JP2018024672A - Condensed heterocyclic compound and pest control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel pest control agent, particularly an insecticide or miticide.SOLUTION: The present invention provides a condensed heterocyclic compound in which a structure D selected from D1-D4 is bonded to a structure Q selected from Q1-Q5, or a salt thereof or an N-oxide thereof.SELECTED DRAWING: None

Description

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

  For example, Patent Documents 1 to 31 disclose fused heterocyclic compounds, but do not disclose any fused heterocyclic compounds according to the present invention. Furthermore, its usefulness as a pest control agent, in particular, an insecticide / acaricide, and an internal or ectoparasite control agent for mammals or birds is not known at all.

International Publication No. 2016/005263 International Publication No. 2015/198859 International Publication No. 2015/133603 International Publication No. 2015/121136 International Publication No. 2015/091945 International Publication No. 2015/087458 International Publication No. 2015/071180 International Publication No. 2015/059088 International Publication No. 2015/002211 International Publication No. 2015/000715 International Publication No. 2014/157600 International Publication No. 2014/148451 International Publication No. 2014/142292 International Publication No. 2014/132972 International Publication No. 2014/132971 International Publication No. 2014/123206 International Publication No. 2014/123205 International Publication No. 2014/104407 International Publication No. 2013/180194 International Publication No. 2013/180193 International Publication No. 2013/191113 International Publication No. 2013/191189 International Publication No. 2013/191112 International Publication No. 2013/191188 International Publication No. 2013/018928 International Publication No. 2012/086848 International Publication No. 2012/074135 International Publication No. 2011/162364 International Publication No. 2011/043404 International Publication No. 2010/125985 International Publication No. 2009/131237

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

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

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

  As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the novel condensed heterocyclic compound represented by the following formula (1) according to the present invention has excellent pest control activity, particularly insecticide / The present invention was completed by discovering that it is an extremely useful compound that exhibits acaricidal activity and has almost no adverse effect on non-target organisms such as mammals, fish and beneficial insects.

  That is, the present invention relates to the following [1] to [19].

[1]
Formula (1):

[In the formula, D substituted with —S (O) _n R ¹ represents a structure represented by D1, D2, D3, or D4;

Q represents a ring represented by Q1, Q2, Q3, Q4 or Q5;

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),
U ¹ represents N (U ^1a ), an oxygen atom or a sulfur atom,
R ¹ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylthio, halo (C ₁ -C _{6) alkylthio,} C 1 -C ₆ alkylsulfinyl, halo _(C 1 ~C _{6) alkylsulfinyl,} C 1 -C ₆ alkylsulfonyl, halo _(C 1 ~C _{6) alkylsulfonyl,} C 1 -C ₆ represents alkoxy, halo _(C 1 _{~C 6)} alkoxy, ^{-OR 10,} cyano or nitro,
R ¹⁰ represents halo (C ₁ -C ₆ ) alkylsulfonyl,
Y1, Y2, Y3 and Y4 are each independently a hydrogen atom, a halogen _atom, C 3 -C ₆ cycloalkyl, substituted with ^{Y a} _(C 3 ~C _{6) cycloalkyl,} C 1 -C ₆ alkyl, Halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkylthio, halo (C ₁ -C ₆ ) alkylthio, C ₁ -C ₆ alkyl Sulfinyl, halo (C ₁ -C ₆ ) alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, halo (C ₁ -C ₆ ) alkylsulfonyl, —NH ₂ , —NHR ^{90 g} , cyano, nitro, V 1 or V 2;
Y5 and Y6 represent independently a hydrogen atom, a halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 ~C ₆₎ alkyl or _C 1 -C ₆ alkylthio,
R ^90g is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halo ( C ₁ -C ₆ ) alkoxycarbonyl, C ₁ -C ₆ alkylsulfonyl or halo (C ₁ -C ₆ ) alkylsulfonyl,
V1 represents the structure represented by V1-1, V1-2, V1-3 or V1-4,

  V2 represents the structure represented by V2-1, V2-2, V2-3 or V2-4,

Z ¹ and Z ² are each independently a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkylthio, halo _(C 1 ~C _{6) alkylthio,} C 1 -C ₆ alkylsulfinyl, halo _(C 1 ~C _{6) alkylsulfinyl,} C 1 -C ₆ alkylsulfonyl, halo _(C 1 _~C 6) When alkylsulfonyl, cyano or nitro is represented and p4, p5, q2, q3 or q4 represents an integer of 2 or more, each Z ¹ and each Z ² may be the same as or different from each other. You may,
Y ^a represents cyano, —C (O) OH or —C (O) NH ₂ ,
U ^1a represents a hydrogen atom or C ₁ -C ₆ alkyl,
p4 represents an integer of 0, 1, 2, 3 or 4;
p5 represents an integer of 0, 1, 2, 3, 4 or 5;
q2 represents an integer of 0, 1 or 2,
q3 represents an integer of 0, 1, 2, or 3,
q4 represents an integer of 0, 1, 2, 3 or 4,
r represents an integer of 0 or 1,
n represents an integer of 0, 1 or 2. ] The condensed heterocyclic compound or its salt represented by these, or those N-oxides.

[2]
R ¹ represents C ₁ -C ₆ alkyl;
R ² , R ³ and R ⁵ are each independently a hydrogen atom, a halogen atom, halo (C ₁ -C ₆ ) alkyl, halo (C ₁ -C ₆ ) alkylthio or halo (C ₁ -C ₆ ) alkoxy. Represent,
R ⁴ represents a hydrogen atom, halo (C ₁ -C ₆ ) alkyl, halo (C ₁ -C ₆ ) alkylthio, halo (C ₁ -C ₆ ) alkoxy or —OR ¹⁰ ,
Y1, Y2, Y3 and Y4 are each independently a hydrogen atom, a halogen _atom, C 3 -C _{6 cycloalkyl,} C 1 -C ₆ alkyl, halo _(C 1 ~C _{6) alkyl,} C 1 -C ₆ alkoxy , Halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkylthio, halo (C ₁ -C ₆ ) alkylthio, C ₁ -C ₆ alkylsulfinyl, halo (C ₁ -C ₆ ) alkylsulfinyl, C _1- C ₆ alkylsulfonyl, halo (C ₁ -C ₆ ) alkylsulfonyl, —NH ₂ , cyano, nitro, V 1 or V ₂ ,
Y5 represents a hydrogen atom,
Z ¹ and Z ² each independently represents a fused heterocyclic compound or a salt thereof or an N-oxide thereof according to the above [1], which represents halo (C ₁ -C ₆ ) alkyl.

[3]
D substituted with —S (O) _n R ¹ represents the structure represented by D1,
G ₁ represents C (Y1),
G ₂ is represents C (Y2),
G ₃ represents C (Y3),
G ₄ represents the condensed heterocyclic compound or the salt thereof or the N-oxide thereof according to the above [2], wherein C 4 represents Y (Y).

[4]
Q is the fused heterocyclic compound or a salt thereof or an N-oxide thereof according to the above [3], wherein Q represents a ring represented by Q1.

[5]
Y1 represents a hydrogen atom,
Y2 represents a hydrogen atom, a halogen _atom, a C 3 -C ₆ cycloalkyl or halo _(C 1 ~C ₆₎ alkyl,
Y3 represents a hydrogen atom, a halogen _atom, C 3 -C _{6 cycloalkyl,} C 1 -C ₆ alkylthio, cyano, halo _(C 1 ~C ₆₎ alkyl or V2,
Y4 represents a hydrogen atom or a halogen atom,
V2 represents the structure represented by V2-3,
q2 is the condensed heterocyclic compound or a salt thereof or the N-oxide thereof according to the above [4], in which q2 represents an integer of 0.

[6]
D substituted with —S (O) _n R ¹ represents the structure represented by D1,
G ₁ represents C (Y1),
G ₂ is represents C (Y2),
G ₃ represents a nitrogen atom,
G ₄ represents the condensed heterocyclic compound or the salt thereof or the N-oxide thereof according to the above [2], wherein C 4 represents Y (Y).

[7]
Q represents a ring represented by Q1,
r is the condensed heterocyclic compound or a salt thereof or the N-oxide thereof according to [6], in which r represents an integer of 0.

[8]
R ⁴ represents halo (C ₁ -C ₆ ) alkyl or halo (C ₁ -C ₆ ) alkoxy,
Y1 and Y4 represent a hydrogen atom,
Y2 represents a hydrogen atom, a halogen atom or a _C 3 -C ₆ cycloalkyl,
n is the condensed heterocyclic compound or the salt thereof or the N-oxide thereof according to the above [7], wherein n represents an integer of 0 or 2.

[9]
Q is the condensed heterocyclic compound or a salt thereof, or an N-oxide thereof according to the above [3], wherein Q represents a ring represented by Q2.

[10]
R ² represents a hydrogen atom or a halogen atom,
R ³ represents a hydrogen atom, halo (C ₁ -C ₆ ) alkyl or halo (C ₁ -C ₆ ) alkylthio,
R ⁴ represents a hydrogen atom, halo (C ₁ -C ₆ ) alkyl, halo (C ₁ -C ₆ ) alkylthio or halo (C ₁ -C ₆ ) alkoxy,
R ⁵ represents a hydrogen atom,
Y1, Y2 and Y4 represent a hydrogen atom,
Y3 is halo _(C 1 _{~C 6)} alkyl,
n is the condensed heterocyclic compound or a salt thereof or the N-oxide thereof according to the above [9], which represents an integer of 2.

[11]
The pest control agent which contains 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of said [1]-[10] as an active ingredient.

[12]
An agrochemical containing one or more selected from the condensed heterocyclic compound according to any one of [1] to [10] above and a salt thereof as an active ingredient.

[13]
Control of internal or ectoparasites of mammals or birds containing one or more selected from the fused heterocyclic compound according to any one of [1] to [10] above and a salt thereof as an active ingredient Agent.

[14]
The control agent according to the above [13], wherein the ectoparasite is a flea or ticks.

[15]
An insecticide or acaricide containing, as an active ingredient, one or more selected from the condensed heterocyclic compound according to any one of [1] to [10] above and a salt thereof.

[16]
The soil treatment agent which contains 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of said [1]-[10] as an active ingredient.

[17]
The soil treatment agent according to [16], wherein the soil treatment is performed by soil irrigation treatment.

[18]
A seed treatment agent comprising one or more selected from the condensed heterocyclic compound according to any one of [1] to [10] above and a salt thereof as an active ingredient.

[19]
The seed treatment agent according to [18], wherein the seed treatment is performed by dipping treatment.

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

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

  The compounds included in the present invention may have geometrical isomers of E-form and Z-form depending on the type of substituent, and the present invention is not limited to these E-form, Z-form or E-form. And a mixture containing the Z-form in an arbitrary ratio.

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

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

  Among the compounds included in the present invention, those that can be converted into a salt according to a conventional method are, for example, salts of hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid , Inorganic acid salts such as sulfuric acid, phosphoric acid, chloric acid, perchloric acid, sulfonic acid salts such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, formic acid, acetic acid , Propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid, succinic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, carboxylic acid salts such as lactic acid, gluconic acid, citric acid, glutamic acid, asparagine Salts of amino acids such as acids, alkali metal salts such as lithium, sodium and potassium, alkalis such as calcium, barium and magnesium Metalloid salt, aluminum salt, tetramethylammonium salt, tetrabutylammonium salt, can be a quaternary ammonium salt such as benzyltrimethylammonium salts.

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

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

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

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

In the present specification, the expression “C _a -C _b alkyl” represents a linear or branched hydrocarbon group having a carbon number of _a to _b , such as a methyl group, an ethyl group, or n-propyl. Specific examples include a group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, n-hexyl group and the like. Selected within a range of each specified number of carbon atoms.

