.77(d,J=7.2Hz,1H), 8.26(d,J=8.2Hz,1H), 8.06(s,1H), 7.68(d,J=8.2Hz ,1H), 7.21(dd,J=7.2,1.5Hz,1H), 4.33(s,3H), 3.12(q,J=7.4Hz,2H), 1.20(t,J=7.4Hz,3H).

Synthesis Example 9: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl) Yl)-3H-imidazo[4,5-c]pyridine (compound No. 1-8-005b of the present invention) and 2-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazole And [1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (compound No.1-8 of the present invention) -005a) synthesis

Step 1: 3-(Ethylthio)-N-[5-(methylamino)-2-(trifluoromethyl)pyridine Synthesis of pyridin-4-yl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxyamide

Dissolve 303 mg of N ³ -methyl-6-(trifluoromethyl)pyridine-3,4-diamine in 15 ml of pyridine, and add 3-(ethylthio)-7-(trifluoromethyl)imidazole at room temperature And [1,2-a]pyridine-2-carboxylic acid 552mg and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 732mg. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the reaction, the solvent was distilled off under reduced pressure. Add 10 ml of water to the obtained residue, and extract with chloroform (10 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain a crude product of 986 mg of the target product. This material can be used directly in the next step without further purification.

Step 2: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl )-3H-imidazo[4,5-c]pyridine (compound No.1-8-005b of the present invention) synthesis

The crude product obtained in step 1 is 3-(ethylthio)-N-[5-(methylamino)-2-(trifluoromethyl)pyridin-4-yl]-7-(trifluoro 986 mg of (methyl)imidazo[1,2-a]pyridine-2-carboxyamide was dissolved in 15 ml of acetic acid, and the mixture was stirred under heating and reflux for 22 hours. After the stirring, the reaction mixture was stirred at room temperature overnight. After the reaction, the solvent was distilled off under reduced pressure. Add 10 ml of water to the obtained residue, and extract with chloroform (10 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 70:30) by medium pressure fractionation liquid chromatography to obtain 358 mg of the target product as a yellow solid.

Melting point: 217-219°C

¹ H-NMR(CDCl ₃ ): δ8.97(s,1H), 8.78(d,J=7.2Hz,1H), 8.20(s,1H), 8.05(s,1H), 7.22(d,J= 7.2Hz, 1H), 4.37 (s, 3H), 3.15 (q, J=7.5Hz, 2H), 1.22 (t, J=7.5Hz, 3H).

Step 3: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl) (Methyl)-3H-imidazo[4,5-c]pyridine (the compound No. 1-8-005a of the present invention) synthesis

To 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)- A solution of 258 mg of 3H-imidazo[4,5-c]pyridine in 8 ml of chloroform was added with 323 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was dissolved in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) by pressure fractionation and liquid chromatography for purification. The obtained solid was added with 10 ml of diisopropyl ether and filtered to obtain 200 mg of the target product as a yellow solid.

Melting point: 245-247°C

¹ H-NMR(CDCl ₃ ): δ9.39(d,J=7.2Hz,1H), 9.00(s,1H), 8.14(s,2H), 7.33(d,J=7.2Hz,1H), 4.20 (s, 3H), 4.07 (q, J=7.5Hz, 2H), 1.46 (t, J=7.5Hz, 3H).

Synthesis Example 10: 2-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3,4-dimethyl-6-( Trifluoromethyl)-3H-imidazo[4,5-c]pyridine Pyridine (compound No. 1-8-003b of the present invention) and 2-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl] -3,4-Dimethyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (Compound No. 1-8-003a of the present invention) synthesis

Step 1: 3-(Ethylthio)-N-[2-methyl-3-(methylamino)-6-(trifluoromethyl)pyridin-4-yl]-6-(trifluoromethyl ) Synthesis of imidazo[1,2-a]pyridine-2-carboxamide

Dissolve 212 mg of N ³ ,2-dimethyl-6-(trifluoromethyl)pyridine-3,4-diamine in 10 ml of pyridine, and add 3-(ethylthio)-6-(trifluoromethyl) at room temperature. Yl)imidazo[1,2-a]pyridine-2-carboxylic acid 200mg, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 264mg and 4-( Dimethylamino)pyridine 9mg. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 3-(ethylthio)-N-[2-methyl-3-(methylamino)-6-(trifluoromethyl)pyridine-4- A crude product of 6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxyamide. This material can be used directly in the next step without further purification.

Step 2: 2-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3,4-dimethyl-6-(trifluoromethyl) (Fluoromethyl)-3H-imidazo[4,5-c]pyridine (Compound No.1-8-003b of the present invention)

The crude product obtained in step 1 is 3-(ethylthio)-N-[2-methyl-3-(methylamino)-6-(trifluoromethyl)pyridin-4-yl]- 6-(Trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxyamide was dissolved in 10ml of acetic acid and stirred under heating under reflux Stir for 3 hours. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 70:30) to obtain 85 mg of the target white solid.

Melting point: 169-171°C

¹ H-NMR(CDCl ₃ ): δ9.01(s,1H), 8.03(s,1H), 7.83(d,J=9.3Hz,1H), 7.54(dd,J=9.3,1.8Hz,1H) , 4.41 (s, 3H), 3.10 (q, J = 7.5 Hz, 2H), 3.08 (s, 3H), 1.22 (t, J = 7.5 Hz, 3H).

Step 3: 2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3,4-dimethyl-6- Synthesis of (trifluoromethyl)-3H-imidazo[4,5-c]pyridine (compound No.1-8-003a of the present invention)

In 2-[3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3,4-dimethyl-6-(trifluoromethyl) Yl)-3H-imidazo[4,5-c]pyridine 49 mg in 3 ml of chloroform solution, and 57 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 37 mg of the target white solid.

Melting point: 200-205°C

¹ H-NMR(CDCl ₃ ): δ9.59(s,1H),7.97(s,1H),7.96(d,J=9.6Hz,1H),7.74(dd,J=9.6,1.5Hz,1H) , 4.25 (s, 3H), 3.96 (q, J = 7.5 Hz, 2H), 3.08 (s, 3H), 1.45 (t, J = 7.5 Hz, 3H).

Synthesis Example 11: 3-(Ethylsulfonyl)-6,7'-bis(trifluoromethyl)-2,2'-biimidazo[1,2-a]pyridine (Compound No. 1 of the present invention) -5-002a) Synthesis

Dissolve 102 mg of 4-(trifluoromethyl)pyridin-2-amine in 4 ml of bromobenzene, and add 2-bromo-1-[3-(ethylsulfonyl)-6-(trifluoromethyl) at room temperature Imidazo[1,2-a]pyridin-2-yl]ethanone 300mg. After the addition, the reaction mixture was stirred under heating and reflux for 5 hours. After the completion of the reaction, 10 ml of 1M sodium hydroxide aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 168 mg of the target white solid.

Melting point: 245-248°C

¹ H-NMR(CDCl ₃ ): δ9.65(s,1H), 8.57(s,1H), 8.30(d,J=7.2Hz,1H), 8.01(s,1H),7.90(d,J= 9.6Hz,1H), 7.63(dd,J=9.6,1.8Hz,1H), 7.03(dd,J=7.2,1.8Hz,1H), 3.73(q,J=7.5Hz,2H),1.33(t, J=7.5Hz, 3H).

Synthesis Example 12: 2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-7-(perfluoroethyl)imidazole And [1,2-c]pyrimidine (compound No.1-3-008a of the present invention) and 3-bromo-2-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazo[ Synthesis of 1,2-a]pyridin-2-yl]-7-(perfluoroethyl)imidazo[1,2-c]pyrimidine (compound No.1-3-010a of the present invention)

Step 1: 2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-7-(perfluoroethyl)imidazo [1,2-c] Synthesis of pyrimidine (compound No.1-3-008a of the present invention)

Dissolve 800 mg of 6-(perfluoroethyl)pyrimidine-4-amine in 10 ml of chlorobenzene, and add 2-bromo-1-[3-(ethylsulfonyl)-6-(trifluoromethyl) at room temperature Imidazo[1,2-a]pyridin-2-yl]ethanone 1780 mg. After the addition, the reaction mixture was stirred under heating and reflux for 3 hours. After the completion of the reaction, 10 ml of 1M sodium hydroxide aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by liquid chromatography with n-hexane-ethyl acetate (gradient from 100:0 to 50:50) dissolution and fractionation to obtain 926 mg of the target product as a yellow solid.

Melting point: 233-239°C

¹ H-NMR(CDCl ₃ ): δ9.63(s,1H),9.19(s,1H),8.64(s,1H),8.05(s,1H),7.92(d,J=9.6Hz,1H) ,7.66(dd,J=9.6,1.5Hz,1H), 3.72(q,J=7.5Hz,2H), 1.35(t,J=7.5Hz,3H).

Step 2: 3-Bromo-2-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-7-(perfluoroethyl Synthesis of imidazo[1,2-c]pyrimidine (Compound No.1-3-010a of the present invention)

To 2-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-7-(perfluoroethyl)imidazo[1 ,2-c] A solution of 150 mg of pyrimidine in 2 ml of N,N-dimethylformamide, and 57 mg of N-bromosuccinimide under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the reaction is over, add 10ml of water to the reaction mixture, and add 10ml of diethyl ether (10ml×2) extraction. The resulting organic layer was washed with saturated aqueous sodium thiosulfate solution, followed by saturated sodium bicarbonate, and then dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 127 mg of the target white solid.

Melting point: 200-205°C

¹ H-NMR(CDCl ₃ ): δ9.61(s,1H),9.20(s,1H),7.99(s,1H),7.96(d,J=9.6Hz,1H),7.68(d,J= 9.6Hz, 1H), 4.00 (q, J=7.5Hz, 2H), 1.46 (t, J=7.5Hz, 3H).

Synthesis Example 13: 2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-5-methyl-7-(all Synthesis of fluoroethyl)imidazo[1,2-c]pyrimidine (compound No.1-3-007a of the present invention)

Dissolve 143 mg of 2-methyl-6-(perfluoroethyl)pyrimidin-4-amine in 4 ml of bromobenzene, and add 2-bromo-1-[3-(ethylsulfonyl)-6-( Trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone 300mg. After the addition, the reaction mixture was stirred under heating and reflux for 5 hours. After the completion of the reaction, 10 ml of 1M sodium hydroxide aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 82 mg of the target product as a pale yellow solid.

Melting point: 224-226°C

¹ H-NMR(CDCl ₃ ): δ9.66(s,1H),8.46(s,1H),7.94(s,1H),7.90(d,J=9.6Hz,1H),7.66(dd,J= 9.6, 1.8Hz, 1H), 3.85 (q, J=7.5Hz, 2H), 2.97 (s, 3H), 1.37 (t, J=7.5Hz, 3H).

Synthesis Example 14: 6-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-2-(trifluoromethyl)imidazole Synthesis of and [2,1-b]thiazole (Compound No.1-12-001a of the present invention)

Dissolve 106 mg of 5-(trifluoromethyl)thiazol-2-amine in 4 ml of bromobenzene, and add 2-bromo-1-[3-(ethylsulfonyl)-6-(trifluoromethyl) at room temperature Imidazo[1,2-a]pyridin-2-yl]ethanone 300mg. After the addition, the reaction mixture was stirred under heating and reflux for 5 hours. After the completion of the reaction, 10 ml of 1M sodium hydroxide aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 153 mg of the target white solid.

Melting point: 219-220℃

¹ H-NMR(CDCl ₃ ): δ9.60(s,1H),8.44(s,1H),7.97-7.94(m,1H),7.87(d,J=9.6Hz,1H),7.62(dd, J=9.6, 1.5Hz, 1H), 3.59 (q, J=7.5Hz, 2H), 1.30 (t, J=7.5Hz, 3H).

Synthesis Example 15: 2-[3-(Ethylthio)-1-methyl-5-(trifluoromethyl)-1H-indol-2-yl]-3-methyl-6-(trifluoromethyl) Group)-3H-imidazo[4,5-b]pyridine (compound No.3-1-001b of the present invention) and 2-[3-(ethylsulfonyl)-1-methyl-5-(three Fluoromethyl)-1H-indol-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No.3-1 of the present invention) -001a) synthesis

Step 1: 1-Methyl-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-5-(trifluoromethyl)-1H-indole-2 -Synthesis of Carboxyamide

Dissolve 573 mg of N ² -methyl-5-(trifluoromethyl)pyridine-2,3-diamine in 10 ml of pyridine, and add 1-methyl-5-(trifluoromethyl)-1H-indino at room temperature Dole-2-carboxylic acid 608 mg, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 959 mg, and 4-(dimethylamino)pyridine 31 mg. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, 20 ml of water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain a crude product of 1.02 g of the target product as a gray solid. This material can be used directly in the next step without further purification.

Step 2: 3-Methyl-2-[1-methyl-5-(trifluoromethyl)-1H-indol-2-yl]-6-(trifluoromethyl)-3H-imidazo[4 ,5-b]Pyridine Synthesis

The crude product obtained in step 1 is 1-methyl-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-5-(trifluoromethyl) 968 mg of -1H-indole-2-carboxyamide was dissolved in 10 ml of acetic acid, and the mixture was stirred under heating and reflux for 3 hours. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) by medium pressure fractionation liquid chromatography to obtain 638 mg of the target substance as a flesh-colored solid.

Melting point: 200-202℃

¹ H-NMR(DMSO-d6): δ8.84(d,J=1.4Hz,1H), 8.64(d,J=1.4Hz,1H), 8.15(s,1H), 7.86(d,J=8.9 Hz,1H), 7.63(dd, J=8.9,1.4Hz,1H), 7.46(s,1H), 4.12(s,3H), 4.06(s,3H).

Step 3: 2-[3-Iodo-1-methyl-5-(trifluoromethyl)-1H-indol-2-yl]-3-methyl-6-(trifluoromethyl)-3H- Synthesis of imidazo[4,5-b]pyridine

In 3-methyl-2-[1-methyl-5-(trifluoromethyl)-1H-indol-2-yl]-6-(trifluoromethyl)-3H-imidazo[4,5 -b] A solution of 478 mg of pyridine in 8 ml of N,N-dimethylformamide, and 405 mg of N-iodosuccinimide at room temperature. After the addition, the reaction mixture was stirred for 7 hours under heating and refluxing. After the completion of the reaction, by adding a saturated sodium thiosulfate aqueous solution to the reaction mixture, the precipitated solid was separated by filtration to obtain 675 mg of the target white solid.

Melting point: 165-167°C

¹ H-NMR(CDCl ₃ ): δ8.82(d,J=1.4Hz,1H), 8.43(d,J=1.4Hz,1H), 7.90-7.87(m,1H), 7.66(dd,J= 8.7, 1.4Hz, 1H), 7.52 (d, J=8.7Hz, 1H), 3.97 (s, 3H), 3.85 (s, 3H).

Step 4: 2-[3-(Ethylthio)-1-methyl-5-(trifluoromethyl)-1H-indol-2-yl]-3-methyl-6-(trifluoromethyl) )-3H-imidazo[4,5-b]pyridine (compound No.3-1-001b of the present invention) synthesis

To 2-[3-iodo-1-methyl-5-(trifluoromethyl)-1H-indol-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo [4,5-b] A solution of 626mg of pyridine in 10ml of 1,4-dioxane, 154mg of diisopropylethylamine, 4,5'-bis(diphenylphosphino)- 69 mg of 9,9'-dimethylxanthene, 54 mg of ginseng (dibenzylideneacetone) dipalladium (0), and 111 mg of ethane mercaptan. After the addition was completed, the inside of the reaction vessel was replaced with nitrogen, and then stirred under heating and reflux for 1.5 hours. After the reaction, the reaction mixture was filtered through diatomaceous earth, and the diatomaceous earth was washed with chloroform. net. The filtrate and washing liquid obtained are blended, and the solvent is distilled off under reduced pressure. The resulting residue was purified by liquid chromatography with n-hexane-ethyl acetate (gradient of 100:0-50:50) dissolution, and fractionation to obtain 545 mg of the target product as a pale yellow solid.

Melting point: 153-155°C

¹ H-NMR(CDCl ₃ ): 88.80(s,1H), 8.40(s,1H), 8.19(s,1H), 7.65(d,J=8.5Hz,1H), 7.55(d,J=8.5Hz) ,1H), 3.95(s,3H), 3.85(s,3H), 2.59(q,J=7.4Hz,2H), 1.00(t,J=7.4Hz,3H).

Step 5: 2-[3-(Ethylsulfonyl)-1-methyl-5-(trifluoromethyl)-1H-indol-2-yl]-3-methyl-6-(trifluoro Synthesis of (Methyl)-3H-imidazo[4,5-b]pyridine (Compound No.3-1-001a of the present invention)

To 2-[3-(ethylthio)-1-methyl-5-(trifluoromethyl)-1H-indol-2-yl]-3-methyl-6-(trifluoromethyl)- To a solution of 250 mg of 3H-imidazo[4,5-b]pyridine in 5 ml of chloroform, 333 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 245 mg of the target white solid.

Melting point: 143-146°C

¹ H-NMR(CDCl ₃ ): δ8.83(s,1H), 8.50(s,1H), 8.40(d, =1.7Hz,1H), 7.75(dd,J=8.5,1.7Hz,1H), 7.63(d,J=8.5Hz,1H), 3.88(s,3H), 3.73(s,3H), 3.30-3.11(m,2H), 1.27(t,J=7.2Hz,3H).

Synthesis Example 16: 2-[3-(Ethylthio)-5-(trifluoromethyl)benzo[b]thiophen-2-yl]-3-methyl-6-(trifluoromethyl)-3H -Imidazo[4,5-b]pyridine (compound No.3-1-002b of the present invention) and 2-[3-(ethylsulfonyl)-5-(trifluoromethyl)benzo[b] Synthesis of thiophen-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.3-1-002a of the present invention)

Step 1: N-[2-(Methylamino)-5-(trifluoromethyl)pyridin-3-yl]-5-(trifluoromethyl)benzo[b]thiophen-2-carboxyamide Synthesis

Dissolve 573 mg of N ² -methyl-5-(trifluoromethyl)pyridine-2,3-diamine in 10 ml of pyridine, and add 5-(trifluoromethyl)benzo[b]thiophene-2- at room temperature 615 mg of carboxylic acid, 959 mg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 31 mg of 4-(dimethylamino)pyridine. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, 20 ml of water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain a crude product of 939 mg of the target product as a gray solid. This material can be used directly in the next step without further purification.

Step 2: 3-Methyl-6-(trifluoromethyl)-2-[5-(trifluoromethyl)benzo[b]thiophen-2-yl]-3H-imidazo[4,5-b ] Synthesis of pyridine

The crude product obtained in step 1 is N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]-5-(trifluoromethyl)benzo[b] 877 mg of thiophene-2-carboxyamide was dissolved in 10 ml of acetic acid, and the mixture was stirred under heating and reflux for 3 hours. After the reaction, the solvent was distilled off under reduced pressure. Add water to the resulting residue 10ml, extract in ethyl acetate (10ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by liquid chromatography with n-hexane-ethyl acetate (gradient from 100:0 to 0:100) dissolution, to obtain 683 mg of the target substance as a flesh-colored solid.

Melting point: 191-193°C

¹ H-NMR(DMSO-d6): δ8.83-8.79(m,1H),8.62-8.59(m,1H),8.53(s,1H),8.44(s,1H),8.36(d,J= 8.5Hz, 1H), 7.80 (d, J=8.5Hz, 1H), 4.24 (s, 3H).

Step 3: 2-[3-Chloro-5-(trifluoromethyl)benzo[b]thiophen-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4 ,5-b]Pyridine Synthesis

To 3-methyl-6-(trifluoromethyl)-2-[5-(trifluoromethyl)benzo[b]thiophen-2-yl]-3H-imidazo[4,5-b]pyridine To a solution of 400 mg of N,N-dimethylformamide in 5 ml, add 590 mg of 1,3-dichloro-5,5-dimethylhydantoin at 80°C. After the addition, the reaction mixture was stirred at 80°C for 1.5 hours. After the completion of the reaction, by adding a saturated sodium thiosulfate aqueous solution to the reaction mixture, the precipitated solid was separated by filtration to obtain 390 mg of the target white solid.

Melting point: 158-160℃

¹ H-NMR(CDCl ₃ ): δ8.81-8.77(m,1H), 8.41-8.38(m,1H), 8.29-8.26(m,1H), 8.06(d,J=8.5Hz,1H), 7.80(d,J=8.5Hz,1H),4.04(s,3H).

Step 4: 2-[3-(Ethylthio)-5-(trifluoromethyl)benzo[b]thiophen-2-yl]-3-methyl-6-(trifluoromethyl)-3H- Imidazo[4,5-b]pyridine (the present invention Compound No.3-1-002b) Synthesis

To 2-[3-chloro-5-(trifluoromethyl)benzo[b]thiophen-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5 -b] A solution of 370 mg of pyridine in 5 ml of N,N-dimethylformamide, and 119 mg of sodium ethanethiol group at 80°C. After the addition, the reaction mixture was stirred at 80°C for 1.5 hours. After the stirring, 159 mg of sodium ethanethiol group was added to the reaction mixture at 80°C. After the completion of the reaction, 20 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (20 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography eluted in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 186 mg of the target yellow solid.

Melting point: 120-122℃

¹ H-NMR(CDCl ₃ ): δ8.78(s,1H), 8.41(s,1H), 8.38(d,J=1.8Hz,1H), 8.06(d,J=8.6Hz,1H), 7.77 -7.74(m,1H),3.96(s,3H), 2.69(q,J=7.4Hz,2H), 1.05(t,J=7.4Hz,3H).

Step 5: 2-[3-(Ethylsulfonyl)-5-(trifluoromethyl)benzo[b]thiophen-2-yl]-3-methyl-6-(trifluoromethyl)- Synthesis of 3H-imidazo[4,5-b]pyridine (compound No.3-1-002a of the present invention)

To 2-[3-(ethylthio)-5-(trifluoromethyl)benzo[b]thiophen-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo [4,5-b] A solution of 147 mg of pyridine in 3 ml of chloroform, and 195 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 4 hours. After the reaction is over, add saturated thiosulfuric acid to the reaction mixture The aqueous sodium solution was extracted in chloroform (10 ml). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 104 mg of the target white solid.