In the present specification, the expression “halo (C _a -C _b ) alkyl” refers to a straight chain composed of _a to _b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, or This represents a branched hydrocarbon group, and when substituted with two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, chlorodifluoromethyl group, trichloromethyl group, bromodifluoromethyl group, 1-fluoroethyl group, 2- Fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2,2 -Trichloroethyl group, 2-bromo-2,2-difluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, 2-chloro-1 , 1,2,2-tetrafluoroethyl group, pentafluoroethyl group, 2,2-difluoropropyl group, 3,3,3- Lifluoropropyl group, 3-bromo-3,3-difluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2 , 3,3,3-hexafluoropropyl group, heptafluoropropyl group, 2,2,2-trifluoro-1- (methyl) ethyl group, 2,2,2-trifluoro-1- (trifluoromethyl) Ethyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3,3,4 Specific examples include, 4,4-heptafluorobutyl group, nonafluorobutyl group and the like, and each is selected within the range of the designated number of carbon atoms.

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

The expression “C _a -C _b alkoxy” represents an alkyl-O— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methoxy group, ethoxy group, n-propyloxy group, i- Specific examples include propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group, etc., and each is selected within the range of the designated number of carbon atoms. The

In the present specification, the expression “halo (C _a -C _b ) alkoxy” represents a haloalkyl-O— group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as a difluoromethoxy group or trifluoromethoxy group. Group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2 Specific examples include -chloro-1,1,2-trifluoroethoxy group, 1,1,2,3,3,3-hexafluoropropyloxy group, and the like, each selected within the range of the designated number of carbon atoms. Is done.

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

The expression “halo (C _a -C _b ) alkylthio” represents a haloalkyl-S— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, difluoromethylthio group, trifluoromethylthio group, chlorodifluoro Methylthio group, bromodifluoromethylthio group, 2,2,2-trifluoroethylthio group, 1,1,2,2-tetrafluoroethylthio group, 2-chloro-1,1,2-trifluoroethylthio group, Pentafluoroethylthio group, 1,1,2,3,3,3-hexafluoropropylthio group, heptafluoropropylthio group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethylthio group , Nonafluorobutylthio group and the like are listed as specific examples, and each is selected within the range of the designated number of carbon atoms.

The expression “C _a -C _b alkylsulfinyl” represents an alkyl-S (O) — group having the above-mentioned meanings consisting of _a to _b carbon atoms, for example, methylsulfinyl group, ethylsulfinyl group, n- Specific examples include propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, i-butylsulfinyl group, s-butylsulfinyl group, tert-butylsulfinyl group, etc. Selected.

The expression “halo (C _a -C _b ) alkylsulfinyl” represents a haloalkyl-S (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, difluoromethylsulfinyl group, trifluoro Methylsulfinyl group, chlorodifluoromethylsulfinyl group, bromodifluoromethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethylsulfinyl group, Nonafluorobutylsulfinyl groups and the like can be mentioned as specific examples, and each is selected within the range of the designated number of carbon atoms.

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

The expression “halo (C _a -C _b ) alkylsulfonyl” represents a haloalkyl-SO ₂ -group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, difluoromethylsulfonyl group, trifluoromethylsulfonyl Group, chlorodifluoromethylsulfonyl group, bromodifluoromethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group, 1,1,2,2-tetrafluoroethylsulfonyl group, 2-chloro-1,1,2- A trifluoroethylsulfonyl group etc. are mentioned as a specific example, and it selects in the range of each designated number of carbon atoms.

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

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

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

The expression “halo (C _a -C _b ) alkoxycarbonyl” represents a haloalkyl-O—C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, a chloromethoxycarbonyl group Specific examples include 2-chloroethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2, -trifluoroethoxycarbonyl group, 2,2,2, -trichloroethoxycarbonyl group, and the like. Is selected within the range of the specified number of carbon atoms.

The notation “(C _a -C _b ) cycloalkyl substituted by Y ^a ” refers to the number of carbon atoms in which a hydrogen atom bonded to a carbon atom is substituted by arbitrary Y ^{a and} consists of _a to _b carbon atoms. Represents the meaning cycloalkyl group, selected in the range of each specified number of carbon atoms. At this time, when two or more substituents Y ^a on each (C _a -C _b ) cycloalkyl group are present, each Y ^a may be the same as or different from each other.

Next, the manufacturing method of this invention compound represented by the said Formula (1) is demonstrated below. The compound of the present invention can be produced, for example, by the following production methods 1 to 8.
[Production Method 1]
Among the compounds of the present invention represented by the formula (1), a compound represented by the formula (1-A) wherein n is an integer of 1 or 2 [hereinafter abbreviated as compound (1-A). ] Is, for example, a compound represented by the formula (1-B) in which n is an integer of 0 among the compounds of the present invention [hereinafter abbreviated as compound (1-B). And an oxidizing agent.

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

  When using a solvent, the solvent used may be inert to the reaction, such as water, lower alcohols such as methanol and ethanol, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. Ethers, aromatic hydrocarbons such as benzene, chlorobenzene, bromobenzene, xylene, and toluene, aliphatic hydrocarbons such as pentane, hexane, and cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane Nitriles such as acetonitrile and propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide Low sulfoxides, acetic acid, etc. Fatty acids or mixed solvents thereof.

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

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

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

The reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set in the range of 5 minutes to 100 hours, and preferably in the range of 1 hour to 48 hours.
[Production Method 2]
Compound (1-C) is, for example, a compound represented by formula (2) [hereinafter abbreviated as compound (2). ] And a compound represented by formula (50) [hereinafter abbreviated as compound (50). ] Can be made to react.

(In the formula, Q, D, R ¹ and n represent the same meaning as described above, and X ₁ represents a chlorine atom, a bromine atom or an iodine atom.)
Compound (1-C) can be produced by reacting compound (2) and compound (50) in a solvent or without solvent in the presence of a palladium catalyst and a base.

  When using a solvent, the solvent used may be inert to the reaction, such as water, lower alcohols such as methanol and ethanol, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. Ethers, aromatic hydrocarbons such as benzene, chlorobenzene, bromobenzene, xylene, and toluene, aliphatic hydrocarbons such as pentane, hexane, and cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane Nitriles such as acetonitrile and propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide Sulfoxides or these Mixed solvent, and the like.

  Examples of the palladium catalyst include palladium-carbon, palladium (II) chloride, palladium (II) acetate, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone). ) Palladium (0), tris (dibenzylideneacetone) dipalladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, dichloromethane adduct, and the like. As an equivalent of a palladium catalyst, it can be used in 0.005 to 20 equivalent with respect to 1 equivalent of compound (2), and 0.01 to 5 equivalent is preferable.

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

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

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

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

Some of the compounds (50) are known compounds, and some of them are commercially available.
[Production Method 3]
Among the compounds of the present invention represented by the formula (1), the compound (1-B) in which n is an integer of 0 is, for example, a compound represented by the formula (3) [hereinafter abbreviated as compound (3). . ] And a compound represented by formula (51) [hereinafter abbreviated as compound (51). ] Can be made to react.

(In the formula, L ¹ represents a leaving group such as a chlorine atom, a bromine atom, and an iodine atom, and Q, D, and R ¹ represent the same meaning as described above.)
Compound (1-B) can be produced by reacting compound (3) and compound (51) in a solvent or without a solvent in the presence of a palladium catalyst, a ligand and a base.

  When a solvent is used, the solvent used may be inert to the reaction. For example, lower alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane , Aromatic hydrocarbons such as benzene, chlorobenzene, bromobenzene, xylene and toluene, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, acetonitrile Nitriles such as propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone, and sulfoxides such as dimethyl sulfoxide Or a mixture of these Medium, and the like.

  Examples of the palladium catalyst include palladium-carbon, palladium (II) chloride, palladium (II) acetate, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone). ) Palladium (0), tris (dibenzylideneacetone) dipalladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, dichloromethane adduct, and the like. As an equivalent of a palladium catalyst, it can be used in 0.005 to 20 equivalent with respect to 1 equivalent of compound (3), and 0.01 to 5 equivalent is preferable.

  Examples of the ligand include 4,5'-bis (diphenylphosphino) -9,9'-dimethylxanthene, 1,10-phenanthroline and the like. The equivalent of the ligand can be used in the range of 0.005 to 20 equivalents relative to 1 equivalent of the compound (3), and preferably in the range of 0.01 to 5 equivalents.

  Examples of the base include pyridine, 2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8- Organic bases such as diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), sodium hydroxide, potassium hydroxide, hydrogen Inorganic bases such as sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like can be mentioned. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to 1 equivalent of the compound (3), and preferably in the range of 1 to 20 equivalents.

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

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

  As the equivalent of the substrate, compound (51) can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of compound (3), and preferably in the range of 1 to 20 equivalents.

Some of the compounds (51) are known compounds, and some of them are commercially available.
[Production Method 4]
Compound (1-C) is, for example, compound (2) and a compound represented by formula (52) [hereinafter abbreviated as compound (52). ] Can be made to react.

(In the formula, Q, D, R ¹ and n represent the same meaning as described above, and X ₂ represents a chlorine atom, a bromine atom or an iodine atom.)
Compound (1-C) can be produced by reacting compound (2) and compound (52) in a solvent or without solvent in the presence of a Grignard reagent and a palladium catalyst.

  When a solvent is used, the solvent used may be inert to the reaction. For example, lower alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane , Aromatic hydrocarbons such as benzene, chlorobenzene, bromobenzene, xylene and toluene, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, acetonitrile Nitriles such as propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone, and sulfoxides such as dimethyl sulfoxide Or a mixture of these Medium, and the like.

  Examples of the Grignard reagent include isopropylmagnesium chloride-lithium chloride complex. The equivalent of the Grignard reagent can be used in the range of 0.5 to 20 equivalents relative to 1 equivalent of compound (2), and preferably in the range of 1 to 5 equivalents.

  Examples of the palladium catalyst include palladium-carbon, palladium (II) chloride, palladium (II) acetate, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone). ) Palladium (0), tris (dibenzylideneacetone) dipalladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, dichloromethane adduct, and the like. As an equivalent of a palladium catalyst, it can be used in 0.005 to 20 equivalent with respect to 1 equivalent of compound (2), and 0.01 to 5 equivalent is preferable.

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

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

  As the equivalent of the substrate, compound (52) can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of compound (2), and preferably in the range of 1 to 20 equivalents.

Some of the compounds (52) are known compounds, and some of them are commercially available.
[Production Method 5]
Among the compounds (1) of the present invention, the compound (1-E) can be produced, for example, by reacting the compound (1-D) with an oxidizing agent.

(In the formula, D, R ¹ , R ³ , R ⁴ , R ⁵ and r have the same meaning as described above.)
Compound (1-E) can be produced by reacting compound (1-D) with an oxidizing agent according to the method described in Production Method 1.
[Production Method 6]
Among the compounds of the present invention (1), the compound (1-G) and the compound (1-H) are, for example, the compounds of the present invention (1) wherein at least one of Y1, Y2, Y3 and Y4 is a halogen atom. It can manufacture by making the compound (1-F) which is these, and a compound (53) or a compound (54) react.

[Wherein, Q, R ¹ , V 2, D and n represent the same meaning as described above, V represents the aforementioned V 1 or C ₃ -C ₆ cycloalkyl, X ^a represents ^a halogen atom, s represents 1, 2, 3 or 4 represents an integer, W ² represents Sn (R ^c ) ₃ , B (OR ^b ) ₂ or the like, R ^c represents C _{1 to} C ₆ alkyl, and R ^b represents a hydrogen atom or C _1. ~C represents a ₆ alkyl. ]
Compound (1-G) is a compound (1-F) and compound (53), Compound (1-H) is a compound (1-F) and compound (54), in a solvent or in the absence of a solvent. , And in the presence of a ligand and a base.

  As the usage-amount of a compound (53) and a compound (54), it can be used by 0.5-50 equivalent with respect to 1 equivalent of compound (1-F), respectively, and 1-20 equivalent is preferable.

  When a solvent is used, the solvent may be inert to the reaction, and examples thereof include the solvents described in Production Method 1.

  Examples of the catalyst include palladium-carbon, palladium chloride (II), palladium acetate (II), bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone). Palladium (0), tris (dibenzylideneacetone) dipalladium (0), copper iodide (I) and the like can be mentioned. As a usage-amount of a catalyst, it can be used by 0.005-20 equivalent with respect to 1 equivalent of compound (1-F), and 0.01-5 equivalent is preferable.