Melting point: 70-75°C

¹ H-NMR(CDCl ₃ ): δ8.85(s,1H), 8.79(d,J=1.5Hz,1H), 8.35(d,J=1.8Hz,1H), 8.13(d,J=8.6Hz ,1H), 7.85(dd,J=8.6,1.8Hz,1H), 3.89(s,3H), 3.38(q,J=7.5Hz,2H), 1.32(t,J=7.5Hz,3H).

Synthesis Example 17: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H- Pyrazolo[4,3-b]pyridine (compound No. 1-10-002b of the present invention) and 2-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1, Synthesis of 2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H-pyrazolo[4,3-b]pyridine (compound No.1-10-002a1 of the present invention)

Step 1: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H-pyridine Synthesis of azolo[4,3-b]pyridine (compound No.1-10-002b of the present invention)

Combine 400 mg of 3-nitro-5-(trifluoromethyl) picoline formaldehyde and 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2 -A solution of 522 mg of amine in 5 ml of xylene was stirred under reflux with heating for 1 hour. After the stirring, 1.50 g of triethyl phosphite was added to the reaction mixture at room temperature. After the addition, the reaction mixture was stirred under heating and reflux for 1 hour. After the reaction, the solvent was distilled off from the reaction mixture. Put the resulting residue in n- Alkane-ethyl acetate (gradient from 100:0 to 50:50) was dissolved in medium pressure fractionation and purified by liquid chromatography to obtain 613 mg of the target product as a pale yellow solid.

Melting point: 161-163°C

¹ H-NMR(CDCl ₃ ): δ9.43-9.41(m,1H), 8.85(d,J=2.1Hz,1H), 8.76(d,J=7.4Hz,1H), 8.53-8.49(m, 1H), 8.05-8.00 (m, 1H), 7.30-7.20 (m, 1H), 2.99 (q, J=7.5Hz, 2H), 1.21 (t, J=7.5Hz, 3H).

Step 2: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H -Synthesis of pyrazolo[4,3-b]pyridine (compound No. 1-10-002a of the present invention)

To 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H-pyrazolo [4,3-b] A solution of 150 mg of pyridine in 5 ml of chloroform, and 204 mg of m-chloroperbenzoic acid (containing 35% by weight of water) was added under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the stirring, 40 mg of m-chloroperbenzoic acid (containing 35% by weight of water) was added to the reaction mixture at room temperature. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the completion of the reaction, 3 ml of saturated sodium thiosulfate aqueous solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 61 mg of the target white solid.

Melting point: 245-247°C

¹ H-NMR(CDCl ₃ ): δ9.44(d,J=7.2Hz,1H), 9.17-9.15(m, 1H), 8.86(d,J=1.8Hz,1H), 8.48-8.43(m, 1H), 8.13-8.09(m,1H), 7.35-7.30(m,1H), 4.04(q,J=7.5Hz,2H), 1.48(t,J=7.5Hz,3H).

Synthesis Example 18: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H- Pyrazolo[4,3-c]pyridine (compound No. 1-11-001b of the present invention) and 2-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1, Synthesis of 2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H-pyrazolo[4,3-c]pyridine (compound No. 1-11-001a of the present invention)

Step 1: Synthesis of 4-azido-6-(trifluoromethyl)nicotinaldehyde

To a solution of 1.50 g of N,N-dimethylformamide in 10 ml of 4-chloro-6-(trifluoromethyl)nicotinaldehyde, add 511 mg of sodium azide under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 3 hours. After the reaction was completed, 10 ml of water was added to the reaction mixture, and the mixture was extracted with diethyl ether (20 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography eluted in n-hexane-ethyl acetate (gradient from 100:0 to 80:20) to obtain 2.13 g of the target white solid.

Melting point: 54-56°C

¹ H-NMR (CDCl ₃ ): δ 10.39 (s, 1H), 9.06 (s, 1H), 7.54 (s, 1H).

Step 2: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H-pyridine Synthesis of azolo[4,3-c]pyridine (Compound No. 1-11-001b of the present invention)

In 4-azido-6-(trifluoromethyl)nicotinaldehyde 200mg and 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-amine 266mg Add 282mg of triethylamine and 0.56ml of 1M titanium(IV) chloride to 1ml of dichloromethane solution in order under ice-cooling. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure. Diatomaceous earth is filtered to the residue, and the diatomaceous earth is washed with 20ml of xylene. The resulting cleaning solution was stirred for 2 hours under heating and refluxing. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (20 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography eluted in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 250 mg of the target product as a pale yellow solid.

Melting point: 183-185°C

¹ H-NMR(CDCl ₃ ): δ9.40-9.37(m,1H), 9.29(d,J=0.9Hz,1H), 8.77(d,J=7.4Hz,1H), 8.14(s,1H) ,8.04-7.99(m,1H),7.30-7.25(m,1H),3.02(q,J=7.4Hz,2H),1.21(t,J=7.4Hz,3H).

Step 3: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H -Synthesis of pyrazolo[4,3-c]pyridine (Compound No. 1-11-001a of the present invention)

To 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-2H-pyrazolo [4,3-c] A solution of 120 mg of pyridine in 5 ml of chloroform, and 65% by mass of m-chloroperbenzoic acid (containing about 30% of % Water) 164mg. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 63 mg of the target white solid.

Melting point: 230-233℃

¹ H-NMR(CDCl ₃ ): δ9.43(d,J=7.4Hz,1H),9.41-9.37(m,1H),9.07(s,1H),8.12-8.06(m,2H),7.36( dd,J=7.4,1.8Hz,1H),4.03(q,J=7.4Hz,2H), 1.48(t,J=7.4Hz,3H).

Synthesis Example 19: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)thiazolo[ 5,4-b]pyridine (compound No.1-13-001b of the present invention) and 2-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a] Synthesis of pyridin-2-yl]-6-(trifluoromethyl)thiazolo[5,4-b]pyridine (compound No.1-13-001a of the present invention)

Step 1: 3-(Ethylthio)-N-[2-mercapto-5-(trifluoromethyl)pyridin-3-yl]-7-(trifluoromethyl)imidazo[1,2-a] Synthesis of Pyridine-2-Carboxamide

Dissolve 500 mg of 3-amino-5-(trifluoromethyl)pyridine-2-thiol in 5 ml of pyridine, and add 3-(ethylthio)-7-(trifluoromethyl)imidazo[1 , 2-a] pyridine-2-carboxylic acid 621 mg, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 820 mg, and 1-hydroxybenzotriazole 10 mg. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the reaction is over, water is added to the reaction mixture, and the precipitated solid is filtered to obtain a brown solid A crude product of 234 mg of the target substance. This material can be used directly in the next step without further purification.

Step 2: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)thiazolo[5 ,4-b) Synthesis of pyridine (compound No.1-13-001b of the present invention)

The crude product obtained in step 1 is 3-(ethylthio)-N-[2-mercapto-5-(trifluoromethyl)pyridin-3-yl]-7-(trifluoromethyl)imidazo [1,2-a] 214 mg of pyridine-2-carboxyamide was dissolved in 5 ml of propionic acid, and the mixture was stirred under heating and reflux for 4 hours. After the stirring, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 20 mg of the target white solid.

Melting point: 150-160℃

¹ H-NMR(CDCl ₃ ): δ8.91-8.87(m,1H), 8.71(d,J=7.5Hz,1H), 8.65-8.61(m,1H), 8.06(s,1H), 7.20( dd,J=7.5,1.5Hz,1H),3.08(q,J=7.4Hz,2H), 1.27(t,J=7.4Hz,3H).

Step 3: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)thiazolo [5,4-b] Synthesis of pyridine (compound No.1-13-001a of the present invention)

To 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)thiazolo[5,4 -b] 20mg of pyridine dissolved in 3ml of chloroform Liquid, 27 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the completion of the reaction, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 15 mg of the target white solid.

Melting point: 243-245°C

¹ H-NMR(CDCl ₃ ): δ9.53(d,J=7.5Hz,1H),8.95-8.93(m,1H),8.63-8.61(m,1H),8.17-8.14(m,1H), 7.30(dd,J=7.5,1.9Hz,1H), 4.10(q,J=7.5Hz,2H), 1.45(t,J=7.5Hz,3H).

Synthesis Example 20: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-iodo-3-methyl-3H- Imidazo[4,5-b]pyridine (compound No.1-1-026b of the present invention), 2-ethylhexyl 3-((2-(3-(ethylthio)-7-(trifluoromethyl )Imidazo[1,2-a]pyridin-2-yl)-3-methyl-3H-imidazo[4,5-b]pyridin-6-yl)thio)propionate (Compound No. of the present invention. 1-1-028b), 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-( (Trifluoromethyl)sulfur)-3H-imidazo[4,5-b]pyridine (compound No.1-1-027b of the present invention) and 2-[3-(ethylsulfonyl)-7-( Trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-((trifluoromethyl)sulfur)-3H-imidazo[4,5-b]pyridine (Compound No.1-1-027a of the present invention) Synthesis

Step 1: 3-(Ethylthio)-N-[5-iodo-2-(methylamino)pyridin-3-yl]-7-(trifluoromethyl)imidazo[1,2-a] Synthesis of Pyridine-2-Carboxamide

Dissolve 1.59 g of 5-iodo-N ² -picoline-2,3-diamine in 15 ml of pyridine, and add 3-(ethylthio)-7-(trifluoromethyl)imidazo[1, 2-a] pyridine-2-carboxylic acid 1.54 g and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 2.45 g. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain a crude product of 2.49 g of the target product as a gray solid. This material can be used directly in the next step without further purification.

¹ H-NMR(CDCl ₃ ): δ8.97(brs,1H), 8.71(d,J=7.2Hz,1H), 8.27(d,J=2.0Hz,1H), 8.07(d,J=2.0Hz ,1H),7.96(s,1H),7.19(dd,J=7.2,2.0Hz,1H),4.78(brs,1H),3.08(q,J=7.4Hz,2H),3.03(d,J= 4.8Hz, 3H), 1.22 (t, J=7.4Hz, 3H).

Step 2: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-iodo-3-methyl-3H-imidazole Synthesis of and [4,5-b]pyridine (Compound No.1-1-026b of the present invention)

The crude product obtained in step 1 is 3-(ethylthio)-N-[5-iodo-2-(methylamino)pyridin-3-yl]-7-(trifluoromethyl)imidazo [1,2-a] 2.49 g of pyridine-2-carboxyamide was dissolved in 15 ml of acetic acid, and stirred under heating and reflux for 3.5 hours. After the completion of the reaction, water was added to the reaction mixture, and the precipitated solid was separated by filtration. The obtained solid was washed with n-hexane to obtain 2.02 g of the target brown solid.

Melting point: 230-233℃

¹ H-NMR(CDCl ₃ ): δ8.76(d,J=7.2Hz,1H), 8.62(d,J=1.7Hz,1H), 8.47(d,J=1.7Hz,1H), 8.03(s ,1H), 7.19(dd,J=7.2,1.7Hz,1H), 4.25(s,3H), 3.11(q,J=7.5Hz,2H), 1.20(t,J=7.5Hz,3H).

Step 3: 2-Ethylhexyl 3-((2-(3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)-3-methan Synthesis of 3-H-imidazo[4,5-b]pyridin-6-yl)thio)propionate (Compound No.1-1-028b of the present invention)

To 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-iodo-3-methyl-3H-imidazo[ 4,5-b] 503 mg of pyridine and a solution of 10 ml of 1,4-dioxane, add 387 mg of diisopropylethylamine and 4,5'-bis(diphenylphosphino)-9 in order at room temperature , 9'-dimethyl xanthene (Xanten) 58 mg, ginseng (dibenzylidene acetone) dipalladium (0) 92 mg and 2-ethylhexyl 3-mercaptopropionate 262 mg. After the addition was completed, the inside of the reaction vessel was replaced with nitrogen, and then stirred under heating and reflux for 4 hours. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and extraction was carried out with diethyl ether (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 80:20) to obtain 599 mg of the target product as a yellow solid.

Melting point: 94-96°C

¹ H-NMR(CDCl ₃ ): δ8.76(d,J=7.2Hz,1H), 8.53(d,J=2.0Hz,1H), 8.27(d,J=2.0Hz,1H), 8.03(s ,1H),7.18(dd,J=7.2,1.9Hz,1H),4.27(s,3H),4.01(dd,J=5.8,1.7Hz,2H),3.20-3.05(m,4H),2.62( t,J=7.3Hz,2H),1.45-1.20(m,12H),0.89(t,J=7.5Hz,6H).

Step 4: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-((trifluoromethyl) (Yl)sulfur)-3H-imidazo[4,5-b]pyridine (Compound No.1-1-027b of the present invention) Synthesis

Under nitrogen, 2-ethylhexyl 3-((2-(3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)-3 -Methyl-3H-imidazo[4,5-b]pyridin-6-yl)thio)propionate 560mg in tetrahydrofuran 5ml solution, add potassium tert-butoxide 159mg under ice cooling. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the stirring, 756 mg of S-(trifluoromethyl)dibenzothiophenium trifluoromethanesulfonate was added to the reaction mixture under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution, and then dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by thin layer chromatography eluted in n-hexane-ethyl acetate (gradient from 100:0 to 80:20) to obtain 69 mg of the target product as a pale yellow solid.

Melting point: 209-210°C

¹ H-NMR(CDCl ₃ ): δ8.77(d,J=7.2Hz,1H), 8.66(d,J=2.0Hz,1H), 8.46(d,J=2.0Hz,1H), 8.05-8.02 (m,1H),7.20(dd,J=7.2,1.9Hz,1H),4.31(s,3H),3.14(q,J=7.4Hz,2H),1.21(t,J=7.4Hz,3H) .

Step 5: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-((三Synthesis of (fluoromethyl)sulfur)-3H-imidazo[4,5-b]pyridine (compound No.1-1-027a of the present invention)

To 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-((trifluoromethyl) Sulfur)-3H-imidazo[4,5-b]pyridine 31mg in 3ml chloroform solution, add 65% by mass m-chloroperbenzoic acid under ice cooling (Contains about 30% by mass of water) 38mg. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the completion of the reaction, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 34 mg of the target white solid.

Melting point: 220-223°C

¹ H-NMR(CDCl ₃ ): δ9.41(d,J=7.4Hz,1H), 8.70(d,J=2.0Hz,1H), 8.41(dJ=2.0Hz,1H), 8.14(s,1H ), 7.31(dd,J=7.4,1.6Hz,1H), 4.16(s,3H), 4.11(q,J=7.4Hz,2H), 1.45(t,J=7.4Hz,3H).

Synthesis Example 21: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl) Synthesis of fluoromethyl)-3H-imidazo[4,5-b]pyridine 4-oxide (compound No.1-14-001a of the present invention)

To 2-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl )-3H-imidazo[4,5-b]pyridine 500mg in 15ml of acetonitrile solution, 65% by mass of m-chloroperbenzoic acid (containing about 30% by mass of water) 834mg was added under ice cooling. After the addition, the reaction mixture was stirred at 50°C for 20 hours. After the stirring, 279 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added to the reaction mixture at room temperature. After the addition, the reaction mixture was stirred at 50°C for 20 hours. After the stirring, 418 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added to the reaction mixture at room temperature. After the addition, the reaction was mixed The mixture was stirred at 50°C for 20 hours. After the completion of the reaction, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (20 ml×2). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 67 mg of the target white solid.

¹ H-NMR(CDCl ₃ ): δ9.35(d,J=7.2Hz,1H), 8.48-8.46(m,1H), 8.19-8.16(m,1H), 7.96(s,1H), 7.35( dd,J=7.2,1.7Hz,1H),4.58(s,3H),3.94(q,J=7.4Hz,2H),1.46(t,J=7.4Hz,3H).

Synthesis Example 22: 8-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-9-methyl-(trifluoromethyl) -9H-imidazo[4,5-c]pyridazine (compound No.1-16-001b of the present invention) and 8-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazo [1,2-a]Pyridin-2-yl]-9-methyl-(trifluoromethyl)-9H-imidazo[4,5-c]pyridazine (The present compound No.1-16-001a )Synthesis

Step 1: 3-(Ethylthio)-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]-6-(trifluoromethyl)imidazo[ Synthesis of 1,2-a]pyridine-2-carboxyamide

Make 4-bromo-N-methyl-6-(trifluoromethyl)pyridazine-3-amine 300mg, 3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a ] 509 mg of pyridine-carboxyamide, 497 mg of potassium phosphate, and 52 mg of N,N'-dimethylethylenediamine were dissolved in 4 ml of N,N-dimethylformamide, and 56 mg of copper (I) iodide was added at room temperature. After the addition was completed, the inside of the reaction vessel was replaced with nitrogen, and then stirred at 90°C for 9 hours. After the completion of the reaction, add 10ml of water to the reaction mixture, add ethyl acetate (10ml×2) extraction. The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain the target 3-(ethylthio)-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl] -The crude product of 6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxyamide. This material can be used directly in the next step without further purification.

Step 2: 8-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-9-methyl-(trifluoromethyl)- Synthesis of 9H-imidazo[4,5-c]pyridazine (Compound No.1-16-001b of the present invention)

Make 3-(ethylthio)-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]-7-(trifluoromethyl)pyridazin-4-yl of the crude product obtained in step 1. (Fluoromethyl)imidazo[1,2-a]pyridine-2-carboxyamide was dissolved in 10 ml of acetic acid, and stirred under heating and reflux for 7 hours. After the reaction, the solvent was distilled off under reduced pressure. 10ml of water was added to the residue obtained, and the mixture was extracted with ethyl acetate (10ml×2). The obtained organic layer was washed with saturated sodium bicarbonate aqueous solution and 28% by mass ammonia in the order, and then with saturated brine, followed by dehydration with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. Dehydrate in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 25:75) by medium pressure fractionation liquid chromatography to obtain 72 mg of the target product as a pale yellow solid.

Melting point: 240-242°C

¹ H-NMR(CDCl ₃ ): δ9.05-9.00(m,1H), 8.23(s,1H), 7.85(d,J=9.8Hz,1H), 7.56(dd,J=9.4,1.6Hz, 1H), 4.55 (s, 3H), 3.16 (q, J=7.4Hz, 2H), 1.25 (t, J=7.4Hz, 3H).

Step 3: 8-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2- a) Synthesis of pyridin-2-yl]-9-methyl-(trifluoromethyl)-9H-imidazo[4,5-c]pyridazine (compound No.1-16-001a of the present invention)

To 8-[3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-9-methyl-(trifluoromethyl)-9H- To a solution of 62 mg of imidazo[4,5-c]pyridazine in 5 ml of chloroform, 81 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the reaction was completed, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 25:75) by medium pressure fractionation liquid chromatography to obtain 66 mg of the target product as a pale yellow solid.

Melting point: 274-276°C

¹ H-NMR(CDCl ₃ ): δ9.70-9.60(m,1H), 8.22(s,1H), 7.99(d,J=9.4Hz,1H), 7.75(dd,J=9.4,1.6Hz, 1H), 4.38 (s, 3H), 4.05 (q, J=7.4Hz, 2H), 1.48 (t, J=7.4Hz, 3H).

Synthesis Example 23: 2-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl) Yl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-054b of the present invention) and 2-[3-(ethylsulfonyl)-6-(trifluoromethyl)imidazole And [1,2-a]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 1-1 of the present invention -054a) Synthesis

Step 1: 3-Methyl-6-(trifluoromethyl)-2-[6-(trifluoromethyl)imidazo[1,2-a]pyrimidin-2-yl]-3H-imidazo[4 ,5-b]Pyridine Synthesis

Dissolve 250 mg of 5-(trifluoromethyl)pyrimidin-2-amine in 10 ml of acetonitrile, 550 mg of 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone was added at room temperature. After the addition, the reaction mixture was stirred under heating and reflux for 7.5 hours. After the reaction was completed, 10 ml of water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain 445 mg of the target yellow solid.

Melting point: 283-285°C

¹ H-NMR(CDCl ₃ ): δ8.92-8.89(m,1H), 8.84(d,J=2.4Hz,1H), 8.73(s,1H), 8.57(s,1H), 8.29(s, 1H), 4.53(s, 3H).

Step 2: 2-[3-Iodo-6-(trifluoromethyl)imidazo[1,2-a]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl)-3H- Synthesis of imidazo[4,5-b]pyridine

In 3-methyl-6-(trifluoromethyl)-2-[6-(trifluoromethyl)imidazo[1,2-a]pyrimidin-2-yl]-3H-imidazo[4,5 -b] A solution of 415 mg of pyridine in 4 ml of N,N-dimethylformamide, and 408 mg of 1,3-diiodo-5,5-dimethylhydantoin at 80°C. After the addition, the reaction mixture was stirred at 80°C for 3 hours. After the completion of the reaction, by adding a saturated sodium thiosulfate aqueous solution to the reaction mixture, the precipitated solid was separated by filtration to obtain 468 mg of the target yellow solid.

Melting point: 260-265°C

¹ H-NMR(CDCl ₃ ): δ9.00-8.86(m,1H), 8.81(d,J=2.4Hz,1H), 8.74(d,J=1.5Hz,1H), 8.42(d,J= 1.5Hz, 1H), 4.43 (s, 3H).

Step 3: 2-[3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl )-3H-imidazo[4,5-b]pyridine (Compound No.1-1-054b of the present invention)

To 2-[3-iodo-6-(trifluoromethyl)imidazo[1,2-a]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo [4,5-b] A solution of 438 mg of pyridine in 10 ml of 1,4-dioxane, 334 mg of diisopropylethylamine, 4,5'-bis(diphenylphosphino)- 9,9'-dimethylxanthene 50mg, ginseng (dibenzylideneacetone) dipalladium (0) 39mg and ethane mercaptan 106mg. After the addition was completed, the inside of the reaction vessel was replaced with nitrogen, and then stirred under heating and reflux for 3 hours. After the completion of the reaction, water was added to the reaction mixture, and the precipitated solid was separated by filtration. The obtained solid was washed with diisopropyl ether to obtain 337 mg of the target yellow solid.

Melting point: 220-222°C

¹ H-NMR(CDCl ₃ ): δ9.27-9.23(m,1H), 8.88(d,J=2.1Hz,1H), 8.75(s,1H), 8.42(s,1H), 4.42(s, 3H), 3.25(q,J=7.5Hz,2H), 1.26(t,J=7.5Hz,3H).