  Examples of the ligand include 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, 1,10-phenanthroline, 1,2-diaminoethane, N, N′-dimethylethylenediamine, and N, N ′. -Dimethylcyclohexane-1, 2-diamine etc. are mentioned. As a usage-amount of a ligand, it can be used by 0.005-20 equivalent with respect to 1 equivalent of compound (1-F), and 0.01-5 equivalent is preferable.

  Examples of the base include pyridine, 2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8- Organic bases such as diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), sodium hydroxide, potassium hydroxide, hydrogen Inorganic bases such as sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium phosphate and the like can be mentioned. As a usage-amount of a base, it can be used by 0.1-100 equivalent with respect to 1 equivalent of compounds (1-F), and 1-20 equivalent is preferable.

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

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

Some of the compound (53) and the compound (54) are known compounds, and some of them are available as commercial products.
[Production Method 7]
Among the compounds (1) of the present invention, the compound (1-B-D1) can be produced, for example, by reacting the compound (11) with the compound (55).

(In the formula, Q, R ¹ , G ₁ , G ₂ , G ₃ and G ₄ represent the same meaning as described above, and X ₃ represents a chlorine atom, a bromine atom or an iodine atom.)
Compound (1-B-D1) can be produced by reacting compound (11) and compound (55) in a solvent or without a solvent, optionally in the presence of a base.

  As the usage-amount of a compound (55), it can be used in 0.5-50 equivalent with respect to 1 equivalent of compound (11), and 1-20 equivalent is preferable.

  When a solvent is used, the solvent may be inert to the reaction, and examples thereof include the solvents described in Production Method 1.

  When a base is used, examples of the base include pyridine, 2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO). , Organic bases such as 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), sodium hydroxide, Inorganic bases such as potassium hydroxide, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like can be mentioned. As a usage-amount of a base, it can be used by 0.1-100 equivalent with respect to 1 equivalent of compound (11), and 1-20 equivalent is preferable.

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

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

Some of the compounds (55) are known compounds, and some of them are available as commercial products.
[Production Method 8]
Among the compounds (1) of the present invention, the compound (1-J) can be produced, for example, by reacting the compound (12) with the compound (56) or the compound (57).

(In the formula, D, R ¹ , R ³ , R ⁵ and n represent the same meaning as described above, and R ²⁰ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl.)
Compound (1-J) can be produced by reacting compound (12) with compound (56) or compound (57) in a solvent or without a solvent, optionally in the presence of a base.

  As the usage-amount of a compound (56) and a compound (57), it can be used by 0.5-50 equivalent with respect to 1 equivalent of a compound (12) respectively, and 1-20 equivalent is preferable.

  When a solvent is used, the solvent may be inert to the reaction, and examples thereof include the solvents described in Production Method 1.

  When a base is used, examples of the base include pyridine, 2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO). , Organic bases such as 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), sodium hydroxide, Inorganic bases such as potassium hydroxide, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like can be mentioned. As a usage-amount of a base, it can be used by 0.1-100 equivalent with respect to 1 equivalent of a compound (12), and 1-20 equivalent is preferable.

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

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

  Some of the compound (56) and the compound (57) are known compounds, and some of them are available as commercial products.

Of the compounds (2) used in production method 2 and production method 4, compound (2-A) where n is an integer of 0 and compound (2-B) where n is an integer of 1 or 2 are, for example, It can be produced according to the production route shown by the following reaction formula.
[Reaction Formula 1]

(In the formula, D, L ¹ , X ₁ , R ¹ and m represent the same meaning as described above, and R ^a represents C _{1 to} C ₆ alkyl.)
[Manufacturing process 1]
Compound represented by formula (8) [hereinafter abbreviated as compound (8). Is reacted with a halogenating agent according to a known method known in the literature, for example, the method described in International Publication No. 2013/018899, etc. [hereinafter, the compound ( 7). Can be manufactured.

Some of the compounds (8) are known compounds, and some of them are available as commercial products.
[Manufacturing process 2]
The compound (7) is reacted with the compound (51) according to the method described in the production method 3, whereby the compound represented by the formula (6) [hereinafter abbreviated as compound (6). Can be manufactured.
[Manufacturing process 3]
The compound (6) was hydrolyzed according to a known method known in the literature, for example, a method described in Bioorganic & Medicinal Chemistry Letters 2012, Vol. 22, p. By carrying out the decomposition reaction, the compound represented by formula (5) [hereinafter abbreviated as compound (5)]. Can be manufactured.
[Manufacturing process 4]
Compound (5) is a compound represented by formula (4) by performing a decarboxylation reaction according to a known method known in the literature, for example, the method described in Japanese Patent Application Publication No. 2001/114776, etc. [Hereinafter abbreviated as compound (4). Can be manufactured.
[Manufacturing process 5]
The compound represented by the formula (2-A) by reacting the compound (4) with a halogenating agent according to the method described in the production step 1 of the reaction formula 1 [hereinafter referred to as the compound (2-A) and Abbreviated. Can be manufactured.
[Manufacturing process 6]
Compound (2-B) can be produced by reacting compound (2-A) with an oxidizing agent according to the method described in Production Method 1.

Of compound (3) used in production method 3, compound (3-D1) can be produced, for example, according to the production route represented by the following reaction formula.
[Reaction Formula 2]

(In the formula, G ₁ , G ₂ , G ₃ , G ₄ , L ¹ , X ₁ and Q have the same meaning as described above.)
[Manufacturing process 1]
Compound represented by formula (10) [hereinafter abbreviated as compound (10). Is reacted with compound (55) according to a known method known in the literature, for example, the method described in Journal of Medicinal Chemistry 2007, 50, 6240, etc. , A compound represented by formula (9) [hereinafter abbreviated as compound (9). Can be manufactured.

Some of the compound (55) and the compound (10) are known compounds, and some of them are commercially available.
[Manufacturing process 2]
Compound (3-D1) can be produced by reacting compound (9) with a halogenating agent according to the method described in Production Process 1 of Reaction Scheme 1.

Compound (10) used in Reaction Scheme 2 can be produced, for example, according to the production route represented by the following reaction formula.
[Reaction Formula 3]

(In the formula, Q and X ₁ represent the same meaning as described above.)
[Manufacturing process 1]
Compound (13) can be produced by reacting compound (14) with methylmagnesium bromide according to a known method.
[Manufacturing process 2]
Compound (10) is compound (13) and a halogenating agent (for example, chlorine, bromine, iodine, iodine monochloride, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5 -Dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, trimethylphenylammonium tribromide, hydrobromic acid, acetic acid solution of hydrogen bromide, etc.) Can be made to react. In some cases, additives such as hydrobromic acid and acetic acid solution of hydrogen bromide may be used.

  This step is produced by reacting compound (13) in the presence of a silylating agent (for example, trimethylsilyl trifluoromethanesulfonate) and a base (for example, pyridine, triethylamine, sodium bicarbonate, potassium carbonate, cesium carbonate, etc.). After making the silylated compound (13), the reaction with the halogenating agent can be carried out. The silylated compound (13) may be directly reacted with a halogenating agent without isolation and purification.

Compound (12) used in production method 8 can be produced, for example, according to the production route represented by the following reaction formula.
[Reaction Formula 5]

(In the formula, D, R ¹ , R ³ , R ⁵ and n have the same meaning as described above.)
By subjecting compound (15) to a hydrogenation reaction according to a known method, for example, the method described in The Journal of Organic Chemistry 2008, Vol. 73, page 9326, etc. Compound (12) can be produced.

  In the reaction of production method 1 to production method 8 and reaction equation 1 to reaction equation 5, the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, washed with water, concentrated or put into ice water, and concentrated after extraction with an organic solvent. The target compound of the present invention can be obtained by carrying out the usual post-treatment. Moreover, when the necessity for purification arises, it can be separated and purified by any purification method such as recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.

  Although the specific example of this invention compound represented by Formula (1) is shown in Table 1-Table 9, the compound included by this invention is not limited only to these.

In the table, Me represents methyl, Et represents ethyl, and J1 to J9 represent the following structures. The number in parentheses represents the number or type of substituents Z to be substituted, and the substitution position. For example, “J1 [p = 0]” represents unsubstituted phenyl, and “J6 [3-CF ₃ ]” The description represents 3-trifluoromethylpyrazol-1-yl.

[Table 1]