Step 4: 2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyrimidin-2-yl]-3-methyl-6-(trifluoro Synthesis of (Methyl)-3H-imidazo[4,5-b]pyridine (Compound No.1-1-054a of the present invention)

In 2-[3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl)- To a solution of 297 mg of 3H-imidazo[4,5-b]pyridine in 7 ml of chloroform, 371 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 3.5 hours. After the stirring, 100 mg of m-chloroperbenzoic acid (containing 35% by weight of water) was added to the reaction mixture at room temperature. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the stirring, m-chloroperbenzoic acid (containing 35% by weight) was added to the reaction mixture at room temperature Water) 50mg. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the completion of the reaction, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 150 mg of the target white solid.

Melting point: 244-248°C

¹ H-NMR(CDCl ₃ ): δ10.00-9.95(m,1H), 9.04(d,J=2.4Hz,1H), 8.80(s,1H), 8.41-8.37(m,1H), 4.30( s,3H), 4.27(q,J=7.5Hz,2H), 1.49(t,J=7.5Hz,3H).

Synthesis Example 24: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl Group)-3H-imidazo[4,5-b]pyridine (compound No.1-1-055b of the present invention) and 2-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazole And [1,2-c]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (the compound No.1-1 of the present invention) -055a) synthesis

Step 1: 3-Methyl-6-(trifluoromethyl)-2-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3H-imidazo[4 ,5-b]Pyridine Synthesis

Dissolve 251 mg of 6-(trifluoromethyl)pyrimidin-4-amine in 10 ml of acetonitrile, and add 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[ 4,5-b]pyridin-2-yl]ethanone 550 mg. After the addition, the reaction mixture was stirred under heating and reflux for 7.5 hours. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain 335 mg of the target yellow solid.

Melting point: 257-260°C

¹ H-NMR(CDCl ₃ ): δ9.22(s,1H), 8.73(d,J=1.2Hz,1H), 8.64(s,1H), 8.29(d,J=1.8Hz,1H), 8.05 (s, 1H), 4.47 (s, 3H).

Step 2: 2-[3-Bromo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl)-3H- Synthesis of imidazo[4,5-b]pyridine

In 3-methyl-6-(trifluoromethyl)-2-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3H-imidazo[4,5 -b] A solution of 300 mg of pyridine in 5 ml of N,N-dimethylformamide, and 244 mg of 1,3-dibromo-5,5-dimethylhydantoin at 80°C. After the addition, the reaction mixture was stirred at 80°C for 30 minutes. After the completion of the reaction, by adding a saturated sodium thiosulfate aqueous solution to the reaction mixture, the precipitated solid was separated by filtration to obtain a crude product of 468 mg of the target product as a yellow solid. This material can be used directly in the next step without further purification.

¹ H-NMR(CDCl ₃ ): δ9.27(s,1H), 8.75(d,J=0.9Hz,1H), 8.43(d,J=1.5Hz,1H), 8.02(s,1H), 4.37 (s,3H).

Step 3: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl )-3H-imidazo[4,5-b]pyridine (compound No.1-1-055b of the present invention) synthesis

The crude product obtained in step 2 is 2-[3-bromo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-methyl-6-(trifluoro (Methyl)-3H-imidazo[4,5-b]pyridine 452mg in 1,4-dioxane 10ml solution, add diisopropylethylamine 377mg, 4,5'-bis in order at room temperature (Diphenylphosphino)-9,9'-dimethylxanthene 56mg, ginseng (dibenzylideneacetone) two palladium (0) 44mg and ethane mercaptan 121mg. After the addition was completed, the inside of the reaction vessel was replaced with nitrogen, and the mixture was stirred under heating and reflux for 6.5 hours. After the stirring, 754 mg of diisopropylethylamine, 112 mg of 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene, and ginseng were added to the reaction mixture at room temperature in order. (Dibenzylideneacetone) 88 mg of dipalladium (0) and 242 mg of ethane mercaptan. After the addition was completed, the inside of the reaction vessel was replaced with nitrogen, and then stirred under heating and reflux for 5 hours. After the completion of the reaction, water was added to the reaction mixture, and the precipitated solid was separated by filtration. The obtained solid was washed with diisopropyl ether to obtain 371 mg of the target substance as a brown solid.

Melting point: 198-200℃

¹ H-NMR(CDCl ₃ ): δ9.54(s,1H), 8.77-8.73(m,1H), 8.41(s,1H), 8.01(s,1H), 4.32(s,3H), 3.24( q,J=7.5Hz,2H),1.26(t,J=7.5Hz,3H).

Step 4: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-methyl-6-(trifluoro Synthesis of (methyl)-3H-imidazo[4,5-b]pyridine (Compound No.1-1-055a of the present invention)

2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-methyl-6-(trifluoromethyl) obtained in step 3 A solution of 315 mg of (methyl)-3H-imidazo[4,5-b]pyridine in 10 ml of chloroform was added with 412 mg of 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 3 hours. After the stirring, 206 mg of m-chloroperbenzoic acid (containing 35% by weight of water) was added to the reaction mixture at room temperature. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the reaction is over, add saturated sodium thiosulfate water to the reaction mixture The solution was extracted in chloroform (10ml×2). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) to obtain 139 mg of the target white solid.

Melting point: 238-240℃

¹ H-NMR (CDCl ₃ ): δ 10.15 (s, 1H), 8.80 (s, 1H), 8.39 (s, 1H), 8.15 (s, 1H), 4.22 (s, 3H), 4.22 (q, J=7.5Hz, 2H), 1.50 (t, J=7.5Hz, 3H).

Synthesis Example 25: 2-[3-(Ethylsulfonyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)imidazole Synthesis of and [1,2-a]pyrazine (Compound No.1-6-002a of the present invention)

Dissolve 103 mg of 5-(trifluoromethyl)pyrazine-2-amine in 4 ml of bromobenzene, and add 2-bromo-1-[3-(ethylsulfonyl)-6-(trifluoromethyl) at room temperature. ) Imidazo[1,2-a]pyridin-2-yl]ethanone 300mg. After the addition, the reaction mixture was stirred under heating and reflux for 5 hours. After the completion of the reaction, 10 ml of 1M sodium hydroxide aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 38 mg of the target white solid.

Melting point: 266-270°C

¹ H-NMR(CDCl ₃ ): δ9.63(s,1H),9.24(s,1H),8.68(s,1H),8.62(s,1H),7.93(d,J=9.3Hz,1H) ,7.66(dd,J=9.3, 1.8Hz,1H), 3.70(q,J=7.5Hz,2H), 1.35(t,J=7.5Hz,3H).

Synthesis Example 26: 2-[7-chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-3H-imidazo[4, 5-c]pyridine (compound No. 1-8-012b of the present invention), 2-[7-chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl]-3- Methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (compound No. 1-8-006b of the present invention) and 2-[7-chloro-3-(ethylthio ) Imidazo[1,2-a]pyridin-2-yl]-1-methyl-6-(trifluoromethyl)-1H-imidazo[4,5-c]pyridine (Compound No. 1 of the present invention) -9-003b) Synthesis

Step 1: N-[5-Amino-2-(trifluoromethyl)pyridin-4-yl]-7-chloro-3-(ethylthio)imidazo[1,2-a]pyridine-2- Synthesis of Carboxyamide

Dissolve 470 mg of 6-(trifluoromethyl)pyridine-3,4-diamine in 7 ml of pyridine, and add 7-chloro-3-(ethylthio)imidazo[1,2-a]pyridine-2 at room temperature -486 mg of carboxylic acid and 752 mg of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, 20 ml of water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain a crude product of 749 mg of the target product as a yellow solid. This material can be used directly in the next step without further purification.

Step 2: 2-[7-Chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl]-6-(trifluoromethyl)-3H-imidazo[4,5 -c] Synthesis of pyridine (Compound No. 1-8-012b of the present invention)

The crude product obtained in step 1 N-[5-amino-2-(trifluoromethyl)pyridin-4-yl]-7-chloro-3-(ethylthio)imidazo[1,2 -a] 749 mg of pyridine-2-carboxyamide was dissolved in 7 ml of propionic acid, and stirred under heating and reflux for 20 hours. After the stirring, the precipitated solid in the reaction mixture was filtered by filtration do not. The obtained solid was washed with water to obtain 761 mg of the target brown solid. This material can be used directly in the next step without further purification.

Step 3: 2-[7-Chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazole And [4,5-c]pyridine (compound No.1-8-006b of the present invention) and 2-[7-chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl Synthesis of]-1-methyl-6-(trifluoromethyl)-1H-imidazo[4,5-c]pyridine (Compound No.1-9-003b of the present invention)

To 63% by mass sodium hydride (dispersed in mineral oil) 219mg N,N-dimethylformamide 10ml solution, under ice-cooling, add 2-[7-chloro-3-(ethylthio)imidazo[1 ,2-a]pyridin-2-yl]-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine 761mg N,N-dimethylformamide solution in 10ml. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the stirring, 940 mg of methyl trifluoromethanesulfonate was added to the reaction mixture under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the completion of the reaction, 20 ml of water was added to the reaction mixture, and the mixture was extracted with diethyl ether (20 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The residue obtained was purified by liquid chromatography in n-hexane-ethyl acetate (gradient of 100:0~50:50) dissolution and fractionation to obtain white solid target 2-[7 -Chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c ]Pyridine 65mg and the target 2-[7-chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl]-1-methyl-6-(trifluoromethyl) -1H-imidazo[4,5-c]pyridine 247mg.

2-[7-Chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4 ,5-c]pyridine melting point: 215-217°C

¹ H-NMR(CDCl ₃ ): δ8.95(s,1H), 8.59(d,J=7.5Hz,1H), 8.19(s,1H),7.74-7.71(m,1H), 7.03(dd, J=7.5,2.1Hz,1H),4.33(s,3H),3.09(q,J=7.5Hz,2H), 1.19(t,J=7.5Hz,3H).

2-[7-Chloro-3-(ethylthio)imidazo[1,2-a]pyridin-2-yl]-1-methyl-6-(trifluoromethyl)-1H-imidazo[4 ,5-c]pyridine melting point: 187-188°C

¹ H-NMR(CDCl ₃ ): δ9.24(s,1H), 8.59(dd,J=7.2,0.6Hz,1H), 7.81(s,1H),7.73-7.69(m,1H), 7.03( dd,J=7.2,1.8Hz,1H), 4.26(s,3H), 3.10(q,J=7.5Hz,2H), 1.20(t,J=7.5Hz,3H).

Synthesis Example 27: 2-[3-(Ethylthio)-6-iodo-8-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6- Synthesis of (trifluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-066b of the present invention)

Step 1: Synthesis of 2-(ethylthio)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone

N,N-dimethyl in 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone 20g For a 80 ml solution of formazan, 4.2 g of ethane mercaptan and 9.4 g of potassium carbonate were added in order under ice cooling. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the stirring, the reaction mixture was stirred at room temperature for 1 hour. After the completion of the reaction, 100 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (100 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The residue obtained in n-hexane-acetic acid The ethyl ester (gradient from 100:0 to 80:20) was dissolved in medium pressure fractionation and purified by liquid chromatography to obtain 13.8 g of the target product as a pale yellow solid.

Melting point: 67-69°C

¹ H-NMR (CDCl ₃ ): δ 8.85-8.80 (m, 1H), 8.45-8.40 (m, 1H), 4.24 (s, 3H), 4.07 (s, 2H), 2.66 (q, J=7.4 Hz,2H),1.31(t,J=7.4Hz,3H).

Step 2: 2-Bromo-2-(ethylthio)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethyl Synthesis of ketones

Dichloro 2-(ethylthio)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone 11.4g To a 100 ml methane solution, 4.2 g of triethylamine was added at room temperature. After the addition, the reaction mixture was cooled to -20°C, and 8.8 g of trimethylsilyl trifluoromethanesulfonate was added. After the addition, the reaction mixture was stirred under ice cooling for 20 minutes. After the stirring, the reaction mixture was cooled to -20°C, and 14.1 g of trimethylphenylammonium tribromide was added. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the reaction, the reaction mixture was titrated to 100 ml of water under ice cooling, and extracted with chloroform (100 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 13.4 g of the target product as a black tea-colored oily substance.

¹ H-NMR (CDCl ₃ ): δ 8.90-8.80 (m, 1H), 8.50-8.40 (m, 1H), 7.14 (s, 1H), 4.27 (s, 3H), 3.05-2.80 (m, 2H) ), 1.39(t,J=7.6Hz,3H).

Step 3: 2-[3-(Ethylthio)-6-iodo-8-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-( Trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 1-1-066b of the present invention) Synthesis

Dissolve 300 mg of 5-iodo-3-(trifluoromethyl)pyridin-2-amine in 8 ml of propionitrile, and add 2-bromo-2-(ethylthio)-1-[3-methyl-6 at room temperature -(Trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone 345mg. After the addition, the reaction mixture was stirred for 1.5 hours under heating and refluxing. After the completion of the reaction, 20 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (20 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. 10 ml of diisopropyl ether was added to the precipitated solid and filtered to obtain 294 mg of the target substance as an orange solid.

Melting point: 222-225°C

¹ H-NMR(CDCl ₃ ): δ9.10-9.00(m,1H), 8.75-8.70(m,1H), 8.40-8.35(m,1H), 7.90-7.85(m,1H), 4.35(s ,3H), 3.18(q,J=7.4Hz,2H), 1.24(t,J=7.4Hz,3H).

Synthesis Example 28: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl-6-(trifluoro Methyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-057b of the present invention), 2-[3-(ethylsulfonyl)-7-(trifluoromethyl) Imidazo[1,2-b]pyridazin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 1 of the present invention) -1-057a) and 2-[3-(ethylsulfinyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl- Synthesis of 6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-057c of the present invention)

Step 1: 2-[3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl-6-(trifluoromethyl) Yl)-3H-imidazo[4,5-b]pyridine (Compound No.1-1-057b of the present invention)

Dissolve 42 mg of 5-(trifluoromethyl)pyridazine-3-amine in 3ml of acetonitrile, and add 2-bromo-2-(ethylthio)-1-[3-methyl-6-(trifluoro (Methyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone 100 mg. After the addition, the reaction mixture was stirred under heating and reflux for 2 hours. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain a crude product of 130 mg of the target product. This material can be used directly in the next step without further purification.

Step 2: 2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl-6-(trifluoromethyl) Fluoromethyl)-3H-imidazo[4,5-b]pyridine (compound No.1-1-057a of the present invention) and 2-[3-(ethylsulfinyl)-7-(trifluoromethyl Yl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (the compound No. of the present invention .1-1-057c) Synthesis

The crude product obtained in step 1 is 2-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl- 6-(Trifluoromethyl)-3H-imidazo[4,5-b]pyridine 120mg in chloroform 10ml solution, add 65% by mass of m-chloroperbenzoic acid (containing about 30% by mass of water) 99mg under ice cooling . After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) by medium pressure fractionation liquid chromatography to obtain 2 of the target product as a light yellow oil. -[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2- b]pyridazin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine 70mg and the target 2-[3-(ethylidene Sulfonyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4 ,5-b] Pyridine 41 mg.

2-[3-(Ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl-6-(trifluoromethyl )-3H-imidazo[4,5-b]pyridine ¹ H-NMR: δ8.90(d,J=1.8Hz,1H),8.79(d,J=1.5Hz,1H),8.55-8.50( m,1H), 8.42(d,J=2.1Hz,1H),4.02(s,3H), 3.75(q,J=7.5Hz,2H), 1.46(t,J=7.5Hz,3H).

2-[3-(Ethylsulfinyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-methyl-6-(trifluoromethyl Group)-3H-imidazo[4,5-b]pyridine ¹ H-NMR: δ8.82(d,J=2.1Hz,1H),8.78-8.74(m,1H),8.49-8.45(m, 1H), 8.42-8.38 (m, 1H), 4.36 (s, 3H), 4.18-4.00 (m, 1H), 3.85-3.70 (m, 1H), 1.55 (t, J=7.5Hz, 3H).

Synthesis Example 29: 5-(Ethylthio)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2-( Trifluoromethyl)imidazo[2,1-b][1,3,4]thiadiazole (compound No.2-1-002b of the present invention) and 5-(ethylsulfonyl)-6-[ 3-Methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2-(trifluoromethyl)imidazo[2,1-b][ 1,3,4] Synthesis of thiadiazole (Compound No. 2--1-002a of the present invention)

Step 1: 5-(Ethylthio)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2-(trifluoromethyl) Synthesis of fluoromethyl)imidazo[2,1-b][1,3,4]thiadiazole (compound No.2-1-002b of the present invention)

Dissolve 195 mg of 5-(trifluoromethyl)-1,3,4-thiadiazol-2-amine in propionitrile 5ml, add 2-bromo-2-(ethylthio)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine-2- Base] ethyl ketone 400mg. After the addition, the reaction mixture was stirred under heating and reflux for 3 hours. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 130 mg of the target white solid.

¹ H-NMR(CDCl ₃ ): δ8.82(d,J=1.2Hz,1H), 8.43(d,J=1.2Hz,1H), 4.24(s,3H), 2.66(q,J=7.5Hz ,2H),1.31(t,J=7.5Hz,3H).

Step 2: 5-(Ethylsulfonyl)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2- Synthesis of (trifluoromethyl)imidazo[2,1-b][1,3,4]thiadiazole (compound No.2-1-002a of the present invention)

In 5-(ethylthio)-6-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-2-(trifluoromethyl Yl)imidazo[2,1-b][1,3,4]thiadiazole 130mg in 10ml chloroform solution, 65% by mass m-chloroperbenzoic acid (containing about 30% by mass of water) 191mg was added under ice cooling . After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The residue obtained was purified by liquid chromatography with n-hexane-ethyl acetate (gradient from 100:0 to 50:50) dissolution, and the target product was obtained as a white solid. 52mg.

Melting point: 231-234°C

¹ H-NMR(CDCl ₃ ): δ8.76(s,1H),8.35(s,1H),4.11(s,3H),3.92(q,J=7.5Hz,2H),1.51(t,J= 7.5Hz, 3H).

Synthesis Example 30: 2-[3-(Ethylthio)-8-fluoro-6-iodoimidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl )-3H-imidazo[4,5-c]pyridine (Compound No. 1-8-008b of the present invention)

Step 1: Synthesis of 2-(ethylthio)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanone

In 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanone 2.36g of N,N-dimethyl For a 25ml solution of methylformamide, 546mg of ethane mercaptan and 1.21g of potassium carbonate were added in order under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the completion of the reaction, 50 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (50 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractional liquid chromatography in n-hexane-ethyl acetate (gradient from 100:0 to 80:20) to obtain 1.70 g of the target white solid.

Melting point: 90-93°C

¹ H-NMR(CDCl ₃ ): 9.03(s,1H), 8.19(d,J=1.0Hz,1H), 4.29(s,3H),4.08(s,2H), 2.65(q,J=7.4Hz) ,2H),1.32(t,J=7.4Hz,3H).

Step 2: 2-Bromo-2-(ethylthio)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethyl Synthesis of ketones

Dichloro 2-(ethylthio)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanone 1.63g A solution of 15 ml of methane, 600 mg of triethylamine was added at room temperature. After the addition, 1.25 g of trimethylsilyl trifluoromethanesulfonate was added to the reaction mixture under ice cooling. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the stirring, 2.02 g of trimethylphenylammonium tribromide was added to the reaction mixture under ice cooling. After the addition, the reaction mixture was stirred under ice cooling for 1 hour. After the reaction, the reaction mixture was titrated to 20 ml of water under ice cooling, and extracted with chloroform (20 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 2.09 g of the target product as a yellow oily substance.

¹ H-NMR (CDCl ₃ ): δ9.06 (s, 1H), 8.19 (s, 1H), 7.12 (s, 1H), 4.31 (s, 3H), 3.01-2.77 (m, 2H), 1.39 ( t,J=7.5Hz,3H).

Step 3: 2-[3-(Ethylthio)-8-fluoro-6-iodoimidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl) Synthesis of -3H-imidazo[4,5-c]pyridine (Compound No. 1-8-008b of the present invention)

Dissolve 250 mg of 3-fluoro-5-iodopyridin-2-amine in 5 ml of acetonitrile, and add 2-bromo-2-(ethylthio)-1-[3-methyl-6-(trifluoromethyl) at room temperature. )-3H-imidazo[4,5-c]pyridin-2-yl]ethanone 400mg. After the addition, the reaction mixture was stirred under heating and reflux for 1 hour. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The precipitated solid was separated by filtration to obtain 338 mg of the target brown solid.

¹ H-NMR(CDCl ₃ ): δ8.96(s,1H), 8.73(d,J=1.5Hz,1H), 8.19(d,J=0.9Hz,1H), 7.33(dd,J=9.0, 1.5Hz, 1H), 4.36 (s, 3H), 3.15 (q, J=7.5Hz, 2H), 1.23 (t, J=7.5Hz, 3H).

Reference Example 1: Synthesis of 2-bromo-1-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone

Step 1: Synthesis of ethyl 7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate

5.0 g of 4-(trifluoromethyl)pyridin-2-amine was dissolved in 50 ml of chlorobenzene, and 6.67 g of ethyl 3-bromo-2-oxopropionate was added at room temperature. After the addition was complete, the reaction mixture was stirred under heating and reflux for 6.5 hours. After the completion of the reaction, 20 ml of 1M sodium hydroxide aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate (20 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. Add a 3M aqueous hydrochloric acid solution to the obtained residue, and wash with 10 ml of ethyl acetate. Next, after adjusting the pH of the water layer to 2 to 3 with a 10M sodium hydroxide aqueous solution, it was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 3.94 g of the target product as a yellow solid.

Melting point: 170-175°C

¹ H-NMR(CDCl ₃ ): δ8.29(s,1H), 8.27(d,J=7.2Hz,1H), 8.01(s,1H), 7.07(dd,J=7.2,1.7Hz,1H) , 4.49(q,J=7.2Hz,2H),1.46(t,J=7.2Hz,3H).