――――――――――――――――― ―――――――――――――――――――――
R ⁴ Y2 Y3 Y4 R ⁴ Y2 Y3 Y4
――――――――――――――――― ―――――――――――――――――――――
CF ₃ HHH OCH ₂ CF ₂ CF ₂ CF ₃ HHH
CF ₃ FHH OCH ₂ CF ₂ CF ₂ CF ₃ FHH
CF ₃ Cl HH OCH ₂ CF ₂ CF ₂ CF ₃ Cl HH
CF ₃ Br HH OCH ₂ CF ₂ CF ₂ CF ₃ Br HH
CF ₃ IHH OCH ₂ CF ₂ CF ₂ CF ₃ IHH
CF ₃ Me HH OCH ₂ CF ₂ CF ₂ CF ₃ Me HH
CF ₃ CF ₃ HH OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ HH
CF ₃ SMe HH OCH ₂ CF ₂ CF ₂ CF ₃ SMe HH
CF ₃ SOMe HH OCH ₂ CF ₂ CF ₂ CF ₃ SOMe HH
CF ₃ SO ₂ Me HH OCH ₂ CF ₂ CF ₂ CF ₃ SO ₂ Me HH
CF ₃ OMe HH OCH ₂ CF ₂ CF ₂ CF ₃ OMe HH
CF ₃ OCF ₃ HH OCH ₂ CF ₂ CF ₂ CF ₃ OCF ₃ HH
CF ₃ NO ₂ HH OCH ₂ CF ₂ CF ₂ CF ₃ NO ₂ HH
CF ₃ NH ₂ HH OCH ₂ CF ₂ CF ₂ CF ₃ NH ₂ HH
CF ₃ CN HH OCH ₂ CF ₂ CF ₂ CF ₃ CN HH
CF ₃ SCF ₃ HH OCH ₂ CF ₂ CF ₂ CF ₃ SCF ₃ HH
CF ₃ SOCF ₃ HH OCH ₂ CF ₂ CF ₂ CF ₃ SOCF ₃ HH
CF ₃ SO ₂ CF ₃ HH OCH ₂ CF ₂ CF ₂ CF ₃ SO ₂ CF ₃ HH
CF ₃ HFH OCH ₂ CF ₂ CF ₂ CF ₃ HFH
CF ₃ H Cl H OCH ₂ CF ₂ CF ₂ CF ₃ H Cl H
CF ₃ H Br H OCH ₂ CF ₂ CF ₂ CF ₃ H Br H
CF ₃ HIH OCH ₂ CF ₂ CF ₂ CF ₃ HIH
CF ₃ H Me H OCH ₂ CF ₂ CF ₂ CF ₃ H Me H
CF ₃ H CF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ H CF ₃ H
CF ₃ H SMe H OCH ₂ CF ₂ CF ₂ CF ₃ H SMe H
CF ₃ H SOMe H OCH ₂ CF ₂ CF ₂ CF ₃ H SOMe H
CF ₃ H SO ₂ Me H OCH ₂ CF ₂ CF ₂ CF ₃ H SO ₂ Me H
CF ₃ H OMe H OCH ₂ CF ₂ CF ₂ CF ₃ H OMe H
CF ₃ H OCF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ H OCF ₃ H
CF ₃ H NO ₂ H OCH ₂ CF ₂ CF ₂ CF ₃ H NO ₂ H
CF ₃ H NH ₂ H OCH ₂ CF ₂ CF ₂ CF ₃ H NH ₂ H
CF ₃ H CN H OCH ₂ CF ₂ CF ₂ CF ₃ H CN H
CF ₃ H SCF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ H SCF ₃ H
CF ₃ H SOCF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ H SOCF ₃ H
CF ₃ H SO ₂ CF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ H SO ₂ CF ₃ H
CF ₃ H J1 [p = 0] H OCH ₂ CF ₂ CF ₂ CF ₃ H J1 [p = 0] H
CF ₃ H J1 [2-CF ₃ ] H OCH ₂ CF ₂ CF ₂ CF ₃ H J1 [2-CF ₃ ] H
CF ₃ H J1 [3-CF ₃ ] H OCH ₂ CF ₂ CF ₂ CF ₃ H J1 [3-CF ₃ ] H
CF ₃ H J1 [4-CF ₃ ] H OCH ₂ CF ₂ CF ₂ CF ₃ H J1 [4-CF ₃ ] H
CF ₃ H J2 H OCH ₂ CF ₂ CF ₂ CF ₃ H J2 H
CF ₃ H J3 H OCH ₂ CF ₂ CF ₂ CF ₃ H J3 H
CF ₃ H J4 H OCH ₂ CF ₂ CF ₂ CF ₃ H J4 H
CF ₃ H J5 H OCH ₂ CF ₂ CF ₂ CF ₃ H J5 H
CF ₃ H J6 [p = 0] H OCH ₂ CF ₂ CF ₂ CF ₃ H J6 [p = 0] H
CF ₃ H J6 [3-CF ₃ ] H OCH ₂ CF ₂ CF ₂ CF ₃ H J6 [3-CF ₃ ] H
CF ₃ H J7 H OCH ₂ CF ₂ CF ₂ CF ₃ H J7 H
CF ₃ H J8 H OCH ₂ CF ₂ CF ₂ CF ₃ H J8 H
CF ₃ H J9 H OCH ₂ CF ₂ CF ₂ CF ₃ H J9 H
CF ₃ HHF OCH ₂ CF ₂ CF ₂ CF ₃ HHF
CF ₃ HH Cl OCH ₂ CF ₂ CF ₂ CF ₃ HH Cl
CF ₃ HH Br OCH ₂ CF ₂ CF ₂ CF ₃ HH Br
CF ₃ HHI OCH ₂ CF ₂ CF ₂ CF ₃ HHI
CF ₃ HH Me OCH ₂ CF ₂ CF ₂ CF ₃ HH Me
CF ₃ HH CF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ HH CF ₃
CF ₃ HH SMe OCH ₂ CF ₂ CF ₂ CF ₃ HH SMe
CF ₃ HH SOMe OCH ₂ CF ₂ CF ₂ CF ₃ HH SOMe
CF ₃ HH SO ₂ Me OCH ₂ CF ₂ CF ₂ CF ₃ HH SO ₂ Me
CF ₃ HH OMe OCH ₂ CF ₂ CF ₂ CF ₃ HH OMe
CF ₃ HH OCF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ HH OCF ₃
CF ₃ HH NO ₂ OCH ₂ CF ₂ CF ₂ CF ₃ HH NO ₂
CF ₃ HH NH ₂ OCH ₂ CF ₂ CF ₂ CF ₃ HH NH ₂
CF ₃ HH CN OCH ₂ CF ₂ CF ₂ CF ₃ HH CN
CF ₃ HH SCF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ HH SCF ₃
CF ₃ HH SOCF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ HH SOCF ₃
CF ₃ HH SO ₂ CF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ HH SO ₂ CF ₃
CF ₃ Cl H Cl OCH ₂ CF ₂ CF ₂ CF ₃ Cl H Cl
CF ₃ Cl HF OCH ₂ CF ₂ CF ₂ CF ₃ Cl HF
CF ₃ Cl H CN OCH ₂ CF ₂ CF ₂ CF ₃ Cl H CN
CF ₃ Br H Br OCH ₂ CF ₂ CF ₂ CF ₃ Br H Br
CF ₃ Br HF OCH ₂ CF ₂ CF ₂ CF ₃ Br HF
CF ₃ Br H CN OCH ₂ CF ₂ CF ₂ CF ₃ Br H CN
CF ₃ IHI OCH ₂ CF ₂ CF ₂ CF ₃ IHI
CF ₃ IHF OCH ₂ CF ₂ CF ₂ CF ₃ IHF
CF ₃ IH CN OCH ₂ CF ₂ CF ₂ CF ₃ IH CN
CF ₃ CF ₃ HF OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ HF
CF ₃ CF ₃ H Cl OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ H Cl
CF ₃ CF ₃ H Br OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ H Br
CF ₃ CF ₃ HI OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ HI
CF ₃ CF ₃ H CN OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ H CN
CF ₃ IFH OCH ₂ CF ₂ CF ₂ CF ₃ IFH
OCH ₂ CF ₃ HHH OCH ₂ CF ₂ CHFCF ₃ HHH
OCH ₂ CF ₃ FHH OCH ₂ CF ₂ CHFCF ₃ FHH
OCH ₂ CF ₃ Cl HH OCH ₂ CF ₂ CHFCF ₃ Cl HH
OCH ₂ CF ₃ Br HH OCH ₂ CF ₂ CHFCF ₃ Br HH
OCH ₂ CF ₃ IHH OCH ₂ CF ₂ CHFCF ₃ IHH
OCH ₂ CF ₃ Me HH OCH ₂ CF ₂ CHFCF ₃ Me HH
OCH ₂ CF ₃ CF ₃ HH OCH ₂ CF ₂ CHFCF ₃ CF ₃ HH
OCH ₂ CF ₃ SMe HH OCH ₂ CF ₂ CHFCF ₃ SMe HH
OCH ₂ CF ₃ SOMe HH OCH ₂ CF ₂ CHFCF ₃ SOMe HH
OCH ₂ CF ₃ SO ₂ Me HH OCH ₂ CF ₂ CHFCF ₃ SO ₂ Me HH
OCH ₂ CF ₃ OMe HH OCH ₂ CF ₂ CHFCF ₃ OMe HH
OCH ₂ CF ₃ OCF ₃ HH OCH ₂ CF ₂ CHFCF ₃ OCF ₃ HH
OCH ₂ CF ₃ NO ₂ HH OCH ₂ CF ₂ CHFCF ₃ NO ₂ HH
OCH ₂ CF ₃ NH ₂ HH OCH ₂ CF ₂ CHFCF ₃ NH ₂ HH
OCH ₂ CF ₃ CN HH OCH ₂ CF ₂ CHFCF ₃ CN HH
OCH ₂ CF ₃ SCF ₃ HH OCH ₂ CF ₂ CHFCF ₃ SCF ₃ HH
OCH ₂ CF ₃ SOCF ₃ HH OCH ₂ CF ₂ CHFCF ₃ SOCF ₃ HH
OCH ₂ CF ₃ SO ₂ CF ₃ HH OCH ₂ CF ₂ CHFCF ₃ SO ₂ CF ₃ HH
OCH ₂ CF ₃ HFH OCH ₂ CF ₂ CHFCF ₃ HFH
OCH ₂ CF ₃ H Cl H OCH ₂ CF ₂ CHFCF ₃ H Cl H
OCH ₂ CF ₃ H Br H OCH ₂ CF ₂ CHFCF ₃ H Br H
OCH ₂ CF ₃ HIH OCH ₂ CF ₂ CHFCF ₃ HIH
OCH ₂ CF ₃ H Me H OCH ₂ CF ₂ CHFCF ₃ H Me H
OCH ₂ CF ₃ H CF ₃ H OCH ₂ CF ₂ CHFCF ₃ H CF ₃ H
OCH ₂ CF ₃ H SMe H OCH ₂ CF ₂ CHFCF ₃ H SMe H
OCH ₂ CF ₃ H SOMe H OCH ₂ CF ₂ CHFCF ₃ H SOMe H
OCH ₂ CF ₃ H SO ₂ Me H OCH ₂ CF ₂ CHFCF ₃ H SO ₂ Me H
OCH ₂ CF ₃ H OMe H OCH ₂ CF ₂ CHFCF ₃ H OMe H
OCH ₂ CF ₃ H OCF ₃ H OCH ₂ CF ₂ CHFCF ₃ H OCF ₃ H
OCH ₂ CF ₃ H NO ₂ H OCH ₂ CF ₂ CHFCF ₃ H NO ₂ H
OCH ₂ CF ₃ H NH ₂ H OCH ₂ CF ₂ CHFCF ₃ H NH ₂ H
OCH ₂ CF ₃ H CN H OCH ₂ CF ₂ CHFCF ₃ H CN H
OCH ₂ CF ₃ H SCF ₃ H OCH ₂ CF ₂ CHFCF ₃ H SCF ₃ H
OCH ₂ CF ₃ H SOCF ₃ H OCH ₂ CF ₂ CHFCF ₃ H SOCF ₃ H
OCH ₂ CF ₃ H SO ₂ CF ₃ H OCH ₂ CF ₂ CHFCF ₃ H SO ₂ CF ₃ H
OCH ₂ CF ₃ H J1 [p = 0] H OCH ₂ CF ₂ CHFCF ₃ H J1 [p = 0] H
OCH ₂ CF ₃ H J1 [2-CF ₃ ] H OCH ₂ CF ₂ CHFCF ₃ H J1 [2-CF ₃ ] H
OCH ₂ CF ₃ H J1 [3-CF ₃ ] H OCH ₂ CF ₂ CHFCF ₃ H J1 [3-CF ₃ ] H
OCH ₂ CF ₃ H J1 [4-CF ₃ ] H OCH ₂ CF ₂ CHFCF ₃ H J1 [4-CF ₃ ] H
OCH ₂ CF ₃ H J2 H OCH ₂ CF ₂ CHFCF ₃ H J2 H
OCH ₂ CF ₃ H J3 H OCH ₂ CF ₂ CHFCF ₃ H J3 H
OCH ₂ CF ₃ H J4 H OCH ₂ CF ₂ CHFCF ₃ H J4 H
OCH ₂ CF ₃ H J5 H OCH ₂ CF ₂ CHFCF ₃ H J5 H
OCH ₂ CF ₃ H J6 [p = 0] H OCH ₂ CF ₂ CHFCF ₃ H J6 [p = 0] H
OCH ₂ CF ₃ H J6 [3-CF ₃ ] H OCH ₂ CF ₂ CHFCF ₃ H J6 [3-CF ₃ ] H
OCH ₂ CF ₃ H J7 H OCH ₂ CF ₂ CHFCF ₃ H J7 H
OCH ₂ CF ₃ H J8 H OCH ₂ CF ₂ CHFCF ₃ H J8 H
OCH ₂ CF ₃ H J9 H OCH ₂ CF ₂ CHFCF ₃ H J9 H
OCH ₂ CF ₃ HHF OCH ₂ CF ₂ CHFCF ₃ HHF
OCH ₂ CF ₃ HH Cl OCH ₂ CF ₂ CHFCF ₃ HH Cl
OCH ₂ CF ₃ HH Br OCH ₂ CF ₂ CHFCF ₃ HH Br
OCH ₂ CF ₃ HHI OCH ₂ CF ₂ CHFCF ₃ HHI
OCH ₂ CF ₃ HH Me OCH ₂ CF ₂ CHFCF ₃ HH Me
OCH ₂ CF ₃ HH CF ₃ OCH ₂ CF ₂ CHFCF ₃ HH CF ₃
OCH ₂ CF ₃ HH SMe OCH ₂ CF ₂ CHFCF ₃ HH SMe
OCH ₂ CF ₃ HH SOMe OCH ₂ CF ₂ CHFCF ₃ HH SOMe
OCH ₂ CF ₃ HH SO ₂ Me OCH ₂ CF ₂ CHFCF ₃ HH SO ₂ Me
OCH ₂ CF ₃ HH OMe OCH ₂ CF ₂ CHFCF ₃ HH OMe
OCH ₂ CF ₃ HH OCF ₃ OCH ₂ CF ₂ CHFCF ₃ HH OCF ₃
OCH ₂ CF ₃ HH NO ₂ OCH ₂ CF ₂ CHFCF ₃ HH NO ₂
OCH ₂ CF ₃ HH NH ₂ OCH ₂ CF ₂ CHFCF ₃ HH NH ₂
OCH ₂ CF ₃ HH CN OCH ₂ CF ₂ CHFCF ₃ HH CN
OCH ₂ CF ₃ HH SCF ₃ OCH ₂ CF ₂ CHFCF ₃ HH SCF ₃
OCH ₂ CF ₃ HH SOCF ₃ OCH ₂ CF ₂ CHFCF ₃ HH SOCF ₃
OCH ₂ CF ₃ HH SO ₂ CF ₃ OCH ₂ CF ₂ CHFCF ₃ HH SO ₂ CF ₃
OCH ₂ CF ₃ Cl H Cl OCH ₂ CF ₂ CHFCF ₃ Cl H Cl
OCH ₂ CF ₃ Cl HF OCH ₂ CF ₂ CHFCF ₃ Cl HF
OCH ₂ CF ₃ Cl H CN OCH ₂ CF ₂ CHFCF ₃ Cl H CN
OCH ₂ CF ₃ Br H Br OCH ₂ CF ₂ CHFCF ₃ Br H Br
OCH ₂ CF ₃ Br HF OCH ₂ CF ₂ CHFCF ₃ Br HF
OCH ₂ CF ₃ Br H CN OCH ₂ CF ₂ CHFCF ₃ Br H CN
OCH ₂ CF ₃ IHI OCH ₂ CF ₂ CHFCF ₃ IHI
OCH ₂ CF ₃ IHF OCH ₂ CF ₂ CHFCF ₃ IHF
OCH ₂ CF ₃ IH CN OCH ₂ CF ₂ CHFCF ₃ IH CN
OCH ₂ CF ₃ CF ₃ HF OCH ₂ CF ₂ CHFCF ₃ CF ₃ HF
OCH ₂ CF ₃ CF ₃ H Cl OCH ₂ CF ₂ CHFCF ₃ CF ₃ H Cl
OCH ₂ CF ₃ CF ₃ H Br OCH ₂ CF ₂ CHFCF ₃ CF ₃ H Br
OCH ₂ CF ₃ CF ₃ HI OCH ₂ CF ₂ CHFCF ₃ CF ₃ HI
OCH ₂ CF ₃ CF ₃ H CN OCH ₂ CF ₂ CHFCF ₃ CF ₃ H CN
OCH ₂ CF ₃ IFH OCH ₂ CF ₂ CHFCF ₃ IFH
OCH ₂ CHF ₂ HHH OCH ₂ CF ₂ CHF ₂ HHH
OCH ₂ CHF ₂ FHH OCH ₂ CF ₂ CHF ₂ FHH
OCH ₂ CHF ₂ Cl HH OCH ₂ CF ₂ CHF ₂ Cl HH
OCH ₂ CHF ₂ Br HH OCH ₂ CF ₂ CHF ₂ Br HH
OCH ₂ CHF ₂ IHH OCH ₂ CF ₂ CHF ₂ IHH
OCH ₂ CHF ₂ Me HH OCH ₂ CF ₂ CHF ₂ Me HH
OCH ₂ CHF ₂ CF ₃ HH OCH ₂ CF ₂ CHF ₂ CF ₃ HH
OCH ₂ CHF ₂ SMe HH OCH ₂ CF ₂ CHF ₂ SMe HH
OCH ₂ CHF ₂ SOMe HH OCH ₂ CF ₂ CHF ₂ SOMe HH
OCH ₂ CHF ₂ SO ₂ Me HH OCH ₂ CF ₂ CHF ₂ SO ₂ Me HH
OCH ₂ CHF ₂ OMe HH OCH ₂ CF ₂ CHF ₂ OMe HH
OCH ₂ CHF ₂ OCF ₃ HH OCH ₂ CF ₂ CHF ₂ OCF ₃ HH
OCH ₂ CHF ₂ NO ₂ HH OCH ₂ CF ₂ CHF ₂ NO ₂ HH
OCH ₂ CHF ₂ NH ₂ HH OCH ₂ CF ₂ CHF ₂ NH ₂ HH
OCH ₂ CHF ₂ CN HH OCH ₂ CF ₂ CHF ₂ CN HH
OCH ₂ CHF ₂ SCF ₃ HH OCH ₂ CF ₂ CHF ₂ SCF ₃ HH
OCH ₂ CHF ₂ SOCF ₃ HH OCH ₂ CF ₂ CHF ₂ SOCF ₃ HH
OCH ₂ CHF ₂ SO ₂ CF ₃ HH OCH ₂ CF ₂ CHF ₂ SO ₂ CF ₃ HH
OCH ₂ CHF ₂ HFH OCH ₂ CF ₂ CHF ₂ HFH
OCH ₂ CHF ₂ H Cl H OCH ₂ CF ₂ CHF ₂ H Cl H
OCH ₂ CHF ₂ H Br H OCH ₂ CF ₂ CHF ₂ H Br H
OCH ₂ CHF ₂ HIH OCH ₂ CF ₂ CHF ₂ HIH
OCH ₂ CHF ₂ H Me H OCH ₂ CF ₂ CHF ₂ H Me H
OCH ₂ CHF ₂ H CF ₃ H OCH ₂ CF ₂ CHF ₂ H CF ₃ H
OCH ₂ CHF ₂ H SMe H OCH ₂ CF ₂ CHF ₂ H SMe H
OCH ₂ CHF ₂ H SOMe H OCH ₂ CF ₂ CHF ₂ H SOMe H
OCH ₂ CHF ₂ H SO ₂ Me H OCH ₂ CF ₂ CHF ₂ H SO ₂ Me H
OCH ₂ CHF ₂ H OMe H OCH ₂ CF ₂ CHF ₂ H OMe H
OCH ₂ CHF ₂ H OCF ₃ H OCH ₂ CF ₂ CHF ₂ H OCF ₃ H
OCH ₂ CHF ₂ H NO ₂ H OCH ₂ CF ₂ CHF ₂ H NO ₂ H
OCH ₂ CHF ₂ H NH ₂ H OCH ₂ CF ₂ CHF ₂ H NH ₂ H
OCH ₂ CHF ₂ H CN H OCH ₂ CF ₂ CHF ₂ H CN H
OCH ₂ CHF ₂ H SCF ₃ H OCH ₂ CF ₂ CHF ₂ H SCF ₃ H
OCH ₂ CHF ₂ H SOCF ₃ H OCH ₂ CF ₂ CHF ₂ H SOCF ₃ H
OCH ₂ CHF ₂ H SO ₂ CF ₃ H OCH ₂ CF ₂ CHF ₂ H SO ₂ CF ₃ H
OCH ₂ CHF ₂ H J1 [p = 0] H OCH ₂ CF ₂ CHF ₂ H J1 [p = 0] H
OCH ₂ CHF ₂ H J1 [2-CF ₃ ] H OCH ₂ CF ₂ CHF ₂ H J1 [2-CF ₃ ] H
OCH ₂ CHF ₂ H J1 [3-CF ₃ ] H OCH ₂ CF ₂ CHF ₂ H J1 [3-CF ₃ ] H
OCH ₂ CHF ₂ H J1 [4-CF ₃ ] H OCH ₂ CF ₂ CHF ₂ H J1 [4-CF ₃ ] H
OCH ₂ CHF ₂ H J2 H OCH ₂ CF ₂ CHF ₂ H J2 H
OCH ₂ CHF ₂ H J3 H OCH ₂ CF ₂ CHF ₂ H J3 H
OCH ₂ CHF ₂ H J4 H OCH ₂ CF ₂ CHF ₂ H J4 H
OCH ₂ CHF ₂ H J5 H OCH ₂ CF ₂ CHF ₂ H J5 H
OCH ₂ CHF ₂ H J6 [p = 0] H OCH ₂ CF ₂ CHF ₂ H J6 [p = 0] H
OCH ₂ CHF ₂ H J6 [3-CF ₃ ] H OCH ₂ CF ₂ CHF ₂ H J6 [3-CF ₃ ] H
OCH ₂ CHF ₂ H J7 H OCH ₂ CF ₂ CHF ₂ H J7 H
OCH ₂ CHF ₂ H J8 H OCH ₂ CF ₂ CHF ₂ H J8 H
OCH ₂ CHF ₂ H J9 H OCH ₂ CF ₂ CHF ₂ H J9 H
OCH ₂ CHF ₂ HHF OCH ₂ CF ₂ CHF ₂ HHF
OCH ₂ CHF ₂ HH Cl OCH ₂ CF ₂ CHF ₂ HH Cl
OCH ₂ CHF ₂ HH Br OCH ₂ CF ₂ CHF ₂ HH Br
OCH ₂ CHF ₂ HHI OCH ₂ CF ₂ CHF ₂ HHI
OCH ₂ CHF ₂ HH Me OCH ₂ CF ₂ CHF ₂ HH Me
OCH ₂ CHF ₂ HH CF ₃ OCH ₂ CF ₂ CHF ₂ HH CF ₃
OCH ₂ CHF ₂ HH SMe OCH ₂ CF ₂ CHF ₂ HH SMe
OCH ₂ CHF ₂ HH SOMe OCH ₂ CF ₂ CHF ₂ HH SOMe
OCH ₂ CHF ₂ HH SO ₂ Me OCH ₂ CF ₂ CHF ₂ HH SO ₂ Me
OCH ₂ CHF ₂ HH OMe OCH ₂ CF ₂ CHF ₂ HH OMe
OCH ₂ CHF ₂ HH OCF ₃ OCH ₂ CF ₂ CHF ₂ HH OCF ₃
OCH ₂ CHF ₂ HH NO ₂ OCH ₂ CF ₂ CHF ₂ HH NO ₂
OCH ₂ CHF ₂ HH NH ₂ OCH ₂ CF ₂ CHF ₂ HH NH ₂
OCH ₂ CHF ₂ HH CN OCH ₂ CF ₂ CHF ₂ HH CN
OCH ₂ CHF ₂ HH SCF ₃ OCH ₂ CF ₂ CHF ₂ HH SCF ₃
OCH ₂ CHF ₂ HH SOCF ₃ OCH ₂ CF ₂ CHF ₂ HH SOCF ₃
OCH ₂ CHF ₂ HH SO ₂ CF ₃ OCH ₂ CF ₂ CHF ₂ HH SO ₂ CF ₃
OCH ₂ CHF ₂ Cl H Cl OCH ₂ CF ₂ CHF ₂ Cl H Cl
OCH ₂ CHF ₂ Cl HF OCH ₂ CF ₂ CHF ₂ Cl HF
OCH ₂ CHF ₂ Cl H CN OCH ₂ CF ₂ CHF ₂ Cl H CN
OCH ₂ CHF ₂ Br H Br OCH ₂ CF ₂ CHF ₂ Br H Br
OCH ₂ CHF ₂ Br HF OCH ₂ CF ₂ CHF ₂ Br HF
OCH ₂ CHF ₂ Br H CN OCH ₂ CF ₂ CHF ₂ Br H CN
OCH ₂ CHF ₂ IHI OCH ₂ CF ₂ CHF ₂ IHI
OCH ₂ CHF ₂ IHF OCH ₂ CF ₂ CHF ₂ IHF
OCH ₂ CHF ₂ IH CN OCH ₂ CF ₂ CHF ₂ IH CN
OCH ₂ CHF ₂ CF ₃ HF OCH ₂ CF ₂ CHF ₂ CF ₃ HF
OCH ₂ CHF ₂ CF ₃ H Cl OCH ₂ CF ₂ CHF ₂ CF ₃ H Cl
OCH ₂ CHF ₂ CF ₃ H Br OCH ₂ CF ₂ CHF ₂ CF ₃ H Br
OCH ₂ CHF ₂ CF ₃ HI OCH ₂ CF ₂ CHF ₂ CF ₃ HI
OCH ₂ CHF ₂ CF ₃ H CN OCH ₂ CF ₂ CHF ₂ CF ₃ H CN
OCH ₂ CHF ₂ IFH OCH ₂ CF ₂ CHF ₂ IFH
OSO ₂ CF ₃ HHH OCH ₂ CF ₂ CF ₃ HHH
OSO ₂ CF ₃ FHH OCH ₂ CF ₂ CF ₃ FHH
OSO ₂ CF ₃ Cl HH OCH ₂ CF ₂ CF ₃ Cl HH
OSO ₂ CF ₃ Br HH OCH ₂ CF ₂ CF ₃ Br HH
OSO ₂ CF ₃ IHH OCH ₂ CF ₂ CF ₃ IHH
OSO ₂ CF ₃ Me HH OCH ₂ CF ₂ CF ₃ Me HH
OSO ₂ CF ₃ CF ₃ HH OCH ₂ CF ₂ CF ₃ CF ₃ HH
OSO ₂ CF ₃ SMe HH OCH ₂ CF ₂ CF ₃ SMe HH
OSO ₂ CF ₃ SOMe HH OCH ₂ CF ₂ CF ₃ SOMe HH
OSO ₂ CF ₃ SO ₂ Me HH OCH ₂ CF ₂ CF ₃ SO ₂ Me HH
OSO ₂ CF ₃ OMe HH OCH ₂ CF ₂ CF ₃ OMe HH
OSO ₂ CF ₃ OCF ₃ HH OCH ₂ CF ₂ CF ₃ OCF ₃ HH
OSO ₂ CF ₃ NO ₂ HH OCH ₂ CF ₂ CF ₃ NO ₂ HH
OSO ₂ CF ₃ NH ₂ HH OCH ₂ CF ₂ CF ₃ NH ₂ HH
OSO ₂ CF ₃ CN HH OCH ₂ CF ₂ CF ₃ CN HH
OSO ₂ CF ₃ SCF ₃ HH OCH ₂ CF ₂ CF ₃ SCF ₃ HH
OSO ₂ CF ₃ SOCF ₃ HH OCH ₂ CF ₂ CF ₃ SOCF ₃ HH
OSO ₂ CF ₃ SO ₂ CF ₃ HH OCH ₂ CF ₂ CF ₃ SO ₂ CF ₃ HH
OSO ₂ CF ₃ HFH OCH ₂ CF ₂ CF ₃ HFH
OSO ₂ CF ₃ H Cl H OCH ₂ CF ₂ CF ₃ H Cl H
OSO ₂ CF ₃ H Br H OCH ₂ CF ₂ CF ₃ H Br H
OSO ₂ CF ₃ HIH OCH ₂ CF ₂ CF ₃ HIH
OSO ₂ CF ₃ H Me H OCH ₂ CF ₂ CF ₃ H Me H
OSO ₂ CF ₃ H CF ₃ H OCH ₂ CF ₂ CF ₃ H CF ₃ H
OSO ₂ CF ₃ H SMe H OCH ₂ CF ₂ CF ₃ H SMe H
OSO ₂ CF ₃ H SOMe H OCH ₂ CF ₂ CF ₃ H SOMe H
OSO ₂ CF ₃ H SO ₂ Me H OCH ₂ CF ₂ CF ₃ H SO ₂ Me H
OSO ₂ CF ₃ H OMe H OCH ₂ CF ₂ CF ₃ H OMe H
OSO ₂ CF ₃ H OCF ₃ H OCH ₂ CF ₂ CF ₃ H OCF ₃ H
OSO ₂ CF ₃ H NO ₂ H OCH ₂ CF ₂ CF ₃ H NO ₂ H
OSO ₂ CF ₃ H NH ₂ H OCH ₂ CF ₂ CF ₃ H NH ₂ H
OSO ₂ CF ₃ H CN H OCH ₂ CF ₂ CF ₃ H CN H
OSO ₂ CF ₃ H SCF ₃ H OCH ₂ CF ₂ CF ₃ H SCF ₃ H
OSO ₂ CF ₃ H SOCF ₃ H OCH ₂ CF ₂ CF ₃ H SOCF ₃ H
OSO ₂ CF ₃ H SO ₂ CF ₃ H OCH ₂ CF ₂ CF ₃ H SO ₂ CF ₃ H
OSO ₂ CF ₃ H J1 [p = 0] H OCH ₂ CF ₂ CF ₃ H J1 [p = 0] H
OSO ₂ CF ₃ H J1 [2-CF ₃ ] H OCH ₂ CF ₂ CF ₃ H J1 [2-CF ₃ ] H
OSO ₂ CF ₃ H J1 [3-CF ₃ ] H OCH ₂ CF ₂ CF ₃ H J1 [3-CF ₃ ] H
OSO ₂ CF ₃ H J1 [4-CF ₃ ] H OCH ₂ CF ₂ CF ₃ H J1 [4-CF ₃ ] H
OSO ₂ CF ₃ H J2 H OCH ₂ CF ₂ CF ₃ H J2 H
OSO ₂ CF ₃ H J3 H OCH ₂ CF ₂ CF ₃ H J3 H
OSO ₂ CF ₃ H J4 H OCH ₂ CF ₂ CF ₃ H J4 H
OSO ₂ CF ₃ H J5 H OCH ₂ CF ₂ CF ₃ H J5 H
OSO ₂ CF ₃ H J6 [p = 0] H OCH ₂ CF ₂ CF ₃ H J6 [p = 0] H
OSO ₂ CF ₃ H J6 [3-CF ₃ ] H OCH ₂ CF ₂ CF ₃ H J6 [3-CF ₃ ] H
OSO ₂ CF ₃ H J7 H OCH ₂ CF ₂ CF ₃ H J7 H
OSO ₂ CF ₃ H J8 H OCH ₂ CF ₂ CF ₃ H J8 H
OSO ₂ CF ₃ H J9 H OCH ₂ CF ₂ CF ₃ H J9 H
OSO ₂ CF ₃ HHF OCH ₂ CF ₂ CF ₃ HHF
OSO ₂ CF ₃ HH Cl OCH ₂ CF ₂ CF ₃ HH Cl
OSO ₂ CF ₃ HH Br OCH ₂ CF ₂ CF ₃ HH Br
OSO ₂ CF ₃ HHI OCH ₂ CF ₂ CF ₃ HHI
OSO ₂ CF ₃ HH Me OCH ₂ CF ₂ CF ₃ HH Me
OSO ₂ CF ₃ HH CF ₃ OCH ₂ CF ₂ CF ₃ HH CF ₃
OSO ₂ CF ₃ HH SMe OCH ₂ CF ₂ CF ₃ HH SMe
OSO ₂ CF ₃ HH SOMe OCH ₂ CF ₂ CF ₃ HH SOMe
OSO ₂ CF ₃ HH SO ₂ Me OCH ₂ CF ₂ CF ₃ HH SO ₂ Me
OSO ₂ CF ₃ HH OMe OCH ₂ CF ₂ CF ₃ HH OMe
OSO ₂ CF ₃ HH OCF ₃ OCH ₂ CF ₂ CF ₃ HH OCF ₃
OSO ₂ CF ₃ HH NO ₂ OCH ₂ CF ₂ CF ₃ HH NO ₂
OSO ₂ CF ₃ HH NH ₂ OCH ₂ CF ₂ CF ₃ HH NH ₂
OSO ₂ CF ₃ HH CN OCH ₂ CF ₂ CF ₃ HH CN
OSO ₂ CF ₃ HH SCF ₃ OCH ₂ CF ₂ CF ₃ HH SCF ₃
OSO ₂ CF ₃ HH SOCF ₃ OCH ₂ CF ₂ CF ₃ HH SOCF ₃
OSO ₂ CF ₃ HH SO ₂ CF ₃ OCH ₂ CF ₂ CF ₃ HH SO ₂ CF ₃
OSO ₂ CF ₃ Cl H Cl OCH ₂ CF ₂ CF ₃ Cl H Cl
OSO ₂ CF ₃ Cl HF OCH ₂ CF ₂ CF ₃ Cl HF
OSO ₂ CF ₃ Cl H CN OCH ₂ CF ₂ CF ₃ Cl H CN
OSO ₂ CF ₃ Br H Br OCH ₂ CF ₂ CF ₃ Br H Br
OSO ₂ CF ₃ Br HF OCH ₂ CF ₂ CF ₃ Br HF
OSO ₂ CF ₃ Br H CN OCH ₂ CF ₂ CF ₃ Br H CN
OSO ₂ CF ₃ IHI OCH ₂ CF ₂ CF ₃ IHI
OSO ₂ CF ₃ IHF OCH ₂ CF ₂ CF ₃ IHF
OSO ₂ CF ₃ IH CN OCH ₂ CF ₂ CF ₃ IH CN
OSO ₂ CF ₃ CF ₃ HF OCH ₂ CF ₂ CF ₃ CF ₃ HF
OSO ₂ CF ₃ CF ₃ H Cl OCH ₂ CF ₂ CF ₃ CF ₃ H Cl
OSO ₂ CF ₃ CF ₃ H Br OCH ₂ CF ₂ CF ₃ CF ₃ H Br
OSO ₂ CF ₃ CF ₃ HI OCH ₂ CF ₂ CF ₃ CF ₃ HI
OSO ₂ CF ₃ CF ₃ H CN OCH ₂ CF ₂ CF ₃ CF ₃ H CN
OSO ₂ CF ₃ IFH OCH ₂ CF ₂ CF ₃ IFH
――――――――――――――――― ―――――――――――――――――――――
[Table 2]