Step 2: Synthesis of ethyl 3-iodo-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate

To ethyl 7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate 3.73g N,N-dimethylformamide 20ml solution, add N- Iodine succinimidyl 6.5g. After the addition, the reaction mixture was stirred at 80°C for 5 hours. After the completion of the reaction, water was added to the reaction mixture, and the precipitated solid was separated by filtration. The obtained solid was dissolved in 20 ml of chloroform, and washed with saturated sodium thiosulfate aqueous solution and then saturated sodium bicarbonate in this order. The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 5.08 g of the target substance as a flesh-colored solid.

Melting point: 183-185°C

¹ H-NMR(CDCl ₃ ): δ8.40(d,J=7.2Hz,1H),7.99(s,1H),7.17(dd,J=7.2,1.7Hz,1H),4.53(q,J= 7.2Hz, 2H), 1.50 (t, J=7.2Hz, 3H).

Step 3: Synthesis of ethyl 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate

A solution of 5.73 g of ethyl 3-iodo-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate in 40 ml of 1,4-dioxane, in order at room temperature Added 5.79g of diisopropylethylamine, 862mg of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and 682mg of ginseng (dibenzylideneacetone) dipalladium (zero value) And ethane mercaptan 1.85g. After the addition was completed, the inside of the reaction vessel was replaced with nitrogen, and the mixture was stirred under heating and reflux for 2 hours. After the reaction, the reaction mixture was filtered through Celite, and the Celite was washed with 30 ml of chloroform. The filtrate and washing liquid obtained are blended, and the solvent is distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) by medium pressure fractionation liquid chromatography to obtain 5.58 g of the target brown solid.

Melting point: 50-52℃

¹ H-NMR(CDCl ₃ ): δ8.67(d,J=7.4Hz,1H), 8.02-8.00(m,1H), 7.15(dd,J=7.4,1.8Hz,1H), 4.52(q, J=7.0Hz,2H), 2.98(q,J=7.5Hz,2H), 1.48(t,J=7.0Hz,3H), 1.20(t,J=7.5Hz,3H).

Step 4: Synthesis of 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid

In ethyl 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate 5.58g in ethanol 60ml and tetrahydrofuran 30ml solution, add 3M at room temperature 10ml of sodium hydroxide aqueous solution. After the addition, the reaction mixture was stirred at room temperature for 5 hours. After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure. A 1M aqueous hydrochloric acid solution was added to the obtained residue, and after the pH of the aqueous layer became 2, it was extracted with ethyl acetate (20ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 3.40 g of the target product as a yellow solid.

Melting point: 163-171°C

¹ H-NMR(CDCl ₃ ): δ8.69(d,J=7.2Hz,1H), 8.19(s,1H), 7.22(dd,J=7.2,1.4Hz,1H), 3.06(q,J= 7.4Hz, 2H), 1.23 (t, J=7.4Hz, 3H) ( _{the peak of the proton of CO 2} H cannot be observed).

Step 5: Synthesis of 3-(ethylthio)-N-methoxy-N-methyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxyamide

To 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid 2.52g dichloromethane 30ml solution, add ethylenedichloride under ice cooling 3.31g and 30mg of N,N-dimethylformamide. After the addition was complete, the reaction mixture was stirred at room temperature for 3 hours. After the stirring, the solvent was distilled off from the reaction mixture under reduced pressure to obtain the crude product, 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine- 2-carboxylic acid chloride. Dissolve the resulting crude product, 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid chloride in 5ml of dichloromethane, and use it separately. A 15 ml solution of 931 mg of N,O-dimethylhydroxyamine hydrochloride and 1.93 g of triethylamine prepared in a container was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 1.5 hours. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The obtained organic layer was washed with dilute hydrochloric acid and saturated sodium bicarbonate aqueous solution in order, and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 2.50 g of the target product as a flesh-colored solid.

Melting point: 82-84°C

¹ H-NMR(CDCl ₃ ): δ8.62(d,J=7.2Hz,1H),7.98-7.95(m,1H),7.14(dd,J=7.2,1.7Hz,1H), 3.80(s, 3H), 3.44 (s, 3H), 2.91 (q, J=7.4Hz, 2H), 1.22 (t, J=7.4Hz, 3H).

Step 6: Synthesis of 1-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone

In a nitrogen environment, in 3-(ethylthio)-N-methoxy-N-methyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxyamide 2.45 g of tetrahydrofuran 25ml solution, add about 3M methylmagnesium bromide diethyl ether solution 2.7ml under ice cooling. After the addition, the reaction mixture was stirred under ice cooling for 1 hour. After the reaction, the reaction mixture was titrated to 4M salt under ice cooling The acid aqueous solution is 10ml, and it is extracted with ethyl acetate (20ml×2). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution, and dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 2.08 g of the target brown solid.

Melting point: 60-64℃

¹ H-NMR(CDCl ₃ ): δ8.67(d,J=7.2Hz,1H),8.03-7.99(m,1H),7.15(dd,J=7.2,1.7Hz,1H),3.01(q, J=7.4Hz, 2H), 2.80(s, 3H), 1.18(t, J=7.4Hz, 3H).

Step 7: Synthesis of 1-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone

A solution of 2.08g of 1-[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone in 40ml of methanol and 20ml of water. Add 13.3 g of Oxone (registered trademark of DuPont). After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the reaction was completed, a 25 ml solution of 2.28 g of sodium thiosulfate in water was added to the reaction mixture. Next, a 10M aqueous sodium hydroxide solution was added to make the water layer alkaline, and then methanol was distilled off under reduced pressure. Ethyl acetate (40mlx2) was added to the resulting residue for extraction. The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 2.11 g of the target product as a yellow solid.

Melting point: 135-138°C

¹ H-NMR(CDCl ₃ ): δ9.44(d,J=7.5Hz,1H), 8.12-8.09(m,1H), 7.27-7.24(m,1H), 3.80(q,J=7.5Hz, 2H), 2.80 (s, 3H), 1.35 (t, J=7.5Hz, 3H).

Step 8: Synthesis of 2-bromo-1-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone

In 15ml solution of 2.05g of 1-[3-(ethylsulfonyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone in 15ml at 10℃ Approximately 10.2 g of 5.1M hydrogen bromide acetic acid solution and 1.13 g of bromine were added sequentially. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the stirring, 205 mg of bromine was added to the reaction mixture, and the mixture was stirred at room temperature overnight. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (20 ml×2). The resulting organic layer was washed with a 5 mass% sodium bisulfite aqueous solution, and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 2.48 g of the target product as a yellow solid.

Melting point: 122-123°C

¹ H-NMR(CDCl ₃ ): δ9.45(d,J=7.5Hz,1H),8.14-8.11(m,1H),7.33-7.27(m,1H),4.78(s,2H),3.78( q,J=7.4Hz,2H),1.37(t,J=7.4Hz,3H).

Reference Example 2: Synthesis of 5-(ethylthio)-2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxylic acid

Step 1: Synthesis of ethyl 2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxylate

4.0 g of 5-(trifluoromethyl)thiazol-2-amine was dissolved in 80 ml of chlorobenzene, and 7.2 g of ethyl 3-bromo-2-oxopropionate was added at room temperature. After the addition, the reaction mixture was stirred under heating and reflux for 3 hours. After the stirring, 3.09 g of ethyl 3-bromo-2-oxopropionate was added to the reaction mixture. After the addition, the reaction mixture was stirred under heating and reflux for 1 hour. End of stirring Then, 2.4 g of ethyl 3-bromo-2-oxopropionate was added to the reaction mixture. After the addition, the reaction mixture was stirred under heating and reflux for 2 hours. After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure. A 1M sodium hydroxide aqueous solution was added to the obtained residue to make the pH of the water layer 8 and then extracted with ethyl acetate (20ml×3). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The precipitated solids are separated by filtration. The obtained solid was washed with diisopropyl ether to obtain 2.12 g of the target white solid.

¹ H-NMR(CDCl ₃ ): δ8.14(s,1H),7.92(s,1H), 4.42(q,J=7.5Hz,2H), 1.43(t,J=7.5Hz,3H).

Step 2: Synthesis of ethyl 5-iodo-2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxylate

In 10ml solution of ethyl 2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxylate 7.97g N,N-dimethylformamide, add N- Iodosuccinimide 3.58g. After the addition, the reaction mixture was stirred at 80°C for 4 hours. After the completion of the reaction, a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain 3.09 g of the target white solid.

¹ H-NMR(CDCl ₃ ): δ7.90-7.86(m,1H), 4.44(q,J=7.5Hz,2H), 1.45(t,J=7.5Hz,3H).

Step 3: Synthesis of ethyl 3-(ethylthio)-2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxylate

A solution of ethyl 5-iodo-2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxylate 2.00g in 20ml 1,4-dioxane, in order at room temperature Add diisopropyl Ethyl amine 1.98g, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene 296mg, ginseng (dibenzylideneacetone) two palladium (0 valence) 234mg and ethane sulfide Alcohol 636mg. After the addition, the inside of the reaction vessel was replaced with nitrogen, and the mixture was stirred under heating and reflux for 4 hours. After the reaction, the reaction mixture was filtered through Celite, and the Celite was washed with 30 ml of chloroform. The filtrate and washing liquid obtained are blended, and the solvent is distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) by medium pressure fractionation liquid chromatography to obtain 1.11 g of the target yellow solid.

¹ H-NMR(CDCl ₃ ): δ8.04-7.98(m,1H), 4.44(q,J=7.5Hz,2H), 2.99(q,J=7.5Hz,2H), 1.46(t,J= 7.5Hz, 3H), 1.23 (t, J=7.5Hz, 3H).

Step 4: Synthesis of 5-(ethylthio)-2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxylic acid

In ethyl 3-(ethylthio)-2-(trifluoromethyl)imidazo[2,1-b]thiazole-6-carboxylate 1.09g in ethanol 10ml and tetrahydrofuran 10ml solution, add at room temperature 6.8ml of 1M sodium hydroxide aqueous solution. After the addition was complete, the reaction mixture was stirred at room temperature overnight. After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure. Add 1M hydrochloric acid aqueous solution to the obtained residue to make the pH of the water layer 2~3, and then extract with chloroform (20ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 896 mg of the target product as a yellow solid.

¹ H-NMR(CDCl ₃ ): 8.06-8.02(m,1H),3.04(q,J=7.5Hz,2H),1.25(t,J=7.5Hz,3H) (the peak value of the proton of _{CO 2 H cannot} Observed).

Reference Example 3: From Step 1 of Reference Example 1, the following compounds were synthesized by the same method as Step 4.

3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid

Melting point: 200-201°C

¹ H-NMR(CDCl ₃ ): δ8.93(s,1H), 8.20(d,J=9.6Hz,1H), 7.56(dd,J=9.6,1.8Hz,1H),3.06(qJ=7.4Hz ,2H),1.23(t,J=7.4Hz,3H) ( _{the peak of the proton of CO 2} H cannot be observed).

3-(Ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyrazine-2-carboxylic acid

Melting point: 175-178°C

¹ H-NMR(CDCl ₃ ): δ9.21(s,1H),8.84(s,1H),3.08(q,J=7.2Hz,2H),1.22(t,J=7.2Hz,3H)(CO ₂ The peak of the proton of H cannot be observed).

Reference Example 4: ^{Synthesis of N 3} ,2-dimethyl-6-(trifluoromethyl)pyridine-3,4-diamine

Step 1: Synthesis of 4-bromo-2-methyl-6-(trifluoromethyl)pyridin-3-amine

To a solution of 3.0 g of 2-methyl-6-(trifluoromethyl)pyridine-3-amine in 30 ml of acetonitrile, 3.03 g of N-bromosuccinimide was added at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 1.5 hours. After the reaction, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) by medium pressure fractionation liquid chromatography to obtain 4.0 g of the target brown solid.

Melting point: 40-41℃

¹ H-NMR (CDCl ₃ ): δ7.61 (s, 1H), 4.40 (brs, 2H), 2.52 (s, 3H).

Step 2: Synthesis of 4-bromo-N,2-dimethyl-6-(trifluoromethyl)pyridin-3-amine

To 63% by mass sodium hydride (dispersed in mineral oil) 537mg N,N-dimethylformamide 5ml solution, add 4-bromo-2-methyl-6-(trifluoromethyl)pyridine under ice cooling -3-amine 3.0g N,N-dimethylformamide 12ml solution. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the stirring, 2.0 g of methyl iodide was added to the reaction mixture under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and extraction was carried out with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) by medium pressure fractionation liquid chromatography to obtain 2.82 g of the target product as a yellow oil.

¹ H-NMR(CDCl ₃ ): δ7.62(s,1H),3.01(s,3H),2.65(s,3H) (the peak of NH proton cannot be observed).

Step 3: ^{Synthesis of N 3} ,2-dimethyl-6-(trifluoromethyl)pyridine-3,4-diamine

Combine 1.0 g of 4-bromo-N,2-dimethyl-6-(trifluoromethyl)pyridin-3-amine, 186 mg of acetone, 243 mg of copper (II) acetone, and 1.81 g of cesium carbonate. A solution of 30 ml of methylpyrrolidone was added to the autoclave reactor. After the addition, 20 ml of 28% by mass ammonia water was added to the reaction mixture at room temperature. After the addition was completed, after sealing the reaction vessel, the reaction mixture was heated to 140°C and stirred for 1 hour. After the completion of the reaction, 20 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (20 ml×2). Saturate the resulting organic layer Dehydration is carried out in the order of salt water and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography eluted in n-hexane-ethyl acetate (gradient from 100:0 to 0:100) to obtain 189 mg of the target white solid.

¹ H-NMR (CDCl ₃ ): 6.84 (s, 1H), 4.53 (brs, 2H), 2.69 (s, 3H), 2.50 (s, 3H) (the peak of the proton of NH cannot be observed).

Reference Example 5: Synthesis of 2-methyl-6-(perfluoroethyl)pyrimidin-4-amine

Step 1: Synthesis of (Z)-ethyl 3-ethoxy-4,4,5,5,5-pentafluoropenta-2-enoate

To a solution of 20.7g of 4,4,5,5,5-pentafluoro-3-oxogel ethyl oxalate in 150ml of acetone, add 24.4g of potassium carbonate and 15.7g of ethyl trifluoromethanesulfonate in order under ice cooling . After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After the reaction, the reaction mixture was filtered through celite, and the celite was washed with 50 ml of acetone. The filtrate and washing liquid obtained are blended, and the solvent is distilled off under reduced pressure. Add 30 ml of water to the obtained residue, and extract in hexane (30 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain a crude product of 20.53 g of the target product as a colorless and transparent oily substance.

¹ H-NMR(CDCl ₃ ): δ5.80(s,1H),4.33(q,J=7.0Hz,2H),4.22(q,J=7.0Hz,2H),1.36(t,J=7.0Hz ,3H),1.32(t,J=7.0Hz,3H).

Step 2: Synthesis of 2-methyl-6-(perfluoroethyl)pyrimidin-4-ol

To acetamidine hydrochloride 6.49g dimethyl sulfoxide 75ml solution, add about 20% by mass of sodium ethoxide ethanol in order at 50℃ Solution 23.3g and (Z)-ethyl 3-ethoxy-4,4,5,5,5-pentafluoropenta-2-enoate 15.0g. After the addition, the reaction mixture was stirred at 50°C for 2 hours. After the stirring, 5.84 g of an ethanol solution of about 20% by mass of sodium ethoxide was added to the reaction mixture at 50°C. After the addition, the reaction mixture was stirred at 50°C for 2.5 hours. After the stirring, the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, 50 ml of water was added to the reaction mixture, and the mixture was extracted with diethyl ether (50 ml×2). Add concentrated hydrochloric acid to the resulting water layer to make the pH of the water layer 1-2, and then extract with chloroform (20ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain a crude product of 7.0 g of the target product as a white solid.

Melting point: 135-138°C

¹ H-NMR (CDCl ₃ ): δ 6.77 (s, 1H), 2.57 (s, 3H) (the peak of the proton of OH cannot be observed).

Step 3: Synthesis of 4-chloro-2-methyl-6-(perfluoroethyl)pyrimidine

To a solution of 8.7 g of 2-methyl-6-(perfluoroethyl)pyrimidin-4-ol in 20 ml of sulfite chloride, 30 mg of N,N-dimethylformamide was added at room temperature. After the addition, the reaction mixture was stirred under heating and reflux for 1 hour. After the reaction, the reaction mixture was allowed to cool to room temperature, titrated in ice water, and extracted with diethyl ether (20 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain a crude product of 9.33 g of the target product as a reddish-brown oily substance.

¹ H-NMR (CDCl ₃ ): δ7.54 (s, 1H), 2.82 (s, 3H).

Step 4: Synthesis of 2-methyl-6-(perfluoroethyl)pyrimidin-4-amine

In 9.33g of crude product of 4-chloro-2-methyl-6-(perfluoroethyl)pyrimidine To a solution of 20 ml of acetonitrile, 20 ml of 28% by mass ammonia water was added at room temperature. After the addition, the reaction mixture was stirred at room temperature for 3 days. After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure. Add 20ml of water to the residue obtained, and extract with ethyl acetate (20ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 6.75 g of the target product as a reddish brown solid.

Melting point: 95-105°C

¹ H-NMR (CDCl ₃ ): δ6.61 (s, 1H), 5.12 (brs, 2H), 2.59 (s, 3H).

Reference Example 6: From Step 1 of Reference Example 5, the following compounds were synthesized by the same method as Step 4.

6-(perfluoroethyl)pyrimidin-4-amine

¹ H-NMR (CDCl ₃ ): δ8.70 (s, 1H), 6.79 (s, 1H), 5.22 (brs, 2H).

Reference Example 7: Synthesis of 4-chloro-6-(perfluoroethyl)nicotinaldehyde

Step 1: Synthesis of 4-chloro-6-(perfluoroethyl)nicotinic acid

Under nitrogen, add about 1.6M n-butyllithium in n-hexane solution 17.9ml in 20ml solution of 2,2,6,6-tetramethylpiperidine 4.04g in tetrahydrofuran at -78°C. After the addition, the reaction mixture was heated to 0°C and stirred for 10 minutes. After the stirring, the reaction mixture was cooled to -78°C, and a solution of 2.3 g of 6-(perfluoroethyl)nicotinic acid in 20 ml of tetrahydrofuran was added. After the addition, the reaction mixture was heated to -40°C and stirred for 1.5 hours. After the stirring, the reaction mixture was cooled to -78°C, and 4.5 g of hexachloroethane was added. After the addition, the reaction mixture was stirred at -78°C for 1.5 hours. reaction After the completion, 25 ml of saturated aqueous ammonium chloride solution was added to the reaction mixture at -78°C. After the addition, the reaction mixture was heated to room temperature, and about 1.0 M sodium hydroxide aqueous solution was added to adjust the pH to 9, and then washed with diethyl ether (20 ml). Concentrated hydrochloric acid was added to the obtained water layer, and after preparing the pH of the aqueous solution to be 2, it was extracted with ethyl acetate (20 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 1.08 g of 4-chloro-6-(perfluoroethyl)nicotinic acid, which is a brown oily substance of the target product.

¹ H-NMR(CDCl ₃ ): δ9.25(s,1H),7.84(s,1H) ( _{the peak of the proton of CO 2} H cannot be observed).

Step 2: Synthesis of [4-chloro-6-(perfluoroethyl)pyridin-3-yl]methanol

To a solution of 1.0g of 4-chloro-6-(perfluoroethyl)nicotinic acid in 10ml of tetrahydrofuran, add 8.5ml of a solution of 0.85M of borane-tetrahydrofuran complex in tetrahydrofuran at -50°C. After the addition, the reaction mixture was warmed to room temperature and stirred overnight. After the reaction, the reaction mixture was titrated to a 1M aqueous hydrochloric acid solution under ice cooling, and extracted with ethyl acetate (20 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 950 mg of target orange oily [4-chloro-6-(perfluoroethyl)pyridin-3-yl]methanol.

¹ H-NMR (CDCl ₃ ): δ8.87 (s, 1H), 7.71 (s, 1H), 4.92 (s, 2H) (the peak of the proton of OH cannot be observed).

Step 3: Synthesis of 4-chloro-6-(perfluoroethyl)nicotinaldehyde

To [4-chloro-6-(perfluoroethyl)pyridin-3-yl]methanol 930mg in dichloromethane 10ml solution, add 3g silica and pyridine chlorochromate in order at room temperature Onium 1.53g. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the stirring, 500 mg of pyridinium chlorochromate was added to the reaction mixture. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After the reaction, the reaction mixture was filtered through Celite, and the Celite was washed with 100 ml of n-hexane-ethyl acetate [2:1 (volume ratio)]. The filtrate and washing liquid obtained are blended, and the solvent is distilled off under reduced pressure. The obtained residue was purified by liquid chromatography with n-hexane-ethyl acetate (gradient from 100:0 to 30:70) dissolution, medium pressure fractionation, and 154 mg of the target yellow oily substance was obtained.

¹ H-NMR (CDCl ₃ ): δ 10.54 (s, 1H), 9.14 (s, 1H), 7.84 (s, 1H).

Reference Example 8: From Step 1 of Reference Example 7, the following compounds were synthesized by the same method as Step 3.

4-chloro-6-(trifluoromethyl)nicotinaldehyde

¹ H-NMR (CDCl ₃ ): δ 10.54 (s, 1H), 9.12 (s, 1H), 7.81 (s, 1H).

Reference Example 9: Synthesis of 3-nitro-5-(trifluoromethyl)picolinaldehyde

A solution of 930 mg of selenium dioxide and 1.46 g of 2-methyl-3-nitro-5-(trifluoromethyl)pyridine in 10 ml of 1,4-dioxane was stirred under heating under reflux for 8 hours. After the stirring, the reaction mixture was filtered through celite, and the celite was washed with 10 ml of 1,4-dioxane. The obtained filtrate and washing liquid were mixed, the solvent was distilled off under reduced pressure, 5 ml of saturated sodium bicarbonate was added, and the mixture was extracted with ethyl acetate (10 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. Will get The residue was dissolved in n-hexane-ethyl acetate (gradient from 100:0 to 50:50) and purified by liquid chromatography. 10 ml of toluene was added to the residue obtained by concentration, and the solvent was distilled off under reduced pressure. Next, 10 ml of toluene was added, and the solvent was distilled off under reduced pressure to obtain 1.07 g of the target product as a brown liquid.