――――――――――――――― ――――――――――――――――
R ⁴ Y2 Y3 R ⁴ Y2 Y3
――――――――――――――― ――――――――――――――――
CF ₃ HH OCH ₂ CF ₂ CF ₂ CF ₃ HH
CF ₃ FH OCH ₂ CF ₂ CF ₂ CF ₃ FH
CF ₃ Cl H OCH ₂ CF ₂ CF ₂ CF ₃ Cl H
CF ₃ Br H OCH ₂ CF ₂ CF ₂ CF ₃ Br H
CF ₃ IH OCH ₂ CF ₂ CF ₂ CF ₃ IH
CF ₃ Me H OCH ₂ CF ₂ CF ₂ CF ₃ Me H
CF ₃ CF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ H
CF ₃ SMe H OCH ₂ CF ₂ CF ₂ CF ₃ SMe H
CF ₃ SOMe H OCH ₂ CF ₂ CF ₂ CF ₃ SOMe H
CF ₃ SO ₂ Me H OCH ₂ CF ₂ CF ₂ CF ₃ SO ₂ Me H
CF ₃ OMe H OCH ₂ CF ₂ CF ₂ CF ₃ OMe H
CF ₃ OCF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ OCF ₃ H
CF ₃ NO ₂ H OCH ₂ CF ₂ CF ₂ CF ₃ NO ₂ H
CF ₃ NH ₂ H OCH ₂ CF ₂ CF ₂ CF ₃ NH ₂ H
CF ₃ CN H OCH ₂ CF ₂ CF ₂ CF ₃ CN H
CF ₃ HF OCH ₂ CF ₂ CF ₂ CF ₃ HF
CF ₃ H Cl OCH ₂ CF ₂ CF ₂ CF ₃ H Cl
CF ₃ H Br OCH ₂ CF ₂ CF ₂ CF ₃ H Br
CF ₃ HI OCH ₂ CF ₂ CF ₂ CF ₃ HI
CF ₃ H Me OCH ₂ CF ₂ CF ₂ CF ₃ H Me
CF ₃ H CF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ H CF ₃
CF ₃ H SMe OCH ₂ CF ₂ CF ₂ CF ₃ H SMe
CF ₃ H SOMe OCH ₂ CF ₂ CF ₂ CF ₃ H SOMe
CF ₃ H SO ₂ Me OCH ₂ CF ₂ CF ₂ CF ₃ H SO ₂ Me
CF ₃ H OMe OCH ₂ CF ₂ CF ₂ CF ₃ H OMe
CF ₃ H OCF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ H OCF ₃
CF ₃ H NO ₂ OCH ₂ CF ₂ CF ₂ CF ₃ H NO ₂
CF ₃ H NH ₂ OCH ₂ CF ₂ CF ₂ CF ₃ H NH ₂
CF ₃ H CN OCH ₂ CF ₂ CF ₂ CF ₃ H CN
CF ₃ IF OCH ₂ CF ₂ CF ₂ CF ₃ IF
OCH ₂ CF ₃ HH OCH ₂ CF ₂ CHFCF ₃ HH
OCH ₂ CF ₃ FH OCH ₂ CF ₂ CHFCF ₃ FH
OCH ₂ CF ₃ Cl H OCH ₂ CF ₂ CHFCF ₃ Cl H
OCH ₂ CF ₃ Br H OCH ₂ CF ₂ CHFCF ₃ Br H
OCH ₂ CF ₃ IH OCH ₂ CF ₂ CHFCF ₃ IH
OCH ₂ CF ₃ Me H OCH ₂ CF ₂ CHFCF ₃ Me H
OCH ₂ CF ₃ CF ₃ H OCH ₂ CF ₂ CHFCF ₃ CF ₃ H
OCH ₂ CF ₃ SMe H OCH ₂ CF ₂ CHFCF ₃ SMe H
OCH ₂ CF ₃ SOMe H OCH ₂ CF ₂ CHFCF ₃ SOMe H
OCH ₂ CF ₃ SO ₂ Me H OCH ₂ CF ₂ CHFCF ₃ SO ₂ Me H
OCH ₂ CF ₃ OMe H OCH ₂ CF ₂ CHFCF ₃ OMe H
OCH ₂ CF ₃ OCF ₃ H OCH ₂ CF ₂ CHFCF ₃ OCF ₃ H
OCH ₂ CF ₃ NO ₂ H OCH ₂ CF ₂ CHFCF ₃ NO ₂ H
OCH ₂ CF ₃ NH ₂ H OCH ₂ CF ₂ CHFCF ₃ NH ₂ H
OCH ₂ CF ₃ CN H OCH ₂ CF ₂ CHFCF ₃ CN H
OCH ₂ CF ₃ HF OCH ₂ CF ₂ CHFCF ₃ HF
OCH ₂ CF ₃ H Cl OCH ₂ CF ₂ CHFCF ₃ H Cl
OCH ₂ CF ₃ H Br OCH ₂ CF ₂ CHFCF ₃ H Br
OCH ₂ CF ₃ HI OCH ₂ CF ₂ CHFCF ₃ HI
OCH ₂ CF ₃ H Me OCH ₂ CF ₂ CHFCF ₃ H Me
OCH ₂ CF ₃ H CF ₃ OCH ₂ CF ₂ CHFCF ₃ H CF ₃
OCH ₂ CF ₃ H SMe OCH ₂ CF ₂ CHFCF ₃ H SMe
OCH ₂ CF ₃ H SOMe OCH ₂ CF ₂ CHFCF ₃ H SOMe
OCH ₂ CF ₃ H SO ₂ Me OCH ₂ CF ₂ CHFCF ₃ H SO ₂ Me
OCH ₂ CF ₃ H OMe OCH ₂ CF ₂ CHFCF ₃ H OMe
OCH ₂ CF ₃ H OCF ₃ OCH ₂ CF ₂ CHFCF ₃ H OCF ₃
OCH ₂ CF ₃ H NO ₂ OCH ₂ CF ₂ CHFCF ₃ H NO ₂
OCH ₂ CF ₃ H NH ₂ OCH ₂ CF ₂ CHFCF ₃ H NH ₂
OCH ₂ CF ₃ H CN OCH ₂ CF ₂ CHFCF ₃ H CN
OCH ₂ CF ₃ IF OCH ₂ CF ₂ CHFCF ₃ IF
OCH ₂ CHF ₂ HH OCH ₂ CF ₂ CHF ₂ HH
OCH ₂ CHF ₂ FH OCH ₂ CF ₂ CHF ₂ FH
OCH ₂ CHF ₂ Cl H OCH ₂ CF ₂ CHF ₂ Cl H
OCH ₂ CHF ₂ Br H OCH ₂ CF ₂ CHF ₂ Br H
OCH ₂ CHF ₂ IH OCH ₂ CF ₂ CHF ₂ IH
OCH ₂ CHF ₂ Me H OCH ₂ CF ₂ CHF ₂ Me H
OCH ₂ CHF ₂ CF ₃ H OCH ₂ CF ₂ CHF ₂ CF ₃ H
OCH ₂ CHF ₂ SMe H OCH ₂ CF ₂ CHF ₂ SMe H
OCH ₂ CHF ₂ SOMe H OCH ₂ CF ₂ CHF ₂ SOMe H
OCH ₂ CHF ₂ SO ₂ Me H OCH ₂ CF ₂ CHF ₂ SO ₂ Me H
OCH ₂ CHF ₂ OMe H OCH ₂ CF ₂ CHF ₂ OMe H
OCH ₂ CHF ₂ OCF ₃ H OCH ₂ CF ₂ CHF ₂ OCF ₃ H
OCH ₂ CHF ₂ NO ₂ H OCH ₂ CF ₂ CHF ₂ NO ₂ H
OCH ₂ CHF ₂ NH ₂ H OCH ₂ CF ₂ CHF ₂ NH ₂ H
OCH ₂ CHF ₂ CN H OCH ₂ CF ₂ CHF ₂ CN H
OCH ₂ CHF ₂ HF OCH ₂ CF ₂ CHF ₂ HF
OCH ₂ CHF ₂ H Cl OCH ₂ CF ₂ CHF ₂ H Cl
OCH ₂ CHF ₂ H Br OCH ₂ CF ₂ CHF ₂ H Br
OCH ₂ CHF ₂ HI OCH ₂ CF ₂ CHF ₂ HI
OCH ₂ CHF ₂ H Me OCH ₂ CF ₂ CHF ₂ H Me
OCH ₂ CHF ₂ H CF ₃ OCH ₂ CF ₂ CHF ₂ H CF ₃
OCH ₂ CHF ₂ H SMe OCH ₂ CF ₂ CHF ₂ H SMe
OCH ₂ CHF ₂ H SOMe OCH ₂ CF ₂ CHF ₂ H SOMe
OCH ₂ CHF ₂ H SO ₂ Me OCH ₂ CF ₂ CHF ₂ H SO ₂ Me
OCH ₂ CHF ₂ H OMe OCH ₂ CF ₂ CHF ₂ H OMe
OCH ₂ CHF ₂ H OCF ₃ OCH ₂ CF ₂ CHF ₂ H OCF ₃
OCH ₂ CHF ₂ H NO ₂ OCH ₂ CF ₂ CHF ₂ H NO ₂
OCH ₂ CHF ₂ H NH ₂ OCH ₂ CF ₂ CHF ₂ H NH ₂
OCH ₂ CHF ₂ H CN OCH ₂ CF ₂ CHF ₂ H CN
OCH ₂ CHF ₂ IF OCH ₂ CF ₂ CHF ₂ IF
OCH ₂ CF ₂ CF ₃ HH OSO ₂ CF ₃ HH
OCH ₂ CF ₂ CF ₃ FH OSO ₂ CF ₃ FH
OCH ₂ CF ₂ CF ₃ Cl H OSO ₂ CF ₃ Cl H
OCH ₂ CF ₂ CF ₃ Br H OSO ₂ CF ₃ Br H
OCH ₂ CF ₂ CF ₃ IH OSO ₂ CF ₃ IH
OCH ₂ CF ₂ CF ₃ Me H OSO ₂ CF ₃ Me H
OCH ₂ CF ₂ CF ₃ CF ₃ H OSO ₂ CF ₃ CF ₃ H
OCH ₂ CF ₂ CF ₃ SMe H OSO ₂ CF ₃ SMe H
OCH ₂ CF ₂ CF ₃ SOMe H OSO ₂ CF ₃ SOMe H
OCH ₂ CF ₂ CF ₃ SO ₂ Me H OSO ₂ CF ₃ SO ₂ Me H
OCH ₂ CF ₂ CF ₃ OMe H OSO ₂ CF ₃ OMe H
OCH ₂ CF ₂ CF ₃ OCF ₃ H OSO ₂ CF ₃ OCF ₃ H
OCH ₂ CF ₂ CF ₃ NO ₂ H OSO ₂ CF ₃ NO ₂ H
OCH ₂ CF ₂ CF ₃ NH ₂ H OSO ₂ CF ₃ NH ₂ H
OCH ₂ CF ₂ CF ₃ CN H OSO ₂ CF ₃ CN H
OCH ₂ CF ₂ CF ₃ HF OSO ₂ CF ₃ HF
OCH ₂ CF ₂ CF ₃ H Cl OSO ₂ CF ₃ H Cl
OCH ₂ CF ₂ CF ₃ H Br OSO ₂ CF ₃ H Br
OCH ₂ CF ₂ CF ₃ HI OSO ₂ CF ₃ HI
OCH ₂ CF ₂ CF ₃ H Me OSO ₂ CF ₃ H Me
OCH ₂ CF ₂ CF ₃ H CF ₃ OSO ₂ CF ₃ H CF ₃
OCH ₂ CF ₂ CF ₃ H SMe OSO ₂ CF ₃ H SMe
OCH ₂ CF ₂ CF ₃ H SOMe OSO ₂ CF ₃ H SOMe
OCH ₂ CF ₂ CF ₃ H SO ₂ Me OSO ₂ CF ₃ H SO ₂ Me
OCH ₂ CF ₂ CF ₃ H OMe OSO ₂ CF ₃ H OMe
OCH ₂ CF ₂ CF ₃ H OCF ₃ OSO ₂ CF ₃ H OCF ₃
OCH ₂ CF ₂ CF ₃ H NO ₂ OSO ₂ CF ₃ H NO ₂
OCH ₂ CF ₂ CF ₃ H NH ₂ OSO ₂ CF ₃ H NH ₂
OCH ₂ CF ₂ CF ₃ H CN OSO ₂ CF ₃ H CN
OCH ₂ CF ₂ CF ₃ IF OSO ₂ CF ₃ IF
――――――――――――――― ――――――――――――――――
[Table 3]