¹ H-NMR (CDCl ₃ ): δ 10.32 (s, 1H), 9.25-9.20 (m, 1H), 8.53-8.49 (m, 1H).

Reference Example 10: Synthesis of 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-amine

Step 1: Synthesis of tert-butyl[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]carbamate

A solution of 3.0 g of 3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid in 30 ml of 2-methyl-2-propanol at room temperature 3.14 g of triethylamine and 3.40 g of diphenyl azide phosphate were added. After the addition, the reaction mixture was stirred under heating and reflux for 2 hours. After the reaction, the solvent was distilled off from the reaction mixture. Add 20ml of water to the residue obtained, and extract with ethyl acetate (20ml×2). The resulting organic layer was washed with saturated sodium bicarbonate aqueous solution, and then dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by fractionation liquid chromatography in n-hexane-ethyl acetate (50:50) elution to obtain 2.12 g of the target product as a pale yellow solid.

¹ H-NMR(CDCl ₃ ): δ8.42(d,J=7.0Hz,1H),7.93-7.88(m,1H),7.13-7.01(m,2H),2.68(q,J=7.4Hz, 2H), 1.56(s, 9H), 1.21(t, J=7.4Hz, 3H).

Step 2: 3-(Ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridine- Synthesis of 2-amine

A solution of 2.0g tert-butyl[3-(ethylthio)-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]carbamate in 10ml of dichloromethane , Add 2.1ml of trifluoroacetic acid under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After the stirring, 10 ml of trifluoroacetic acid was added to the reaction mixture. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After the reaction, the solvent was distilled off from the reaction mixture. Add 20 ml of water to the obtained residue, and extract with chloroform (20 ml×2). The resulting organic layer was washed with 1M sodium hydroxide aqueous solution and dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 1.69 g of the target product as a yellow oily substance.

¹ H-NMR(CDCl ₃ ): δ8.31(d,J=7.0Hz,1H),7.63-7.58(m,1H),6.98(dd,J=7.0,1.6Hz,1H), 4.41(brs, 2H), 2.63(q,J=7.4Hz,2H), 1.21(t,J=7.4Hz,3H).

Reference Example 11: Synthesis of 3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxyamide

In a solution of 1.34 g of 3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid in 20 ml of dichloromethane, add ethylene dichloride under ice cooling 882mg and N,N-dimethylformamide 10mg. After the addition was complete, the reaction mixture was stirred at room temperature for 2.5 hours. After the stirring, the solvent was distilled off from the reaction mixture under reduced pressure to obtain the crude product, 3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2 -Carboxylic acid chloride. Dissolve the resulting crude product, 3-(ethylthio)-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid chloride in 2ml of tetrahydrofuran, and put it in another container Modification of 28 qualities The amount of% ammonia water is 20ml, and it is added under ice-cooling. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the completion of the reaction, 10 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 1.8 g of the target product as a pale yellow solid.

¹ H-NMR(CDCl ₃ ): δ8.90(s,1H), 7.71(d,J=9.4Hz1H), 7.47(dd,J=9.4,2.0Hz,1H), 7.38(brs,1H), 5.66 (brs,1H),3.03(q,J=7.4Hz,2H),1.21(t,J=7.4Hz,3H).

Reference Example 12: Synthesis of 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone

Step 1: Synthesis of (S)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanol

Dissolve 37.7 g of N ² -methyl-5-(trifluoromethyl)pyridine-2,3-diamine in 150 ml of pyridine, and add (S)-(-)-2-acetoxypropane at -20°C Acetyl chloride 32.8g. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After the stirring, the solvent was distilled off from the reaction mixture under reduced pressure. The obtained residue was dissolved in 150 ml of ethanol, and 39.4 ml of 10M sodium hydroxide aqueous solution was added at room temperature. After the addition, the reaction mixture was stirred under heating and reflux for 2 hours. After the stirring, 20 ml of a 10M aqueous sodium hydroxide solution was added to the reaction mixture at room temperature. After the addition, the reaction mixture was stirred for 4.5 hours under heating under reflux. After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure. Concentrated hydrochloric acid was added to the residue obtained, and the aqueous solution was prepared so that the pH of the aqueous solution became 4, and then extracted with ethyl acetate (100 ml×2). The resulting organic layer was dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain (S)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5 -b]pyridin-2-yl]ethanol 59.8g.

¹ H-NMR (CDCl ₃ ): δ8.65 (s, 1H), 8.23 (s, 1H), 5.20 (brs, 1H), 3.97 (s, 3H), 2.99 (brs, 1H), 1.75 (d, J=6.3Hz, 3H).

Step 2: Synthesis of 1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone

The temperature of (S)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanol 48.3g in 200ml acetic acid solution was heated to 90 At ℃, add 50ml solution of 14.8g chromium oxide (VI) in water. After the addition, the reaction mixture was stirred for 1.5 hours under heating and refluxing. After the stirring, a solution of 5 g of chromium oxide (VI) in 10 ml of water was added to the reaction mixture at 90°C. After the addition, the reaction mixture was stirred for 1.5 hours under heating and refluxing. After the reaction, the reaction mixture was titrated to 800 ml of water at room temperature. The precipitated solids are separated by filtration. By washing the obtained solid with water, 1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine-2, which is a brown solid, is obtained -Base] ethyl ketone 35.6g.

Melting point: 106-108°C

¹ H-NMR(CDCl ₃ ): δ8.82(d,J=1.5Hz,1H), 8.43(d,J=1.5Hz,1H), 4.23(s,3H), 2.86(s,3H).

Step 3: Synthesis of 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone

Dissolve 35.6g of 1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]ethanone in 300ml of toluene and about 5.1M hydrogen bromide Acetic acid Liquid 150ml solution, add 25.8g bromine under ice cooling. After the addition, the reaction mixture was stirred at room temperature for 2 hours. After the stirring, 3.12 g of bromine was added to the reaction mixture at room temperature. After the addition, the reaction mixture was stirred at room temperature for 1 hour. After the stirring, 2.58 g of bromine was added to the reaction mixture at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After the completion of the reaction, the reaction mixture was added with a 10 M sodium hydroxide aqueous solution under ice cooling to adjust the pH to 3, and then extracted with toluene (200 ml×2). After washing the resulting organic layer with saturated sodium bisulfite aqueous solution, it is dehydrated in the order of saturated brine and then anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The precipitated solids are separated by filtration. The obtained solid was washed with diisopropyl ether to obtain 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5 -b]pyridin-2-yl]ethanone 36.6g.

Melting point: 90-91℃

¹ H-NMR(CDCl ₃ ): δ8.86(d,J=1.8Hz,1H), 8.47(d,J=1.8Hz,1H), 4.85(s,2H), 4.26(s,3H).

Reference Example 13: Synthesis of 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanone

Step 1: Synthesis of (S)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanol

Dissolve 3.34 g of N ³ -methyl-6-(trifluoromethyl)pyridine-3,4-diamine in 20 ml of pyridine, and add (S)-(-)-2-acetoxypropane at -20°C Acetyl chloride 2.89g. After the addition was complete, the reaction mixture was stirred at room temperature for 20 minutes. After the stirring, the solvent was distilled off from the reaction mixture under reduced pressure. The obtained residue was dissolved in 20 ml of ethanol, and 3.5 ml of 10M sodium hydroxide aqueous solution was added at room temperature. After the addition, the reaction mixture was stirred under heating and reflux for 1 hour. After the stirring, 1.8 ml of a 10M aqueous sodium hydroxide solution was added to the reaction mixture at room temperature. After the addition, the reaction mixture was stirred under heating and reflux for 2 hours. After the completion of the reaction, 50 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (50 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The obtained residue was purified by liquid chromatography in n-hexane-ethyl acetate (gradient of 100:0-50:50) dissolution and fractionation to obtain 3.0 g of the target product as a pale pink solid.

Melting point: 97-100°C

¹ H-NMR(CDCl ₃ ): δ8.84(s,1H), 8.04(d,J=0.7Hz,1H),5.31-5.14(m,1H),4.02(s,3H),3.03(d, J=7.2Hz, 1H), 1.78 (d, J=6.5Hz, 3H).

Step 2: Synthesis of 1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanone

The temperature of (S)-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanol 3.0g in 30ml acetic acid solution was heated to 90 At ℃, add 1.22g of chromium oxide (VI) in 10ml of water. After the addition, the reaction mixture was stirred under heating and reflux for 1 hour. After the completion of the reaction, 50 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (50 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure to obtain 1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c] as a light yellow solid. Pyridin-2-yl] ethyl ketone 2.59g.

Melting point: 136-140°C

¹ H-NMR(CDCl ₃ ): δ9.03(s,1H), 8.19(d,J=0.9Hz,1H), 4.28(s,3H), 2.89(s,3H).

Step 3: Synthesis of 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanone

To a solution of 2.55 g of 1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl]ethanone in 30ml of dichloromethane, add at room temperature 1.16g triethylamine. After the addition, 2.44 g of trimethylsilyl trifluoromethanesulfonate was added to the reaction mixture under ice cooling. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the stirring, 3.95 g of trimethylphenylammonium tribromide was added to the reaction mixture under ice cooling. After the addition, the reaction mixture was stirred under ice cooling for 30 minutes. After the reaction, 50 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (30 ml×2). The resulting organic layer was dehydrated with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure. The precipitated solids are separated by filtration. The obtained solid was washed with n-hexane to obtain 2-bromo-1-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5- c]Pyridin-2-yl]ethanone 2.66g.

Melting point: 127-131°C

¹ H-NMR(CDCl ₃ ): δ9.07(s,1H), 8.21(d,J=1.0Hz,1H), 4.87(s,2H), 4.31(s,3H).

The compound of the present invention can be synthesized according to the aforementioned manufacturing method and synthesis example. Although examples of fused heterocyclic compounds prepared in the same manner as Synthesis Example 1 to Synthesis Example 30 are shown in Table 5 to Table 23, and examples of the production intermediates are shown in Table 24 to Table 31, this Condensed heterocyclic compounds included in the invention and their preparation Manufacturing intermediates are not limited to these.

Still, the description of "Me" in the table means methyl, and the following is the same, "Et" means ethyl, "Pr-c" means cyclopropyl, "Bu-n" means n-butyl, and "Bu-t" means For tertiary butyl, "Ph" means phenyl, "Ac" means acetyl, and "TMS" means trimethylsilyl. The substituents represented by Z1 to Z21 in the table represent the following structures. In addition, "*1" in the table indicates that the compound is solid, "*2" indicates that the compound is oily or resinous, "*5" indicates that the compound is decomposed when the melting point of the compound is measured, and "mp" indicates the melting point (unit: °C) ). In addition, in the description of the melting point in the table, ">" indicates that the compound has a higher melting point than the marked temperature. For example, the mark ">250" means that the compound has not melted at 250°C.

^{The 1} H-NMR data of the compound of the present invention and the production intermediate are shown in Table 32. In addition, the proton nuclear magnetic resonance chemical shift value is measured using Me ₄ Si (tetramethylsilane) as a reference substance in a deuterated chloroform solvent at 300 MHz (model; ECX300 or ECP300, manufactured by JEOL). However, No.i-3-042 and No.i-3-048 are measured in deuterated dimethyl sulfide solvent, and No.i-1-037 is measured in heavy water solvent.

The symbols in the proton nuclear magnetic resonance chemical shift values indicate the following meanings.

s: singlet, brs: wide singlet, d: doublet, dd: doublet Heavy state, t: triplet state, q: quartet state, m: multiplet state

Next, the usefulness of the pest control agent as the compound of the present invention will be specifically described in the following test examples, but the present invention is not limited to these.

Test example 1: Insecticidal test for brown planthopper

Dilute the 10% emulsion of the compound of the present invention (depending on the compound and test the 10% hydrating agent) with the water added with the spreading agent to prepare a 500 ppm concentration of the medicinal solution. Soak the sheath of rice leaf in the liquid for about 10 seconds. After the immersion operation is over, the leaf sheath of the rice leaf treated with the liquid medicine is air-dried and put into the test tube. Here, 5 3rd instar larvae of Nilaparvata lugens (Nilaparvata lugens) were placed in each test tube, covered with a sponge, and kept in a constant temperature room at 25°C. After 6 days of containment, the number of dead insects of the brown planthopper in the test tube was investigated, and the dead insect rate (%) was calculated (the number of dead insects ÷ the number of tested insects × 100). Still, the experiment is carried out in a 2-continuous system.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 90%.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-005a, 1-1-006a, 1-1-009a, 1-1-015a, 1-1-020a, 1-1- 023a, 1-1-024a, 1-1-035a, 1-1-036a, 1-1-038a, 1-1-039a, 1-1-040a, 1-1-042a, 1-1-043a, 1-1-044a, 1-1-049a, 1-1-052a, 1-1-057a, 1-1-057c, 1-1-058a, 1-1-064a, 1-1-072a, 1- 1-074a, 1-1-095a, 1-1-096a, 1-1-097a, 1-1-099a, 1-1-100a, 1-1-105a, 1-1-106a, 1-1- 116a, 1-1-1117a, 1-1-1122a, 1-1-1123a, 1-1-1124a, 1-1-1125a, 1-1-1138a, 1-1-1166a, 1-1-1170a, 1-1-171a, 1-1-173a, 1-1-182a, 1-1-183a, 1-1-183b, 1-1-185a, 1-1-189a, 1-1-190a, 1- 1-191a, 1-1-192a, 1-1-193a, 1-1-196a, 1-1-197a, 1-1-198a, 1-2-001a, 1-2-002a, 1-3- 001a, 1-3-003a, 1-3-005a, 1-3-007a, 1-4-002a, 1-5-002a, 1-8-002a, 1-8-005a, 1-8-010a, 1-8-016a, 1-9-002a, 1-11-001a, 1-11-001b, 1-11-002a, 1-11-003a, 1-11-004a, 1-11-004b, 1- 11-008a, 1-11-009a, 1-12-003a, 1-12-004a, 1-12-006a, 1-12-007a, 1-12-008a, 1-12-009a, 1-12 012a, 1-14-001a, 1-16-001a, 1-16-001b, 2-1-001a, 3-1-002a

Test Example 2: Insecticidal Test on Plutella xylostella

Dilute the 10% emulsion of the compound of the present invention (depending on the compound and test 10% hydrating agent) with the water added with the spreading agent to prepare a 500 ppm concentration of the medicinal solution. Soak the cabbage leaves in the liquid for about 10 seconds. After the dipping operation is over, the cabbage leaves treated with the liquid medicine are air-dried and placed in a shallow dish. Here, the 3rd instar larvae of the diamondback moth (Plutella xylostella) were placed in 5 larvae in each tray, covered with a lid, and stored in a thermostatic chamber at 25°C. Six days after containment, the number of dead insects of the diamondback moth in the platter was investigated, and the mortality rate was calculated from the same calculation formula as in Test Example 1. Still, the experiment is carried out in a 2-continuous system.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 90%.

Compounds of the present invention: 1-1-1-001a, 1-1-1-001b, 1-1-1-001c, 1--1-002a, 1--1-002b, 1--1-003a, 1-1-1-003c, 1-1-1 004a, 1-1-005a, 1-1-005c, 1-1-006a, 1-1-007a, 1-1-008a, 1-1-009a, 1-1-011a, 1-1-012a, 1-1-012b, 1-1-013a, 1-1-013b, 1-1-013c, 1-1-014a, 1-1-014b, 1-1-014c, 1-1-015a, 1- 1-015b, 1-1-016a, 1-1-016b, 1-1-016c, 1-1-017a, 1-1-018a, 1-1-019a, 1-1-020a, 1-1-1 020b, 1-1-021b, 1-1-022a, 1-1-023a, 1-1-023b, 1-1-023c, 1-1-024a, 1-1-026a, 1-1-027a, 1-1-027b, 1-1-029a, 1-1-030a, 1-1-030b, 1-1-030c, 1-1-032a, 1-1-033a, 1-1-034a, 1- 1-035a, 1-1-036a, 1-1-037a, 1-1-038a, 1-1-039a, 1-1-040a, 1-1-040c, 1-1-041a, 1-1-1 042a, 1-1-043a, 1-1-044a, 1-1-045a, 1-1-045b, 1-1-046a, 1-1-047a, 1-1-048a, 1-1-049a, 1-1-049b, 1-1-050a, 1-1-050b, 1-1-051a, 1-1-051b, 1-1-052a, 1-1-052b, 1-1-053a, 1- 1-054a, 1-1-1055a, 1--1-056a, 1-1-057a, 1-1-057c, 1--1-058a, 1--1-058b, 1--1-059a, 1-1-1 060a, 1-1-060b, 1-1-061a, 1-1-062a, 1-1-063a, 1-1-063b, 1-1-064a, 1-1-065a, 1-1-066a, 1-1-067a, 1-1-068a, 1-1-069a, 1-1-069b, 1-1-070a, 1-1-070b, 1-1-071a, 1-1-072a, 1- 1-072b, 1-1-072c, 1-1-073b, 1-1-074a, 1-1-076a, 1-1-077a, 1-1-077b, 1-1-080a, 1-1- 081a, 1-1-082a, 1-1-083a, 1-1 -084a, 1-1-085a, 1-1-086a, 1-1-087a, 1-1-088a, 1-1-089a, 1-1-090a, 1-1-091a, 1-1-092a , 1-1-093a, 1-1-093b, 1-1-094a, 1-1-094b, 1-1-094c, 1-1-095a, 1-1-096a, 1-1-097a, 1 -1-099a, 1-1-100a, 1-1-101a, 1-1-101b, 1-1-103a, 1-1-103b, 1-1-104a, 1-1-105a, 1-1 -105b, 1-1-105c, 1-1-106a, 1-1-106b, 1-1-106c, 1-1-107a, 1-1-108a, 1-1-109a, 1-1-109b , 1-1-1110a, 1-1-1110c, 1-1-1111a, 1-1-1112a, 1-1-1112b, 1-1-1113a, 1-1-1113b, 1-1-1114a, 1 -1-114b, 1-1-115a, 1-1-115b, 1-1-116a, 1-1-117a, 1-1-118a, 1-1-118c, 1-1-120c, 1-1 -121a, 1-1-1122a, 1-1-1123a, 1-1-1124a, 1-1-1124b, 1-1-1125a, 1-1-1126a, 1-1-1127a, 1-1-1128a , 1-1-130a, 1-1-131a, 1-1-132a, 1-1-133a, 1-1-134a, 1-1-135a, 1-1-136a, 1-1-137a, 1 -1-138a, 1-1-139a, 1-1-139b, 1-1-140a, 1-1-141a, 1-1-142a, 1-1-142b, 1-1-143a, 1-1 -144a, 1-1-1145a, 1-1-1145b, 1-1-1146a, 1-1-1147a, 1-1-1148a, 1-1-1149a, 1-1-1150a, 1-1-1151a , 1-1-152a, 1-1-153a, 1-1-153b, 1-1-154a, 1-1-155a, 1-1-156a, 1-1-157a, 1-1-158a, 1 -1-159a, 1-1-160a, 1-1-161a, 1-1-162a, 1-1-163a, 1-1-164a, 1-1-165a, 1-1-166a, 1-1 -167a, 1-1-1168a, 1-1-1169a, 1-1-1170a, 1-1-1171a, 1-1-1171b, 1-1-1172a, 1-1-1173a, 1-1-1174a , 1-1-175a, 1-1-176a, 1-1- 177a, 1-1-178a, 1-1-179a, 1-1-180a, 1-1-181a, 1-1-182a, 1-1-183a, 1-1-183b, 1-1-185a, 1-1-186a, 1-1-187a, 1-1-188a, 1-1-189a, 1-1-190a, 1-1-191a, 1-1-192a, 1-1-193a, 1- 1-194a, 1-1-195a, 1-1-196a, 1-1-197a, 1-1-198a, 1-1-199a, 1-2-001a, 1-2-002a, 1-2- 004a, 1-2-004b, 1-2-004c, 1-2-005a, 1-2-006a, 1-3-001a, 1-3-002a, 1-3-003a, 1-3-004a, 1-3-005a, 1-3-006a, 1-3-007a, 1-3-008a, 1-3-009a, 1-3-010a, 1-3-011a, 1-3-012a, 1- 3-013a, 1-3-014a, 1-3-015a, 1-4-001a, 1-4-002a, 1-4-003a, 1-4-003b, 1-4-004a, 1-5- 001a, 1-5-002a, 1-5-003a, 1-5-004a, 1-6-001a, 1-6-002a, 1-7-001a, 1-8-001b, 1-8-002a, 1-8-002b, 1-8-003a, 1-8-003b, 1-8-004b, 1-8-005a, 1-8-005b, 1-8-006a, 1-8-006b, 1- 8-007a, 1-8-008a, 1-8-009a, 1-8-010a, 1-8-011a, 1-8-013a, 1-8-013b, 1-8-014a, 1-8- 014b, 1-8-015a, 1-8-015b, 1-8-016a, 1-9-002a, 1-9-002b, 1-9-003a, 1-9-003b, 1-10-001a, 1-10-001b, 1-10-001c, 1-10-002a, 1-10-002b, 1-10-002c, 1-10-003a, 1-10-004a, 1-10-005a, 1- 10-006a, 1-11-001a, 1-11-001b, 1-11-001c, 1-11-002a, 1-11-003a, 1-11-003b, 1-11-004a, 1-11- 004b, 1-11-004c, 1-11-005a, 1-11-005b, 1-11-006a, 1-11-006b, 1-11-007a, 1-11-007b, 1-11-00 7c, 1-11-008a, 1-11-008b, 1-11-009a, 1-11-009b, 1-12-001a, 1-12-002a, 1-12-003a, 1-12-004a, 1-12-005a, 1-12-006a, 1-12-007a, 1-12-008a, 1-12-009a, 1-12-010a, 1-12-011a, 1-12-012a, 1- 13-001a, 1-14-001a, 1-14-002a, 1-15-002a, 1-15-003a, 1-15-004a, 1-15-005a, 1-15-006a, 1-15 007a, 1-16-001a, 1-16-001b, 2-1-001a, 2-1-001b, 2-1-002a, 2-1-003a, 2-1-004a, 3-1-001a, 3-1-001b, 3--1-001c, 3--1-002a, 3--1-002b, 3--1-002c

Test Example 3: Insecticidal Test on Spodoptera litura

Dilute the 10% emulsion of the compound of the present invention (depending on the compound and test the 10% hydrating agent) with the water added with the spreading agent to prepare a 500 ppm concentration of the medicinal solution. Soak the cabbage leaves in the liquid for about 10 seconds. After the dipping operation is over, the cabbage leaves treated with the liquid medicine are air-dried and placed in a shallow dish. Here, 5 third-instar larvae of Spodoptera litura were placed in each tray, covered with a lid, and placed in a 25°C constant temperature chamber. After 6 days of containment, the number of dead insects of Spodoptera litura in the platter was investigated, and the mortality rate was calculated from the same calculation formula as in Test Example 1. Still, the experiment is carried out in a 2-continuous system.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 90%.

Compounds of the present invention: 1-1-1-001a, 1-1-1-001b, 1-1-1-001c, 1--1-002a, 1--1-002b, 1--1-003a, 1-1-1-004a, 1-1-1 005a, 1-1-005c, 1-1-006a, 1-1-007a, 1-1-009a, 1-1-011a, 1-1-012a, 1-1-013a, 1-1-013b, 1-1-013c, 1-1-014a, 1-1-014c, 1-1-015a, 1-1-015b, 1-1-016a, 1-1-016b, 1-1-016c, 1- 1-017a, 1-1-1-018a, 1--1-019a, 1--1-020a, 1--1-020b, 1--1-023a, 1--1-023b, 1--1-023c, 1-1-1 024a, 1-1-026a, 1-1-027a, 1-1-027b, 1-1-029a, 1-1-030a, 1-1-030b, 1-1-030c, 1-1-032a, 1-1-033a, 1-1-034a, 1-1-036a, 1-1-037a, 1-1-038a, 1-1-039a, 1-1-040a, 1-1-040c, 1- 1-041a, 1-1-042a, 1-1-043a, 1-1-044a, 1-1-045a, 1-1-045b, 1-1-046a, 1-1-047a, 1-1- 048a, 1-1-049a, 1-1-049b, 1-1-050a, 1-1-051a, 1-1-051b, 1-1-052a, 1-1-053a, 1-1-056a, 1-1-057a, 1-1-057c, 1-1-058a, 1-1-059a, 1-1-060a, 1-1-061a, 1-1-062a, 1-1-063a, 1- 1-064a, 1-1-065a, 1-1-066a, 1-1-067a, 1-1-068a, 1-1-069a, 1-1-070a, 1-1-070b, 1-1- 071a, 1-1-072a, 1-1-072b, 1-1-072c, 1-1-074a, 1-1-076a, 1-1-077a, 1-1-077b, 1-1-080a, 1-1-081a, 1-1-082a, 1-1-083a, 1-1-084a, 1-1-085a, 1-1-087a, 1-1-089a, 1-1-090a, 1- 1-091a, 1-1-092a, 1-1-093a, 1-1-093b, 1-1-094a, 1-1-094b, 1-1-094c, 1-1-095a, 1-1- 096a, 1-1-097a, 1-1-099a, 1-1 -100a, 1-1-101a, 1-1-103a, 1-1-103b, 1-1-104a, 1-1-105a, 1-1-105b, 1-1-106a, 1-1-109a , 1-1-1110a, 1-1-1110c, 1-1-1111a, 1-1-1112a, 1-1-1113a, 1-1-1114a, 1-1-1114b, 1-1-1115a, 1 -1-115b, 1-1-118a, 1-1-122a, 1-1-123a, 1-1-124a, 1-1-124b, 1-1-125a, 1-1-126a, 1-1 -127a, 1-1-1128a, 1-1-1129a, 1-1-1130a, 1-1-1131a, 1-1-1132a, 1-1-1133a, 1-1-1134a, 1-1-1135a , 1-1-135b, 1-1-136a, 1-1-137a, 1-1-138a, 1-1-139a, 1-1-139b, 1-1-140a, 1-1-141a, 1 -1-142a, 1-1-142b, 1-1-143a, 1-1-144a, 1-1-145a, 1-1-145b, 1-1-146a, 1-1-147a, 1-1 -148a, 1-1-149a, 1-1-150a, 1-1-151a, 1-1-152a, 1-1-153a, 1-1-153b, 1-1-154a, 1-1-155a , 1-1-156a, 1-1-157a, 1-1-158a, 1-1-159a, 1-1-160a, 1-1-161a, 1-1-162a, 1-1-163a, 1 -1-164a, 1-1-165a, 1-1-166a, 1-1-167a, 1-1-168a, 1-1-169a, 1-1-170a, 1-1-171a, 1-1 -171b, 1-1-172a, 1-1-173a, 1-1-174a, 1-1-175a, 1-1-176a, 1-1-177a, 1-1-178a, 1-1-179a , 1-1-180a, 1-1-181a, 1-1-182a, 1-1-183a, 1-1-183b, 1-1-185a, 1-1-186a, 1-1-187a, 1 -1-188a, 1-1-1189a, 1-1-1190a, 1-1-1191a, 1-1-1192a, 1-1-1193a, 1-1-1194a, 1-1-1195a, 1-1 -196a, 1-1-197a, 1-1-198a, 1-2-001a, 1-2-002a, 1-2-004a, 1-2-004b, 1-2-004c, 1-2-005a , 1-2-006a, 1-3-001a, 1-3- 002a,1-3-003a,1-3-004a,1-3-005a,1-3-006a,1-3-007a,1-3-008a,1-3-009a,1-3-010a, 1-3-011a, 1-3-012a, 1-3-013a, 1-3-014a, 1-3-015a, 1-4-001a, 1-4-002a, 1-4-003a, 1- 4-003b, 1-4-004a, 1-5-001a, 1-5-002a, 1-5-003a, 1-5-004a, 1-6-001a, 1-6-002a, 1-7- 001a, 1-8-002a, 1-8-002b, 1-8-003a, 1-8-003b, 1-8-005a, 1-8-005b, 1-8-006a, 1-8-006b, 1-8-007a, 1-8-008a, 1-8-009a, 1-8-010a, 1-8-011a, 1-8-013a, 1-8-013b, 1-8-014a, 1- 8-015a, 1-8-016a, 1-9-002a, 1-9-002b, 1-9-003a, 1-10-001a, 1-10-001b, 1-10-001c, 1-10- 002a, 1-10-002b, 1-10-002c, 1-10-003a, 1-10-004a, 1-10-005a, 1-10-006a, 1-11-001a, 1-11-001b, 1-11-001c, 1-11-002a, 1-11-003a, 1-11-004a, 1-11-004b, 1-11-004c, 1-11-005a, 1-11-005b, 1- 11-006a, 1-11-007a, 1-11-007b, 1-11-007c, 1-11-008a, 1-11-008b, 1-11-009a, 1-11-009b, 1-12 001a, 1-12-002a, 1-12-003a, 1-12-004a, 1-12-005a, 1-12-006a, 1-12-007a, 1-12-008a, 1-12-009a, 1- 15-005a, 1-15-006a, 1-15-007a, 1-16-001a, 2-1-001a, 2-1-001b, 2-1-003a, 2-1-004a, 3-1- 001a, 3--1-001c, 3--1-002a, 3--1-002b, 3--1-002c

Test Example 4: Insecticidal activity on Western flower thrips

Put moist filter paper on a styrene cup with an inner diameter of 7 cm, and place a 3 cm square green bean leaf on it, and inoculate 20 larvae of Frankliniella occidentalis per leaf. Dilute the 10% emulsion of the compound of the present invention (depending on the compound and test the 10% hydrating agent) with the water added with the spreading agent to prepare a 500 ppm concentration of the medicinal solution. Use a rotating scattering tower for the prepared liquid medicine, and spread 2.5 ml (2.5 mg/cm ² ) in each styrene cup.

Two days later, the number of dead insects of the ingested western flower thrips and the food hazard of kidney beans were investigated. The mortality rate was calculated from the same calculation formula as in Test Example 1.

The hazard of ingestion is as follows. 1: 0-20% food hazard, 2: 20-50% food hazard, 3: 50-70% food hazard, 4: more than 70% food hazard. Still, the experiment is carried out in a 2-continuous system.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 50% and a food hazard of more than 2%.

Compounds of the present invention: 1-1-001a, 1-1-002b, 1-1-003a, 1-1-005a, 1-1-006a, 1-1-023c, 1-1-035a, 1-1- 036a, 1-1-038a, 1-1-039a, 1-1-042a, 1-1-043a, 1-1-049a, 1-1-050a, 1-1-051a, 1-1-052a, 1-1-052b, 1-1-053a, 1-1-054b, 1-1-055b, 1-1-056a, 1-1-057a, 1-1-057c, 1-1-061a, 1- 1-062a, 1-1-063a, 1-1-064a, 1-1-067a, 1-1-068a, 1-1-069b, 1-1-070a, 1-1-071a, 1-1-1 072a, 1-1-074a, 1-1-076a, 1-1-080a, 1-1-081a, 1-1-082a, 1-1-087a, 1-1-089a, 1-1-090a, 1-1-093a, 1-1-095a, 1-1-096a, 1-1-097a, 1-1-099a, 1-1-105a, 1-1-106b, 1-1-109a, 1- 1-110a, 1-1-1112a, 1-1-1114a, 1-1-1115a, 1-1-1117a, 1-1-1120c, 1-1-1122a, 1-1-1123a, 1-1-1 125a, 1-1-126a, 1-1-127a, 1-1-128a, 1-1-129a, 1-1-133a, 1-1-133a, 1-1-134a, 1-1-135a, 1-1-136a, 1-1-137a, 1-1-139a, 1-1-154a, 1-1-155a, 1-1-159a, 1-1-159b, 1-1-160a, 1- 1-161a, 1-1-1165a, 1-1-166a, 1-1-1171a, 1-1-1172a, 1-1-1173a, 1-1-1175a, 1-1-1180a, 1-1-1 190a, 1-1-191a, 1-1-194a, 1-1-195a, 1-1-196a, 1-1-198a, 1-2-006a, 1-3-012a, 1-4-003a, 1-4-004a, 1-8-007a, 1-8-008a, 1-8-011a, 1-8-013a, 1-8-014a, 1-8-015a, 1-8-016a, 1- 9-002a, 1-9-003a, 1-10-003a, 1-11-003a, 1-11-004a, 1-11-006a, 1-11-007a, 1-11-007c, 1-11- 009b, 1-12-009a, 2- 1- 002a, 3--1-001a, 3--1-001b, 3--1-001c, 3--1-002a

Test Example 5: Insecticidal Test on Myzus persicae

Spread moist degreased cotton on a glass tray with an inner diameter of 3 cm, place cabbage leaves cut into the same diameter on it, and place 4 wingless adults of the green peach aphid (Myzus persicae). After 1 day, the 10% emulsion of the compound of the present invention (depending on the compound and test 10% hydrating agent) is diluted with the water added with the spreading agent to prepare a 500 ppm concentration of the medicinal solution. Spread the prepared liquid medicine in a rotating scattering tower (2.5 mg/cm ² ), cover it and store it in a 25°C constant temperature chamber. After 6 days of containment, the number of dead insects of the green peach aphid in the platter was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1. Still, the experiment is carried out in a 2-continuous system.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 90%.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-002b, 1-1-003a, 1-1-004a, 1-1-004b, 1-1-004c, 1-1- 005a, 1-1-006a, 1-1-007a, 1-1-009a, 1-1-011a, 1-1-012a, 1-1-012b, 1-1-013a, 1-1-013c, 1-1-014a, 1-1-014c, 1-1-015a, 1-1-015b, 1-1-016c, 1-1-017a, 1-1-018a, 1-1-019a, 1- 1-020a, 1--1-023a, 1-1-1-024a, 1--1-025c, 1--1-026a, 1--1-027a, 1-1-032a, 1--1-033a, 1-1-1 034a, 1-1-035a, 1-1-036a, 1-1-037a, 1-1-038a, 1-1-039a, 1-1-040b, 1-1-040c, 1-1-041a, 1-1-042a, 1-1-043a, 1-1-044a, 1-1-045b, 1-1-046a, 1-1-047a, 1-1-048a, 1-1-049a, 1- 1-049b, 1-1-050a, 1-1-051a, 1-1-052a, 1-1-053a, 1-1-056a, 1-1-057a, 1-1-057c, 1-1- 058a, 1-1-059a, 1-1-060a, 1-1-061a, 1-1-062a, 1-1-063a, 1-1-064a, 1-1-065a, 1-1-066a, 1-1-067a, 1-1-068a, 1-1-071a, 1-1-072a, 1-1-073b, 1-1-074a, 1-1-077a, 1-1-077b, 1- 1-080a, 1-1-082a, 1-1-086a, 1-1-087a, 1-1-090a, 1-1-091a, 1-1-093a, 1-1-093b, 1-1- 095a, 1-1-096a, 1-1-097a, 1-1-099a, 1-1-100a, 1-1-101a, 1-1-102a, 1-1-105a, 1-1-106a, 1-1-106b, 1-1-1106c, 1-1-1107a, 1-1-1108a, 1-1-1109a, 1-1-1110a, 1-1-1112a, 1-1-1113a, 1- 1-115a, 1-1-1116a, 1-1-1117a, 1-1-1118a, 1-1-1120c, 1-1-1121a, 1-1-1122a, 1-1-1123a, 1-1-1 125a, 1-1-128a, 1-1-129a, 1-1 -130a, 1-1-1131a, 1-1-1132a, 1-1-1133a, 1-1-1135a, 1-1-1136a, 1-1-1137a, 1-1-1138a, 1-1-1139a , 1-1-140a, 1-1-142a, 1-1-143a, 1-1-146a, 1-1-149a, 1-1-154a, 1-1-155a, 1-1-156a, 1 ^{-1 - 158a, 1 - 1-159a,} 1-1 - 160a, 1-1-161a, 1-1-163a, 1-1-165a, 1-1-166a, 1-1-168a, 1-1 -169a, 1-1-170a, 1-1-171a, 1-1-172a, 1-1-173a, 1-1-175a, 1-1-180a, 1-1-181a, 1-1-183a , 1-1-185a, 1-1-187a, 1-1-188a, 1-1-189a, 1-1-190a, 1-1-191a, 1-1-192a, 1-1-193a, 1 -1-194a, 1-1-195a, 1-1-196a, 1-1-197a, 1-1-198a, 1-1-199a, 1-2-001a, 1 - 2-002a, 1-3 ^{-001a, 1-3 - 002a, 1-3-003a,} 1-3-004a, 1-3-005a, 1-3-006a, 1-3-007a, 1 - 3-009a, 1-3-010a ^{, 1-3 - 011a, 1-3-012a, 1-4-001a} , 1-4-002a, 1-4-003a, 1-4-004a, 1-5-001a, 1-5-0026,1 -5-003a, 1-5-004a, 1-6-001a, 1-6-002a, 1-8-002a, 1-8-002b, 1-8-003a, 1-8-003b, 1-8 -004b, 1-8-005a, 1-8-006a, 1-8-008a, 1-8-010a, 1-8-013a, 1 - 8-014a, 1-8-015b, 1-8 - 016a , 1-9-002a, 1-9-003a, 1-10-001a, 1-10-001b, 1-10-002a, 1-10-002b, 1-10-002c, 1-10-003a, 1 -10-004a, 1-11-001a, 1-11-001b, 1-11-002a, 1-11-003a, 1-11-004a, 1 - 11 - 007a, 1-11-007b, 1-11 -007c, 1-11-008a, 1-11-009a, 1-12-001a, 1 - 12-002a, 1-12 - 003a, 1 - ^{12 - 004a, 1-12-005a, 1-12-006a,} 1-12-007a, 1-12-008a, 1-14 - 001a, 1-14-002a, 1 - 15 - 003a, 1-15 - 004a, 1-15-007a, 1-16-001a, 1-17-001a, 2-1-001a, 2-1-002a, 2 - 1 - 003a, 2 - 1 - 004a, 3-1-001a, 3-1-001c, 3--1-002a

Test Example 6: Insecticidal test on silver leaf whitefly

Put moist filter paper on a styrene cup with an inner diameter of 7 cm, and place a 3 cm green bean leaf on it. Dilute the 10% emulsion of the compound of the present invention (depending on the compound and test the 10% hydrating agent) with the water added with the spreading agent to prepare a 500 ppm concentration of the drug solution, using a rotating scattering tower, the drug solution per styrene Spread 2.5ml (2.5mg/cm ² ) in each cup. After the leaves were air-dried, the adults of Bemisia argentifolii (Bemisia argentifolii) were placed, covered with a cover, and stored in a thermostat room at 25°C. The number of dead insects after 5 days was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1. Still, the experiment is carried out in a 2-continuous system.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 90%.

Compounds of the present invention: 1-1-035a, 1-1-036a, 1-1-043a, 1-1-049a, 1-1-047a, 1-1-094a, 1-1-095a, 1-1- 096a, 1-1-099a, 1-1-125a, 1-3-001a, 1-14-001a, 3--1-002a

Test Example 7: Soil irrigation treatment test for Myzus persicae

The 10% emulsion of the compound of the present invention is diluted with tap water to prepare a medicinal solution with a concentration of 500 ppm.

The soil part of the plant head of the cabbage seedling (2.5 current leaf stage) planted in a plastic cup was irrigated with 10 ml of the above-mentioned medicinal solution. After the irrigation treatment, the cabbage seedlings were placed in the greenhouse. One day after the irrigation treatment, the adults of the green peach aphid (Myzus persicae) were released at 20 per plant. After the worms are treated, the cabbage seedlings are placed in the greenhouse. Six days after the release of the insects, the number of remaining insects of the green peach aphid was investigated, and the control value was calculated from the following calculation formula.

Control value (%)={1-(Cb×Tai)/(Cai×Tb)}×100

The text in the formula means the following.

Cb: Number of insects before treatment in the non-treatment zone

Cai: The number of surviving insects in the final survey in the untreated area

Tb: Number of insects before treatment in the treatment area

Tai: The number of surviving insects in the final survey of the processing area

As a result, among the tested compounds, the following compounds showed more than 90% of the control value.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-003a, 1-1-004a, 1-1-005a, 1-1-006a, 1-1-012a, 1-1- 013a, 1-1-014a, 1-1-016a, 1-1-017a, 1-1-018a, 1-1-029a, 1-1-032a, 1-1-035a, 1-1-039a, 1-1-042a, 1-1-043a, 1-1-049a, 1-1-057a, 1-1-058a, 1-1-060a, 1-1-074a, 1-1-093a, 1- 1-097a, 1-1-1106a, 1-1-1112a, 1-1-1113a, 1-1-1122a, 1-1-1125a, 1-1-1154a, 1-1-1160a, 1-1-1 170a, 1-1-173a, 1-8-002a, 1-8-003a, 1-8-005a, 1-8-006a, 1-8-010a, 1-8-013a, 1-9-002a, 1-12-008a, 1-14-001a, 1-16-001a, 2-1-002a

Test Example 8: Infiltration and migration test for brown planthopper

The 10% emulsion of the compound of the present invention is diluted with tap water to prepare a medicinal solution with a concentration of 20 ppm, and the roots of rice cell seedlings (2 current leaf stage) are immersed. After 7 days, the rice was cut out and placed in a test tube, where 5 third-instar larvae of Nilaparvata lugens were placed in each test tube, covered with a sponge, and placed in a 25°C constant temperature chamber. Six days after the release of the insects, the number of dead insects of the brown planthopper was investigated, and the mortality rate (%) was calculated (the number of dead insects ÷ the number of tested insects × 100). Still, the experiment is carried out in a 2-continuous system.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 90%.

Compounds of the present invention: 1-1-1-001a, 1-1-1-001b, 1--1-002a, 1--1-005a, 1--1-006a, 1-1-013a, 1-1-1014a, 1-1-1 017a, 1-1-018a, 1-1-020a, 1-1-030a, 1-1-032a, 1-1-035a, 1-1-036a, 1-1-038a, 1-1-039a, 1-1-042a, 1-1-043a, 1-1-044a, 1-1-049a, 1-1-052a, 1-1-057a, 1-1-057c, 1-1-058a, 1- 1-067a, 1-1-070a, 1-1-072a, 1-1-074a, 1-1-076a, 1-1-077a, 1-1-092a, 1-1-093a, 1-1- 095a, 1-1-096a, 1-1-097a, 1-1-099a, 1-1-105a, 1-1-106a, 1-1-107a, 1-1-109a, 1-1-111a, 1-1-113a, 1-1-1117a, 1-1-1122a, 1-1-1125a, 1-1-1131a, 1-1-1133a, 1-1-1136a, 1-1-1138a, 1- 1-145b, 1-1-154a, 1-1-157a, 1-1-160a, 1-1-165a, 1-1-166a, 1-1-168a, 1-1-170a, 1-1- 173a, 1-1-180a, 1-1-182a, 1-1-183a, 1-1-185a, 1-1-189a, 1-1-190a, 1-1-191a, 1-1-192a, 1-1-193a, 1-1-194a, 1-1-195a, 1-1-196a, 1-1-197a, 1-1-198a, 1-2-002a, 1-3-001a, 1- 3-005a, 1-3-007a, 1-3-015a, 1-8-002a, 1-8-005a, 1-8-006a, 1-8-008a, 1-8-010a, 1-8- 013a, 1-8-016a, 1-9-002a, 1-11-001a, 1-11-002a, 1-11-003a, 1-11-004a, 1-11-007a, 1-11-009a, 1-12-006a, 1-12-008a, 1-12-009a, 1-14-001a, 1-14-002a, 1-16-001a, 2-1-002a, 3-1-002b

Test Example 9: Soil irrigation treatment test for Plutella xylostella

The 10% emulsion of the compound of the present invention is diluted with tap water to prepare a medicinal solution with a concentration of 500 ppm.

The soil part of the plant head of the cabbage seedling (2.5 current leaf stage) planted in a plastic cup was irrigated with 10 ml of the above-mentioned medicinal solution. After the irrigation treatment, the cabbage seedlings were placed in the greenhouse. After 5 days from the irrigation treatment, cut out the leaves of cabbage and put them in a shallow dish, where 5 3rd instar larvae of Plutella xylostella were placed in each dish, covered with a lid, and placed in a 25°C constant temperature chamber . Six days after containment, the number of dead insects of the diamondback moth in the platter was investigated, and the mortality rate was calculated from the same calculation formula as in Test Example 1. Still, the experiment is carried out in a 2-continuous system.