――――――― ―――――――――― ――――――――― ―――――――――
R ⁴ Y3 R ⁴ Y3 R ⁴ Y3 R ⁴ Y3
――――――― ―――――――――― ――――――――― ―――――――――
CF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ H OCH ₂ CHF ₂ H OCH ₂ CF ₂ CHF ₂ H
CF ₃ F OCH ₂ CF ₂ CF ₂ CF ₃ F OCH ₂ CHF ₂ F OCH ₂ CF ₂ CHF ₂ F
CF ₃ Cl OCH ₂ CF ₂ CF ₂ CF ₃ Cl OCH ₂ CHF ₂ Cl OCH ₂ CF ₂ CHF ₂ Cl
CF ₃ Br OCH ₂ CF ₂ CF ₂ CF ₃ Br OCH ₂ CHF ₂ Br OCH ₂ CF ₂ CHF ₂ Br
CF ₃ I OCH ₂ CF ₂ CF ₂ CF ₃ I OCH ₂ CHF ₂ I OCH ₂ CF ₂ CHF ₂ I
CF ₃ Me OCH ₂ CF ₂ CF ₂ CF ₃ Me OCH ₂ CHF ₂ Me OCH ₂ CF ₂ CHF ₂ Me
CF ₃ CF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ OCH ₂ CHF ₂ CF ₃ OCH ₂ CF ₂ CHF ₂ CF ₃
CF ₃ SMe OCH ₂ CF ₂ CF ₂ CF ₃ SMe OCH ₂ CHF ₂ SMe OCH ₂ CF ₂ CHF ₂ SMe
CF ₃ SOMe OCH ₂ CF ₂ CF ₂ CF ₃ SOMe OCH ₂ CHF ₂ SOMe OCH ₂ CF ₂ CHF ₂ SOMe
CF ₃ SO ₂ Me OCH ₂ CF ₂ CF ₂ CF ₃ SO ₂ Me OCH ₂ CHF ₂ SO ₂ Me OCH ₂ CF ₂ CHF ₂ SO ₂ Me
CF ₃ OMe OCH ₂ CF ₂ CF ₂ CF ₃ OMe OCH ₂ CHF ₂ OMe OCH ₂ CF ₂ CHF ₂ OMe
CF ₃ OCF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ OCF ₃ OCH ₂ CHF ₂ OCF ₃ OCH ₂ CF ₂ CHF ₂ OCF ₃
CF ₃ NO ₂ OCH ₂ CF ₂ CF ₂ CF ₃ NO ₂ OCH ₂ CHF ₂ NO ₂ OCH ₂ CF ₂ CHF ₂ NO ₂
CF ₃ NH ₂ OCH ₂ CF ₂ CF ₂ CF ₃ NH ₂ OCH ₂ CHF ₂ NH ₂ OCH ₂ CF ₂ CHF ₂ NH ₂
CF ₃ CN OCH ₂ CF ₂ CF ₂ CF ₃ CN OCH ₂ CHF ₂ CN OCH ₂ CF ₂ CHF ₂ CN
CF ₃ J9 OCH ₂ CF ₂ CF ₂ CF ₃ J9 OCH ₂ CHF ₂ J9 OCH ₂ CF ₂ CHF ₂ J9
OCH ₂ CF ₃ H OCH ₂ CF ₂ CHFCF ₃ H OCH ₂ CF ₂ CF ₃ H OSO ₂ CF ₃ H
OCH ₂ CF ₃ F OCH ₂ CF ₂ CHFCF ₃ F OCH ₂ CF ₂ CF ₃ F OSO ₂ CF ₃ F
OCH ₂ CF ₃ Cl OCH ₂ CF ₂ CHFCF ₃ Cl OCH ₂ CF ₂ CF ₃ Cl OSO ₂ CF ₃ Cl
OCH ₂ CF ₃ Br OCH ₂ CF ₂ CHFCF ₃ Br OCH ₂ CF ₂ CF ₃ Br OSO ₂ CF ₃ Br
OCH ₂ CF ₃ I OCH ₂ CF ₂ CHFCF ₃ I OCH ₂ CF ₂ CF ₃ I OSO ₂ CF ₃ I
OCH ₂ CF ₃ Me OCH ₂ CF ₂ CHFCF ₃ Me OCH ₂ CF ₂ CF ₃ Me OSO ₂ CF ₃ Me
OCH ₂ CF ₃ CF ₃ OCH ₂ CF ₂ CHFCF ₃ CF ₃ OCH ₂ CF ₂ CF ₃ CF ₃ OSO ₂ CF ₃ CF ₃
OCH ₂ CF ₃ SMe OCH ₂ CF ₂ CHFCF ₃ SMe OCH ₂ CF ₂ CF ₃ SMe OSO ₂ CF ₃ SMe
OCH ₂ CF ₃ SOMe OCH ₂ CF ₂ CHFCF ₃ SOMe OCH ₂ CF ₂ CF ₃ SOMe OSO ₂ CF ₃ SOMe
OCH ₂ CF ₃ SO ₂ Me OCH ₂ CF ₂ CHFCF ₃ SO ₂ Me OCH ₂ CF ₂ CF ₃ SO ₂ Me OSO ₂ CF ₃ SO ₂ Me
OCH ₂ CF ₃ OMe OCH ₂ CF ₂ CHFCF ₃ OMe OCH ₂ CF ₂ CF ₃ OMe OSO ₂ CF ₃ OMe
OCH ₂ CF ₃ OCF ₃ OCH ₂ CF ₂ CHFCF ₃ OCF ₃ OCH ₂ CF ₂ CF ₃ OCF ₃ OSO ₂ CF ₃ OCF ₃
OCH ₂ CF ₃ NO ₂ OCH ₂ CF ₂ CHFCF ₃ NO ₂ OCH ₂ CF ₂ CF ₃ NO ₂ OSO ₂ CF ₃ NO ₂
OCH ₂ CF ₃ NH ₂ OCH ₂ CF ₂ CHFCF ₃ NH ₂ OCH ₂ CF ₂ CF ₃ NH ₂ OSO ₂ CF ₃ NH ₂
OCH ₂ CF ₃ CN OCH ₂ CF ₂ CHFCF ₃ CN OCH ₂ CF ₂ CF ₃ CN OSO ₂ CF ₃ CN
OCH ₂ CF ₃ J9 OCH ₂ CF ₂ CHFCF ₃ J9 OCH ₂ CF ₂ CF ₃ J9 OSO ₂ CF ₃ J9
――――――― ―――――――――― ――――――――― ―――――――――
[Table 4]