As a result, among the tested compounds, the following compounds showed more than 90% of the control value.

Compounds of the present invention: 1-1-001a, 1-1-001c, 1-1-002a, 1-1-003a, 1-1-004a, 1-1-005a, 1-1-006a, 1-1- 013a, 1-1-014a, 1-1-015a, 1-1-016a, 1-1-018a, 1-1-029a, 1-1-030a, 1-1-039a, 1-1-042a, 1-1-043a, 1-1-049a, 1-1-050a, 1-1-052a, 1-1-056a, 1-1-057a, 1-1-058a, 1-1-059a, 1- 1-060a, 1-1-063a, 1-1-069a, 1-1-070a, 1-1-074a, 1-1-076a, 1-1-077a, 1-1-080a, 1-1- 082a, 1-1-090a, 1-1-093a, 1-1-096a, 1-1-097a, 1-1-099a, 1-1-103a, 1-1-103b, 1-1-105a, 1-1-106a, 1-1-1107a, 1-1-1109a, 1-1-1111a, 1-1-1112a, 1-1-1113a, 1-1-1117a, 1-1-1122a, 1- 1-125a, 1-1-1126a, 1-1-1127a, 1-1-1128a, 1-1-1129a, 1-1-1132a, 1-1-1133a, 1-1-1135a, 1-1-1 136a, 1-1-140a, 1-1-143a, 1-1-146a, 1-1-154a, 1-1-157a, 1-1-160a, 1-1-165a, 1-1-166a, 1-1-170a, 1-1-172a, 1-1-173a, 1-1-182a, 1-3-001a, 1-3-004a, 1-3-013a, 1-3-014a, 1- 4-001a, 1-4-004a, 1-8-002a, 1-8-003a, 1-8-005a, 1-8-006a, 1-8-007a, 1-8-008a, 1-8- 010a, 1-8-013a, 1-8-016a, 1-9-002a, 1-10-002a, 1-11-001a, 1-11-002a, 1-11-003a, 1-11-004a, 1-11-007a, 1-11-008a, 1-11-009a, 1-12-008a, 1-12-009a, 1-12-011a, 1--14-001a, 1--14-002a, 1- 15-005a, 1-16-001a, 2-1-002a

Test Example 10: Effect test on soybean aphid in seed treatment

2.4 mg of the compound of the present invention was diluted with 97.6 μl of acetone. Put 4 soybean seeds into a 50ml plastic tube, pour the above-mentioned diluent into it, and stir the seeds so that the compound fully adheres to completely evaporate the acetone. Plant the treated seeds at 4 seeds/pot and place them in the greenhouse. After the primary leaves are unfolded, the adults of the soybean aphid (Aphis glycines) are released 2 pieces. Investigate the number of surviving insects 7 days after releasing the insects, and calculate the control value from the following calculation formula.

Control value (%)={1-(Cb×Tai)/(Cai×Tb)}×100

The text in the formula means the following.

Cb: Number of insects before treatment in the non-treatment zone

Cai: The number of surviving insects in the final survey in the untreated area

Tb: Number of insects before treatment in the treatment area

Tai: The number of surviving insects in the final survey of the processing area

As a result, among the tested compounds, the following compounds showed more than 90% of the control value.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-003a, 1-1-004a, 1-1-005a, 1-1-006a, 1-1-012a, 1-1- 013a, 1-1-014a, 1-1-016a, 1-1-017a, 1-1-018a, 1-1-029a, 1-1-032a, 1-1-035a, 1-1-039a, 1-1-042a, 1-1-043a, 1-1-049a, 1-1-057a, 1-1-058a, 1-1-060a, 1-1-074a, 1-1-093a, 1- 1-097a, 1-1-1106a, 1-1-1112a, 1-1-1113a, 1-1-1122a, 1-1-1125a, 1-1-1126a, 1-1-1154a, 1-1-1 160a, 1-1-170a, 1-1-172a, 1-1-173a, 1-3-001a, 1-8-002a, 1-8-003a, 1-8-005a, 1-8-006a, 1-8-010a, 1-8-013a, 1-9-002a, 1-12-008a, 1--14-001a, 1-16-001a

Test Example 11: Effect test on Rhipicephalus sanguineus

Dissolve 3.5 mg of the compound of the present invention in 3.5 ml of acetone to prepare a drug solution with a concentration of 1000 ppm. After applying 350 μl of the chemical solution to ^{the bottom and side surfaces of a glass container with 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 glass container used is 35cm ² , and the treatment dose is 10μg/cm ² .

Place 5 first nymphs (mixed male and female) of Rhipicephalus sanguineus in the glass container treated as above, and cover the lid and store in a thermostatic room at 25°C. Four days after the release of the insects, the number of dead insects in the tick was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 50%.

Compounds of the present invention: 1-1-001a, 1-1-001b, 1-1-002a, 1-1-003a, 1-1-003b, 1-1-003c, 1-1-004a, 1-1- 004b, 1-1-004c, 1-1-005a, 1-1-005b, 1-1-006a, 1-1-006b, 1-1-010a, 1-1-011a, 1-1-012a, 1-1-013a, 1-1-014a, 1-1-014b, 1-1-016a, 1-1-016c, 1-1-017a, 1-1-018a, 1-1-020a, 1- 1-022a, 1--1-023c, 1--1-026a, 1--1-023c, 1--1-027b, 1--1-035a, 1--1-039a, 1-1-1040a, 1-1-1 042a, 1-1-043a, 1-1-045a, 1-1-046a, 1-1-047a, 1-1-049a, 1-1-051a, 1-1-052b, 1-1-053a, 1-1-055a, 1-1-057a, 1-1-057c, 1-1-059b, 1-1-060a, 1-1-062a, 1-1-063a, 1-1-065a, 1- 1-067a, 1-1-068a, 1-1-071a, 1-1-072a, 1-1-072b, 1-1-075a, 1-1-080a, 1-1-083a, 1-1- 088a, 1-1-093a, 1-1-093b, 1-1-094a, 1-1-094b, 1-1-095a, 1-1-096a, 1-1-099a, 1-1-103a, 1-1-105a, 1-1-105b, 1-1-105c, 1-1-106a, 1-1-106b, 1-1-106c, 1-1-107a, 1-1-108a, 1- 1-109a, 1-1-1110a, 1-1-1110c, 1-1-1111a, 1-1-1111b, 1-1-1112a, 1-1-1113a, 1-1-1114a, 1-1-1 114b, 1-1-1115a, 1-1-1115b, 1-1-1116a, 1-1-1118b, 1-1-1118c, 1-1-1120c, 1-1-1124a, 1-1-1124b, 1-1-125a, 1-1-126a, 1-1-129a, 1-1-130a, 1-1-132a, 1-1-133a, 1-1-134a, 1-1-136a, 1- 1-137a, 1-1-1138a, 1-1-1139b, 1-1-1140a, 1-1-1142a, 1-1-1143a, 1-1-1144a, 1-1-1145a, 1-1-1 146a, 1-1-147a, 1-1-150a, 1-1 -151a, 1-1-152a, 1-1-153a, 1-1-153b, 1-1-155a, 1-1-156a, 1-1-158a, 1-1-159a, 1-1-159b , 1-1-160a, 1-1-161a, 1-1-162a, 1-1-163a, 1-1-164a, 1-1-165a, 1-1-169b, 1-1-170a, 1 -1-171a, 1-1-171b, 1-1-172a, 1-1-172b, 1-1-173b, 1-1-175a, 1-1-176a, 1-1-183a, 1-1 -190a, 1-1-196a, 1-3-004a, 1-3-005a, 1-3-011a, 1-3-013a, 1-3-014a, 1-3-015a, 1-4-004a , 1-5-001a, 1-6-001a, 1-8-002a, 1-8-005a, 1-8-006a, 1-8-006b, 1-8-008a, 1-8-010a, 1 -8-011a, 1-8-013a, 1-8-014a, 1-8-014b, 1-8-015b, 1-9-002a, 1-9-002b, 1-9-003a, 1-10 -002c, 1-10-004a, 1-10-005a, 1-11-004a, 1-11-004c, 1-11-005a, 1-11-006a, 1-11-007c, 1-11-008a , 1-11-008b, 1-12-004a, 1-12-007a, 1-12-010a, 1-12-011a, 1-12-012a, 1-14-002a, 1-15-003a, 1 -15-005a, 1-15-006a, 1-16-001a, 2-1-002a, 2-1-003a, 2-1-003b, 3-1-002a, 3-1-002b, 3-1 -002c

Test Example 12: Effect test on cat fleas

Dissolve 3.5 mg of the compound of the present invention in 3.5 ml of acetone to prepare a drug solution with a concentration of 1000 ppm. After applying 350 μl of the chemical solution to ^{the bottom and side surfaces of a glass container with 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. Since the inner wall of the glass container used is 35 cm ² , the amount of treatment drug is 10 μg/cm ² .

Place 5 adult cat fleas (Ctenocephalides felis) (mixed male and female) in the glass container treated above, cover it and store it in a thermostatic chamber at 25°C. Four days after the release of the insects, the number of dead insects of the fleas was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1.

As a result, among the tested compounds, the following compounds showed a mortality rate of more than 50%.

Compounds of the present invention: 1-1-1-001a, 1-1-1-001b, 1-1-1-001c, 1--1-002a, 1--1-002b, 1--1-003a, 1-1-1-003b, 1-1-1 003c, 1-1-004a, 1-1-004b, 1-1-004c, 1-1-005a, 1-1-005b, 1-1-005c, 1-1-006a, 1-1-007a, 1-1-009a, 1-1-012a, 1-1-013a, 1-1-013b, 1-1-013c, 1-1-014a, 1-1-014c, 1-1-015a, 1- 1-015b, 1-1-016a, 1-1-016b, 1-1-016c, 1-1-017a, 1-1-018a, 1-1-019a, 1-1-020a, 1-1-1 023a, 1-1-023b, 1-1-023c, 1-1-024a, 1-1-025c, 1-1-026a, 1-1-027a, 1-1-027b, 1-1-029a, 1-1-030a, 1-1-032a, 1-1-033a, 1-1-034a, 1-1-035a, 1-1-036a, 1-1-037a, 1-1-039a, 1- 1-040c, 1-1-041a, 1-1-042a, 1-1-043a, 1-1-044a, 1-1-045a, 1-1-046a, 1-1-047a, 1-1- 047b, 1-1-048a, 1-1-048b, 1-1-049a, 1-1-050a, 1-1-050b, 1-1-051a, 1-1-051b, 1-1-052a, 1-1-052b, 1-1-053a, 1-1-054b, 1-1-055a, 1-1-056a, 1-1-057a, 1-1-057c, 1-1-058a, 1- 1-058b, 1--1-059b, 1--1-060a, 1--1-060b, 1-1-061a, 1-1-062a, 1-1-062b, 1--1-063a, 1-1-1 063b, 1-1-064a, 1-1-065a, 1-1-066a, 1-1-066b, 1-1-067a, 1-1-067b, 1-1-068a, 1-1-069a, 1-1-070a, 1-1-071a, 1-1-072a, 1-1-072b, 1-1-072c, 1-1-073b, 1-1-074a, 1-1-074b, 1- 1-075a, 1-1-1-076a, 1--1-077a, 1--1-077b, 1--1-080a, 1-1-081a, 1--1-082a, 1-1-084a, 1-1-1 085a, 1-1-086a, 1-1-087a, 1-1 -088a, 1-1-089a, 1-1-090a, 1-1-091a, 1-1-092a, 1-1-093a, 1-1-093b, 1-1-094a, 1-1-094b , 1-1-094c, 1-1-095a, 1-1-096a, 1-1-097a, 1-1-099a, 1-1-101a, 1-1-102a, 1-1-103a, 1 -1-103b, 1-1-104a, 1-1-105a, 1-1-105b, 1-1-105c, 1-1-106a, 1-1-106b, 1-1-106c, 1-1 -107a, 1-1-1108a, 1-1-1109a, 1-1-1110a, 1-1-1110c, 1-1-1111a, 1-1-1111b, 1-1-1112a, 1-1-1113a , 1-1-114a, 1-1-114b, 1-1-115a, 1-1-115b, 1-1-116a, 1-1-117a, 1-1-118a, 1-1-118b, 1 -1-119c, 1-1-122a, 1-1-123a, 1-1-124a, 1-1-124b, 1-1-125a, 1-1-126a, 1-1-127a, 1-1 -127b, 1-1-1128a, 1-1-1129a, 1-1-1130a, 1-1-1130b, 1-1-1132a, 1-1-1133a, 1-1-1134a, 1-1-1135a , 1-1-135b, 1-1-136a, 1-1-137a, 1-1-138a, 1-1-139a, 1-1-139b, 1-1-140a, 1-1-141a, 1 -1-142a, 1-1-142b, 1-1-143a, 1-1-144a, 1-1-145a, 1-1-145b, 1-1-146a, 1-1-147a, 1-1 -148a, 1-1-148b, 1-1-150a, 1-1-151a, 1-1-153a, 1-1-154a, 1-1-155a, 1-1-156a, 1-1-157a , 1-1-158a, 1-1-159a, 1-1-159b, 1-1-160a, 1-1-161a, 1-1-162a, 1-1-163a, 1-1-164a, 1 -1-165a, 1-1-166a, 1-1-167b, 1-1-169a, 1-1-169b, 1-1-170a, 1-1-171a, 1-1-1722, 1-1 -173b,1-1-175a,,1-1-180a,1-1-181a,1-1-183a,1-1-186a,1-1-187a,1-1-190a,1-1- 191a, 1-1-192a, 1-1-193a, 1-1 -194a, 1-1-196a, 1-1-197a, 1-1-198a, 1-1-199a, 1-2-001a, 1-3-001a, 1-3-002a, 1-3-003a , 1-3-004a, 1-3-005a, 1-3-006a, 1-3-007a, 1-3-008a, 1-3-009a, 1-3-010a, 1-3-011a, 1 -3-012a, 1-3-013a, 1-3-014a, 1-3-015a, 1-4-001a, 1-4-002a, 1-4-003a, 1-4-003b, 1-4 -004a, 1-5-001a, 1-5-002a, 1-5-003a, 1-5-004a, 1-8-002a, 1-8-002b, 1-8-003a, 1-8-004b , 1-8-005a, 1-8-006a, 1-8-006b, 1-8-007a, 1-8-007b, 1-8-008a, 1-8-009a, 1-8-010a, 1 -8-011a, 1-8-013a, 1-8-013c, 1-8-014a, 1-8-014b, 1-8-016a, 1-8-016b, 1-9-002a, 1-9 -002b, 1-9-003a, 1-9-003b, 1-10-001b, 1-10-002a, 1-10-002b, 1-10-002c, 1-10-003a, 1-10-004a , 1-11-001a, 1-11-001b, 1-11-001c, 1-11-003a, 1-11-004a, 1-11-004c, 1-11-005b, 1-11-006a, 1 -11-007b, 1-11-007c, 1-11-008a, 1-11-008b, 1-11-009a, 1-11-009b, 1-12-001a, 1-12-002a, 1-12 -003a, 1-12-006a, 1-1-2007a, 1-12-008a, 1-12-009a, 1-12-010a, 1-12-011a, 1-12-012a, 1-14-001a ,1-14-002a,1-15-003a,1-15-004a,1-15-005a,1-15-006a,1-15-007a,1-16-001a,1-16-001b,1 -17-001a, 2-1-001a, 2-1-002a, 2-1-003a, 2-1-003b, 3-1-001a, 3-1-001b, 3-1-001c, 3-1 -002a, 3--1-002b, 3--1-002c

Test Example 13: Rhipicephalus sanguineus orally administered to rats (Rhipicephalus sanguineus) Parasitic control test

Dissolve 5 mg of the compound of the present invention in 5 ml of olive oil to prepare a drug solution for administration. The medicinal solution was administered orally using a gastric tube in an amount of 10 ml per kg of the body weight of the rat. Oral administration was repeated in 2 per group. One hour after the drug solution was administered, 50 first nymphs (mixed male and female) of Rhipicephalus sanguineus (Rhipicephalus sanguineus) were wormed per rat. Investigate the number of parasites of the test mites after 3 days of release, and use the following formula to calculate the control rate.

Control rate (%)=100×(1-the number of parasitic ticks in the drug-administered group/the number of parasitic ticks in the non-drug-administered group).

As a result, among the tested compounds, the following compounds showed a control rate of more than 70%.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-003a, 1-1-006a, 1-1-015a, 1-1-016a, 1-1-096a, 1-1- 171a, 1-1-1103a, 1-3-1011a, 1-9-002a, 1-12-010a, 1-12-007a

Test Example 14: Insecticidal test for housefly

Dissolve 2 mg of the compound of the present invention in 1 ml of acetone to prepare a drug solution with a concentration of 2 μg/μl. After the female adult housefly (Musca domestica) was put to sleep with carbon dioxide gas, the above-prepared medicinal solution was applied with a topical application device (manufactured by Burkard Scientific), and 1 μl was applied to the back side of the chest of the pest. After the liquid medicine is treated, transfer the treated pests into a plastic cup with an inner diameter of 7.5 cm and a height of 4 cm with a lid, and store it in a constant temperature room at 25°C. Three days after the treatment, the number of dead insects was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1. Still, the experiment was repeated with 5 animals and 2 replicates.

As a result, the following compounds showed a mortality rate of more than 70%.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-003a, 1-1-013a, 1-1-015a, 1-1-016a, 1-1-051a, 1-1- 067a, 1-1-070a, 1-1-103a, 1-1-122a, 1-8-005a, 1-12-007a

Test Example 15: Insecticidal Test on German Cockroach

Dissolve 2 mg of the compound of the present invention in 0.2 ml of acetone to prepare a drug solution with a concentration of 10 μg/μl. After the male adults of the German cockroach (Blattela germanica) were put to sleep with carbon dioxide gas, the above-prepared medicinal solution was applied with a topical application device (manufactured by Burkard Scientific) to apply 1 μl to the abdomen of the pest. After the liquid medicine is treated, the waist-height shallow pan with an inner diameter of 6 cm and a height of 6 cm is moved and stored in a constant temperature room at 25°C. Three days after the treatment, the number of depressive insects and the number of dead insects were investigated, and the depressive insect mortality rate was calculated from the following calculation formula. Still, the experiment was repeated with 5 animals and 4 replicates.

Depression rate of dead insects (%) = (depression number + number of dead insects) / number of tested insects × 100

As a result, the following compounds showed a mortality rate of more than 70%.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-003a, 1-1-013a, 1-1-015a, 1-1-016a, 1-1-067a, 1-1- 070a, 1-1-103a, 1-1-122a, 1-8-005a, 1-11-007a, 1-12-007a

Test Example 16: Insecticidal Test on Yamato Termites

Prepare a 10% emulsion of the compound of the present invention. The emulsion was diluted with water to prepare a chemical solution with a concentration of 100 ppm. Titrate 0.5ml of the medicinal solution with 10g of river sand, and mix the river sand with the medicinal solution. Spread 1% agar (2cm square) on a shallow dish with an inner diameter of 4cm, and put in the river sand treated with the above-mentioned medicament and the filter paper used as bait. After putting Reticulitermes speratus here, keep it in a constant temperature room at 25°C. The number of dead insects was investigated 10 days after the treatment, and the dead insect rate was calculated from the same calculation formula as in Test Example 1. Still, the test system was repeated with 2.

As a result, the following compounds showed a mortality rate of more than 70%.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-003a, 1-1-013a, 1-1-015a, 1-1-016a, 1-1-051a, 1-1- 067a, 1-1-070a, 1-1-103a, 1-1-122a, 1-8-005a, 1-11-007a, 1-12-007a

Test Example 17: Insecticidal Test for Underground House Mosquitoes

Dissolve 2 mg of the compound of the present invention in 0.2 ml of dimethyl sulfoxide to prepare a 1% (w/v) dimethyl sulfoxide solution. This solution was diluted 100 times with distilled water to prepare a chemical solution with a compound concentration of 100 ppm. A 1.9ml plastic container (Cellstar 24 well plate, manufactured by GREINER) was used as the test container. Add 0.7ml of water containing 10-30 larvae of Culex pipiens molestus 1 day after hatching, and 0.2ml of aqueous solution for suspended aquarium fish feed (manufactured by Tetrajapan) as bait. Add 0.1ml of the drug solution prepared above and store it in a constant temperature room at 25°C. One day after the treatment, the number of dead insects was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1. Still, the test system was repeated with 2.

As a result, the following compounds showed a 100% mortality rate.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-003a, 1-1-013a, 1-1-015a, 1-1-016a, 1-1-051a, 1-1- 067a, 1-1-070a, 1-1-103a, 1-1-122a, 1-8-005a, 1-11-007a, 1-12-007a

Test Example 18: Insecticidal test on Aedes albopictus larvae

Dissolve 2 mg of the compound of the present invention in 0.2 ml of dimethyl sulfoxide to prepare a 1% (w/v) dimethyl sulfoxide solution. Add 0.01ml of this solution to 0.99ml of pure water to prepare a 0.01% (w/v) medicinal solution. A 0.3 ml plastic container (Cellstar 96 well cell culture plate, manufactured by GREINER) was used as the test container. After placing 0.09 ml of distilled water containing 30 Aedes albopictus larvae one day after hatching in the test container, 0.01 ml of the drug solution was titrated to a final concentration of 10 ppm. Cover the test container and store it in a constant temperature room at 25°C. Three days after the treatment, the number of dead insects was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1.

As a result, the following compounds showed a mortality rate of more than 70%.