――――――― ―――――――――― ――――――――― ―――――――――
R ⁴ Y2 R ⁴ Y2 R ⁴ Y2 R ⁴ Y2
――――――― ―――――――――― ――――――――― ―――――――――
CF ₃ H OCH ₂ CF ₂ CF ₂ CF ₃ H OCH ₂ CHF ₂ H OCH ₂ CF ₂ CHF ₂ H
CF ₃ F OCH ₂ CF ₂ CF ₂ CF ₃ F OCH ₂ CHF ₂ F OCH ₂ CF ₂ CHF ₂ F
CF ₃ Cl OCH ₂ CF ₂ CF ₂ CF ₃ Cl OCH ₂ CHF ₂ Cl OCH ₂ CF ₂ CHF ₂ Cl
CF ₃ Br OCH ₂ CF ₂ CF ₂ CF ₃ Br OCH ₂ CHF ₂ Br OCH ₂ CF ₂ CHF ₂ Br
CF ₃ I OCH ₂ CF ₂ CF ₂ CF ₃ I OCH ₂ CHF ₂ I OCH ₂ CF ₂ CHF ₂ I
CF ₃ Me OCH ₂ CF ₂ CF ₂ CF ₃ Me OCH ₂ CHF ₂ Me OCH ₂ CF ₂ CHF ₂ Me
CF ₃ CF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ CF ₃ OCH ₂ CHF ₂ CF ₃ OCH ₂ CF ₂ CHF ₂ CF ₃
CF ₃ SMe OCH ₂ CF ₂ CF ₂ CF ₃ SMe OCH ₂ CHF ₂ SMe OCH ₂ CF ₂ CHF ₂ SMe
CF ₃ SOMe OCH ₂ CF ₂ CF ₂ CF ₃ SOMe OCH ₂ CHF ₂ SOMe OCH ₂ CF ₂ CHF ₂ SOMe
CF ₃ SO ₂ Me OCH ₂ CF ₂ CF ₂ CF ₃ SO ₂ Me OCH ₂ CHF ₂ SO ₂ Me OCH ₂ CF ₂ CHF ₂ SO ₂ Me
CF ₃ OMe OCH ₂ CF ₂ CF ₂ CF ₃ OMe OCH ₂ CHF ₂ OMe OCH ₂ CF ₂ CHF ₂ OMe
CF ₃ OCF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ OCF ₃ OCH ₂ CHF ₂ OCF ₃ OCH ₂ CF ₂ CHF ₂ OCF ₃
CF ₃ NO ₂ OCH ₂ CF ₂ CF ₂ CF ₃ NO ₂ OCH ₂ CHF ₂ NO ₂ OCH ₂ CF ₂ CHF ₂ NO ₂
CF ₃ NH ₂ OCH ₂ CF ₂ CF ₂ CF ₃ NH ₂ OCH ₂ CHF ₂ NH ₂ OCH ₂ CF ₂ CHF ₂ NH ₂
CF ₃ CN OCH ₂ CF ₂ CF ₂ CF ₃ CN OCH ₂ CHF ₂ CN OCH ₂ CF ₂ CHF ₂ CN
CF ₃ J9 OCH ₂ CF ₂ CF ₂ CF ₃ J9 OCH ₂ CHF ₂ J9 OCH ₂ CF ₂ CHF ₂ J9
OCH ₂ CF ₃ H OCH ₂ CF ₂ CHFCF ₃ H OCH ₂ CF ₂ CF ₃ H OSO ₂ CF ₃ H
OCH ₂ CF ₃ F OCH ₂ CF ₂ CHFCF ₃ F OCH ₂ CF ₂ CF ₃ F OSO ₂ CF ₃ F
OCH ₂ CF ₃ Cl OCH ₂ CF ₂ CHFCF ₃ Cl OCH ₂ CF ₂ CF ₃ Cl OSO ₂ CF ₃ Cl
OCH ₂ CF ₃ Br OCH ₂ CF ₂ CHFCF ₃ Br OCH ₂ CF ₂ CF ₃ Br OSO ₂ CF ₃ Br
OCH ₂ CF ₃ I OCH ₂ CF ₂ CHFCF ₃ I OCH ₂ CF ₂ CF ₃ I OSO ₂ CF ₃ I
OCH ₂ CF ₃ Me OCH ₂ CF ₂ CHFCF ₃ Me OCH ₂ CF ₂ CF ₃ Me OSO ₂ CF ₃ Me
OCH ₂ CF ₃ CF ₃ OCH ₂ CF ₂ CHFCF ₃ CF ₃ OCH ₂ CF ₂ CF ₃ CF ₃ OSO ₂ CF ₃ CF ₃
OCH ₂ CF ₃ SMe OCH ₂ CF ₂ CHFCF ₃ SMe OCH ₂ CF ₂ CF ₃ SMe OSO ₂ CF ₃ SMe
OCH ₂ CF ₃ SOMe OCH ₂ CF ₂ CHFCF ₃ SOMe OCH ₂ CF ₂ CF ₃ SOMe OSO ₂ CF ₃ SOMe
OCH ₂ CF ₃ SO ₂ Me OCH ₂ CF ₂ CHFCF ₃ SO ₂ Me OCH ₂ CF ₂ CF ₃ SO ₂ Me OSO ₂ CF ₃ SO ₂ Me
OCH ₂ CF ₃ OMe OCH ₂ CF ₂ CHFCF ₃ OMe OCH ₂ CF ₂ CF ₃ OMe OSO ₂ CF ₃ OMe
OCH ₂ CF ₃ OCF ₃ OCH ₂ CF ₂ CHFCF ₃ OCF ₃ OCH ₂ CF ₂ CF ₃ OCF ₃ OSO ₂ CF ₃ OCF ₃
OCH ₂ CF ₃ NO ₂ OCH ₂ CF ₂ CHFCF ₃ NO ₂ OCH ₂ CF ₂ CF ₃ NO ₂ OSO ₂ CF ₃ NO ₂
OCH ₂ CF ₃ NH ₂ OCH ₂ CF ₂ CHFCF ₃ NH ₂ OCH ₂ CF ₂ CF ₃ NH ₂ OSO ₂ CF ₃ NH ₂
OCH ₂ CF ₃ CN OCH ₂ CF ₂ CHFCF ₃ CN OCH ₂ CF ₂ CF ₃ CN OSO ₂ CF ₃ CN
OCH ₂ CF ₃ J9 OCH ₂ CF ₂ CHFCF ₃ J9 OCH ₂ CF ₂ CF ₃ J9 OSO ₂ CF ₃ J9
――――――― ―――――――――― ――――――――― ―――――――――
[Table 5]