Compounds of the present invention: 1-1-001a, 1-1-002a, 1-1-003a, 1-1-004a, 1-1-005a, 1-1-006a, 1-1-012a, 1-1- 013a, 1-1-014a, 1-1-015a, 1-1-016a, 1-1-017a, 1-1-018a, 1-1-020a, 1-1-023c, 1-1-042a, 1-1-043a, 1-1-044a, 1-1-046a, 1-1-049a, 1-1-051a, 1-1-053a, 1-1-055a, 1-1-057a, 1- 1-060a, 1-1-062a, 1-1-067a, 1-1-068a, 1-1-070a, 1-1-071a, 1-1-072a, 1-1-093a, 1-1- 094a, 1-1-095a, 1-1-096a, 1-1-099a, 1-1-103a, 1-1-105a, 1-1-106a, 1-1-109a, 1-1-110a, 1-1-111a, 1-1-1112a, 1-1-1113a, 1-1-1115a, 1-1-1116a, 1-1-1118a, 1-1-1122a, 1-1-1123a, 1- 1-124b, 1-1-1125a, 1-1-1126a, 1-1-1140a, 1-1-1143a, 1-1-1146a, 1-1-1160a, 1-1-1165a, 1-1-1 171a, 1-1-172a, 1-1-175a, 1-1-183a, 1-1-190a, 1-1-196a, 1-1-197a, 1-3-004a, 1-3-005a, 1-3-011a, 1-3-014a, 1-3-015a, 1-4-004a, 1-5-001a, 1-8-005a, 1-8-006a, 1-8-008a, 1- 8-010a, 1-8-013a, 1-8-014a, 1-9-002a, 1-10-005a, 1-10-006a, 1-11-004a, 1-11-006a, 1-11- 007a, 1-12-007a, 1-12-009a, 1-12-010a, 1-12-011a, 1-12-012a, 1-14-002a, 1-15-003a, 1-15-005a, 1-15-006a, 2--1-002a, 2--1-003a, 3--1-002a

[Industrial availability]

The compound of the present invention shows excellent pest control activity, and has almost no adverse effects on non-standard organisms such as mammals, fish and beneficial insects, and is an extremely useful compound.

Claims (25)

A condensed heterocyclic compound represented by formula (1) or its salt or the N-oxide,

[In the formula, _{D substituted by -S(O) n} R ¹ represents a ring represented by any of D1, D2 or D3,

Q represents a ring represented by any of Q1, Q2, Q3 or Q4,

G ₁ means C(Y1), G ₇ means C(Y2), G ₃ means C(Y3), G ₄ means C(Y4), G ₅ represents a nitrogen atom or C(Y5), T ₁ represents N (T _1a ), oxygen atom or sulfur atom, A ¹ represents N (A ^1a ), oxygen atom or sulfur atom, A ² represents a nitrogen atom or C(R ² ), A ³ represents a nitrogen atom or C(R ³ ), A ⁴ represents a nitrogen atom or C(R ⁴ ), A ⁵ represents a nitrogen atom or C(R ⁵ ), A ⁸ represents a nitrogen atom or C(R ⁸ ), R ¹ represents a C ₁ -C ₆ alkyl group, R ^1a represents C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio , C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl or cyano base, R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ Haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, -C(O)R ^20a , -C(O)OH, hydroxyl, -NH _2. -NHR ^20g , -N(R ^20h )R ^20g , mercapto, cyano or nitro, R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ haloalkenyl group, a C ₂ -C ₆ haloalkynyl group, a C ₁ -C ₈ alkane Oxy, C ₁ -C ₈ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio , R ^3a are substituted with any of (C ₁ -C ₆₎ alkylthio, C ₁ -C ₆ alkylsulfinyl acyl, C ₁ -C ₆ alkylsulfinyl acyl halides, C ₁ -C ₆ alkyl Sulfonyl, C ₁ -C ₆ haloalkylsulfonyl, -C(O)R ^30a , -C(O)OH, hydroxyl, -OC(O)R ^30e , -OS(O) ₂ R ^30f , -NH ₂ , -NHR ^30g , -N(R ^30h )R ^30g , mercapto, -SC(O)R ³⁰ⁱ , -SF ₅ , cyano, nitro, phenyl, phenyl optionally substituted ^{by R 3b} , Heterocyclic group or heterocyclic group optionally substituted ^{by R 3b,} R ^3a represents a C ₁ -C ₈ alkoxycarbonyl group, R ^3b represents a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a cyano group or a nitro group, R ⁴ represents hydrogen atom, halogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ haloalkynyl, C ₁ -C ₈ alkane Oxy, C ₁ -C ₈ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio , R ^4a is substituted with any of the (C ₁ -C ₆₎ alkylthio, C ₁ -C ₆ alkylsulfinyl acyl, C ₁ -C ₆ alkylsulfinyl acyl halides, C ₁ -C ₆ alkyl Sulfonyl, C ₁ -C ₆ haloalkylsulfonyl, -C(O)R ^40a , -C(O)OH, hydroxyl, -OC(O)R ^40e , -OS(O) ₂ R ^40f , -NH ₂ , -NHR ^40g , -N(R ^40h )R ^40g , mercapto, -SC(O)R ⁴⁰ⁱ , -SF ₅ , cyano, nitro, phenyl, phenyl optionally substituted ^{by R 4b} , Heterocyclic group or heterocyclic group optionally substituted ^{by R 4b,} R ^4a represents a C ₁ -C ₈ alkoxycarbonyl group, R ^4b represents a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a cyano group or a nitro group, R ⁵ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ Haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, -C(O)R ^50a , -C(O)OH, hydroxyl, -NH _2. -NHR ^50g , -N(R ^50h )R ^50g , mercapto, cyano or nitro, R ⁶ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ Haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, -C(O)R ^60a , -C(O)OH, hydroxyl, -NH _2. -NHR ^60g , -N(R ^60h )R ^60g , mercapto, cyano or nitro, R ⁷ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfonyl, mercapto, -SF ₅ , cyano or nitro, R ⁸ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group or a cyano group, A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, ^{A 1a-a} is substituted with any of the (C ₁ -C ₆₎ alkyl, ^{A 1a-a} arbitrarily substituted The (C ₁ -C ₆ ) haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkane Group, C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl Group, C ₁ -C ₆ haloalkylsulfinyl group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ haloalkylsulfinyl group, C(O)R ^10a , hydroxyl or cyano group, A ^1a-a represents C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ haloalkoxycarbonyl, C ₁ -C ₆ Alkylcarbonyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ A haloalkylsulfinyl group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ haloalkylsulfinyl group, a hydroxyl group or a cyano group, T _1a represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ Cycloalkyl (C ₁ -C ₆ )alkyl or C ₃ -C ₆ halocycloalkyl (C ₁ -C ₆ )alkyl, Y1, Y2, Y3, and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, ^a (C ₁ -C ₆ )alkyl group optionally substituted by Y a, are the optionally substituted (C ₁ -C ₆₎ haloalkyl Y ^a, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, optionally substituted by Y ^a are the (C ₂ -C ₆₎ alkenyl Group, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, (C ₂ -C ₆ )alkynyl ^{optionally substituted by Y b} _{, C 1} -C ₈ alkoxy, C ₁ -C ₈ Haloalkoxy, (C ₁ -C ₈ )alkoxy ^{optionally substituted by Y a} _{, C 2} -C ₆ alkenyloxy, C ₂ -C ₆ haloalkenyloxy, optionally substituted ^{by Y a} (C ₂ -C ₆ )alkenyloxy, C ₂ -C ₆ alkynyloxy, C ₂ -C ₆ haloalkynyloxy, (C ₂ -C ₆ )alkynyl ^{optionally substituted by Y a} Oxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ cycloalkyl (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ halocycloalkyl ( C ₁ -C ₆ )alkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 2} -C ₆ alkenylthio, C ₂ -C ₆ haloalkenyl group, C ₂ -C ₆ alkynyl group, C ₂ -C ₆ haloalkynyl group, C ₁ -C ₆ alkylsulfinyl acyl, C ₁ -C ₆ haloalkylsulfinyl, (C ₁ -C ₆ )alkylsulfinyl ^{optionally substituted by Y a} _{, C 2} -C ₆ alkenylsulfinyl, C ₂ -C ₆ haloalkenyl Sulfinyl, C ₂ -C ₆ alkynylsulfinyl, C ₂ -C ₆ haloalkynylsulfinyl, C ₁ -C ₆ alkyl sulfinyl, C ₁ -C ₆ haloalkylsulfonyl Alkyl, (C ₁ -C ₆ )alkylsulfonyl optionally substituted by Y ^a _{, C 2} -C ₆ alkenylsulfonyl, C ₂ -C ₆ haloalkenylsulfonyl, C ₂ -C ₆ alkynyl sulfonyl, C ₂ -C ₆ haloalkynyl sulfonyl, -C(O)R ^90a , -C(O)NHR ^90b , -C(O)N(R ^90c )R ^90b , -C (O)OH, -C(=NOR ^90d )R ^90a , -C(O)NH ₂ , hydroxyl, -OC(O)R ^90e , -OS(O) ₂ R ^90f , -NH ₂ , -NHR ^90g , -N(R ^90h )R ^90g , sulfhydryl, -SC(O)R ⁹⁰ⁱ , -S(O) ₂ NHR ^90j , -S(O) ₂ N(R ^90k )R ^90j , _{-SF 5} , cyano, nitro Group, phenyl group, phenyl group ^{optionally substituted by Y c} , heterocyclic group Or a heterocyclic group optionally substituted ^{by Y c,} Y5 and Y6 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl Aceto, C ₁ -C ₆ haloalkylsulfonyl, mercapto, -SF ₅ , cyano, nitro, phenyl or phenyl optionally substituted ^{by Y c,} Y ^a represents C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ haloalkoxycarbonyl, C ₁ -C ₆ alkyl Carbonyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkane A sulfinyl group, a C ₁ -C ₆ alkyl sulfinyl group, a C ₁ -C ₆ haloalkyl sulfinyl group, a hydroxyl group or a cyano group, Y ^b represents C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, trimethylsilyl, C ₁ -C ₈ alkoxy, phenyl or phenyl optionally substituted ^{by Y b2,} Y ^b2 represents C ₁ -C ₆ haloalkyl, Y ^c represents a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a cyano group or a nitro group, R ^10a , R ^20a , R ^30a , R ^30e , R ^40a , R ^40e , R ^50a , R ^60a and R ^90a each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ haloalkoxy, R ^20g , R ^20h , R ^30f , R ^30g , R ^30h , R ³⁰ⁱ , R ^40f , R ^40g , R ^40h , R ⁴⁰ⁱ , R ^50g , R ^50h , R ^60g , R ^60h , R ^90b , R ^90c , R ⁹⁰ⁱ , R ^90j and R ^90k each independently represent a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, R ^90d represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, R ^90e represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₆ alkylamine Group, C ₁ -C ₆ haloalkylamino group, di(C ₁ -C ₆ )alkylamino group or di(C ₁ -C ₆ )haloalkylamino group, R ^90f represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkylamino, C ₁ -C ₆ haloalkylamino, di (C ₁ -C ₆ ) alkane Amino group or di(C ₁ -C ₆ )haloalkylamino group, R ^90g and R ^90h each independently represent C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₈ alkane Oxycarbonyl, C ₁ -C ₈ haloalkoxycarbonyl, C ₁ -C ₆ alkylaminocarbonyl, C ₁ -C ₆ haloalkylaminocarbonyl, C ₁ -C ₆ alkylaminothiocarbonyl, C ₁ -C ₆ haloalkylaminothiocarbonyl, phenylcarbonyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylaminosulfonyl Acyl or di(C ₁ -C ₆ )alkylaminosulfonyl, n represents an integer of 0, 1, or 2]. Such as the fused heterocyclic compound of claim 1 or its salt or such Of N-oxide, of which, D substituted by -S(O) _n R ¹ represents a ring represented by D1, G ₁ means C(Y1), G ₂ means C(Y2), G ₃ means C(Y3), G ₄ means C(Y4), A ² means C(R ² ), A ³ means C(R ³ ), R ¹ represents a C ₁ -C ₆ alkyl group, R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, R ⁵ , R ⁶ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, R ⁷ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group, A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, (C1-C ₆ )alkyl ^{optionally substituted by A 1a-a} _{, C 2} -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₈ alkoxy, C ₃ -C ₆ cycloalkyl or C(O)R ^10a , A ^1a-a represents a C ₁ -C ₈ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfinyl group or a cyano group, R ^10a represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₈ alkoxy group, Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, a (C ₂ -C ₆ )alkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ halo substituted by Y ^b Alkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C _1- C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, -C(O)R ^90a , -C(O)NHR ^90b , -C(O)N(R ^90c )R ^90b ,- C(O)OH, hydroxyl, -OC(O)R ^90e , -OS(O) ₂ R ^90f , -NH ₂ , -NHR ^90g , -N(R ^90h )R ^90g , sulfhydryl, -SC(O)R ⁹⁰ⁱ , -S(O) ₂ NHR ^90j , -S(O) ₂ N(R ^90k )R ^90j , _{-SF 5} , cyano, nitro, phenyl, phenyl optionally substituted ^{by Y c, heterocycle} Group or heterocyclic group optionally substituted ^{by Y c,} Y ^a represents a C ₁ -C ₈ alkoxycarbonyl group. Such as the fused heterocyclic compound or its salt or the N-oxide of claim 1, wherein D substituted by -S(O) _n R ¹ represents a ring represented by D2, Q represents the ring represented by Q1, A ¹ means N(A ^1a ), A ² means C(R ² ), A ³ means C(R ³ ), A ⁴ means C(R ⁴ ), A ⁵ represents a nitrogen atom, R ¹ represents a C ₁ -C ₆ alkyl group, R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ )alkyl ^{optionally substituted by A 1a-a} _{, C 2} -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₈ alkoxy, C ₃ -C ₆ cycloalkyl or C(O)R ^10a , A ^1a-a represents a C ₁ -C ₈ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfinyl group or a cyano group, R ^10a represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₈ alkoxy group, Y5 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, Y6 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group, a phenyl group, or a phenyl group optionally substituted ^{by Y c.} Such as the fused heterocyclic compound or its salt or the N-oxide of claim 1, wherein D substituted by -S(O) _n R ¹ represents a ring represented by D3, Q represents the ring represented by Q1, G ₁ means C(Y1), G ₂ means C(Y2), G ₃ means C(Y3), G ₄ means C(Y4), T ₁ represents N (T _1a ) or sulfur atom, A ¹ means N(A ^1a ), A ² means C(R ² ), A ³ means C(R ³ ), A ⁴ means C(R ⁴ ), A ⁵ represents a nitrogen atom, R ¹ represents a C ₁ -C ₆ alkyl group, R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, R ³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, a C ₁ -C ₆ Alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ halo Alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, A ^1a represents a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ )alkyl ^{optionally substituted by A 1a-a} _{, C 2} -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₈ alkoxy, C ₃ -C ₆ cycloalkyl or C(O)R ^10a , A ^1a-a represents a C ₁ -C ₈ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfinyl group or a cyano group, R ^10a represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₈ alkoxy group, T _1a represents a hydrogen atom or a C ₁ -C ₆ alkyl group, Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy Group, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, cyano or nitro. Such as the condensed heterocyclic compound or its salt or the N-oxide of claim 2, wherein Q represents the ring represented by Q1, A ¹ means N(A ^1a ), R ¹ represents a C ₁ -C ₆ alkyl group, R ³ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, R ⁴ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, A ^1a represents a hydrogen atom or a C ₁ -C ₆ alkyl group. Such as the fused heterocyclic compound or its salt or the N-oxide of claim 5, wherein, A ⁴ means C(R ⁴ ), A ⁵ represents a nitrogen atom, R ² represents a hydrogen atom, R ⁴ represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group, Y1 represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group, Y2 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a (C ₂ -C ₆ )alkynyl group ^{optionally substituted by Y b,} C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfinyl, -NH ₂ , -NHR ^90g , nitro, cyano, phenyl, phenyl ^{optionally substituted by Y c} , thiophene-2- Yl, pyridin-3-yl or pyridin-4-yl, Y3 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a (C ₂ -C ₆ )alkynyl group ^{optionally substituted by Y b,} C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by Y a} _{, C 1} -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, -C(O)R ^90a , -C(O)N(R ^90c )R ^90b , -C(O)OH, cyano or nitro, Y4 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkyl group Sulfonyl, -N(R ^90h )R ^90g or cyano, Y ^a represents a C ₁ -C ₈ alkoxycarbonyl group, Y ^b represents C ₃ -C ₆ cycloalkyl, trimethylsilyl, C ₁ -C ₈ alkoxy or phenyl optionally substituted ^{by Y b2,} Y ^c represents a halogen atom or a C ₁ -C ₆ haloalkyl group, R ^90a represents C ₁ -C ₆ alkyl or C ₁ -C ₈ alkoxy, R ^90b and R ^90c each independently represent a C ₁ -C ₆ alkyl group, R ^90g represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkylcarbonyl, C ₁ -C ₈ alkoxycarbonyl or phenylcarbonyl, R ^90h represents a C ₁ -C ₆ alkyl group. Such as the fused heterocyclic compound or its salt or the N-oxide of claim 5, wherein, A ⁴ represents a nitrogen atom, A ⁵ means C(R ⁵ ), R ² represents a hydrogen atom, R ³ represents C ₁ -C ₆ haloalkyl, R ⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group, Y1 represents a hydrogen atom, Y2 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group, Y3 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ haloalkyl group or a cyano group, Y4 represents a hydrogen atom, a halogen atom, or a C ₁ -C ₈ alkoxy group. Such as the condensed heterocyclic compound or its salt or the N-oxide of claim 2, wherein Q represents the ring represented by Q2, A ⁴ represents a nitrogen atom or C(R ⁴ ), A ⁵ represents a nitrogen atom or C(R ⁵ ), (except that A ⁴ and A ⁵ represent a nitrogen atom together) R ¹ represents a C ₁ -C ₆ alkyl group, R ² represents a hydrogen atom, R ³ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, R ⁴ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl. Such as the fused heterocyclic compound or its salt or the N-oxide of claim 8, wherein A ⁴ represents a nitrogen atom, A ⁵ means C(R ⁵ ), R ³ represents C ₁ -C ₆ haloalkyl, R ⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group, R ⁶ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group, Y1 and Y4 represent hydrogen atoms, Y2 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group, Y3 represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group. Such as the fused heterocyclic compound of claim 2 or its salt or the And other N-oxides, of which, Q represents the ring represented by Q3, A ⁴ represents a nitrogen atom or C(R ⁴ ), A ⁵ represents a nitrogen atom or C(R ⁵ ), (except that A ⁴ and A ⁵ represent a nitrogen atom together) R ¹ represents a C ₁ -C ₆ alkyl group, R ² represents a hydrogen atom, R ³ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 3a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl, R ⁴ represents hydrogen atom, halogen atom, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkylthio, (C ₁ -C ₆ )alkylthio ^{optionally substituted by R 4a} _{, C 1} -C ₆ haloalkylsulfinyl or C ₁ -C ₆ haloalkylsulfinyl. Such as the condensed heterocyclic compound or its salt or the N-oxide of claim 10, wherein, A ⁴ represents a nitrogen atom, A ⁵ means C(R ⁵ ), R ³ represents C ₁ -C ₆ haloalkyl, R ⁵ represents a hydrogen atom, R ⁶ represents a hydrogen atom, Y1 represents a hydrogen atom, Y2 and Y3 each independently represent a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group, Y4 represents a hydrogen atom or a halogen atom. Such as the condensed heterocyclic compound or its salt or the N-oxide of claim 2, wherein Q represents a ring represented by Q4. Such as the condensed heterocyclic compound or its salt or the N-oxide of claim 12, wherein, R ¹ represents a C ₁ -C ₆ alkyl group, R ⁶ represents a hydrogen atom or a C ₁ -C ₆ alkyl group, R ⁷ represents C ₁ -C ₆ haloalkyl, R ⁸ represents a hydrogen atom or a C ₁ -C ₆ alkyl group, Y1 and Y4 represent hydrogen atoms, Y2 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ haloalkyl group, Y3 represents a hydrogen atom or a C ₁ -C ₆ haloalkyl group. Such as the fused heterocyclic compound or its salt or the N-oxide of claim 3, wherein, R ¹ represents a C ₁ -C ₆ alkyl group, R ² represents a hydrogen atom, R ³ represents C ₁ -C ₆ haloalkyl, R ⁴ represents a hydrogen atom, A ^1a represents a C ₁ -C ₆ alkyl group, Y5 represents a hydrogen atom, Y6 represents a halogen atom, a C ₁ -C ₆ haloalkyl group or a phenyl group optionally substituted ^{by Y c,} Y ^c represents C ₁ -C ₆ haloalkyl. Such as the fused heterocyclic compound of claim 4 or its salt or the And other N-oxides, of which, R ¹ represents a C ₁ -C ₆ alkyl group, R ² represents a hydrogen atom, R ³ represents C ₁ -C ₆ haloalkyl, R ⁴ represents a hydrogen atom, A ^1a represents a C ₁ -C ₆ alkyl group, T _1a represents a C ₁ -C ₆ alkyl group, Y1, Y3 and Y4 represent hydrogen atoms, Y2 represents C ₁ -C ₆ haloalkyl. Such as the condensed heterocyclic compound or its salt or the N-oxide of claim 2, wherein A ¹ represents N (A ^1a ) or oxygen atom, R ² represents a hydrogen atom, R ³ represents a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ haloalkylthio group, a C ₁ -C ₆ haloalkylsulfinyl group or a C ₁ -C ₆ haloalkylsulfinyl group, R ⁴ represents a hydrogen atom, R ⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group, R ⁶ represents a hydrogen atom, A ^1a represents a C ₁ -C ₆ alkyl group, Y1 and Y4 represent hydrogen atoms, Y2 and Y3 each independently represent a hydrogen atom or a C ₁ -C ₆ haloalkyl group. A pest control agent, which contains one or more selected from the group consisting of fused heterocyclic compounds and their salts in any one of claims 1 to 16 as active ingredients. A pesticide containing one or more of the fused heterocyclic compounds and their salts selected from any one of claims 1 to 16 as active ingredients. A control agent for internal or external parasites of mammals or birds, which contains one or more of the fused heterocyclic compounds selected from any one of claims 1 to 16 and their salts as active ingredients. Such as the control agent of claim 19, wherein the external parasites are Siphonaptera or ticks. An insecticide or acaricide, which contains one or more of the fused heterocyclic compounds and their salts selected from any one of claims 1 to 16 as active ingredients. A seed treatment agent containing one or two or more selected from the condensed heterocyclic compound and the salt thereof according to any one of claims 1 to 16 as an active ingredient. The seed treatment agent of claim 22, wherein the seed treatment is performed by dipping. A soil treatment agent containing one or two or more selected from the group consisting of fused heterocyclic compounds and salts thereof according to any one of claims 1 to 16 as active ingredients. Such as the soil treatment agent of claim 24, wherein the soil treatment is performed by soil irrigation treatment.