―――――――――――― ――――――――――――― ――――――――――――――
R ⁴ G ₅ Y6 R ⁴ G ₅ Y6 R ⁴ G ₅ Y6
―――――――――――― ――――――――――――― ――――――――――――――
CF ₃ CH H CF ₃ CH Me CF ₃ N Br
CF ₃ CH F CF ₃ CH CF ₃ CF ₃ NI
CF ₃ CH Cl CF ₃ NH CF ₃ N Me
CF ₃ CH Br CF ₃ NF CF ₃ N CF ₃
CF ₃ CH I CF ₃ N Cl CF ₃ N SMe
OCH ₂ CHF ₂ CH H OCH ₂ CHF ₂ CH Me OCH ₂ CHF ₂ N Br
OCH ₂ CHF ₂ CH F OCH ₂ CHF ₂ CH CF ₃ OCH ₂ CHF ₂ NI
OCH ₂ CHF ₂ CH Cl OCH ₂ CHF ₂ NH OCH ₂ CHF ₂ N Me
OCH ₂ CHF ₂ CH Br OCH ₂ CHF ₂ NF OCH ₂ CHF ₂ N CF ₃
OCH ₂ CHF ₂ CH I OCH ₂ CHF ₂ N Cl OCH ₂ CHF ₂ N SMe
OCH ₂ CF ₂ CF ₂ CF ₃ CH H OCH ₂ CF ₂ CF ₂ CF ₃ CH Me OCH ₂ CF ₂ CF ₂ CF ₃ N Br
OCH ₂ CF ₂ CF ₂ CF ₃ CH F OCH ₂ CF ₂ CF ₂ CF ₃ CH CF ₃ OCH ₂ CF ₂ CF ₂ CF ₃ NI
OCH ₂ CF ₂ CF ₂ CF ₃ CH Cl OCH ₂ CF ₂ CF ₂ CF ₃ NH OCH ₂ CF ₂ CF ₂ CF ₃ N Me
OCH ₂ CF ₂ CF ₂ CF ₃ CH Br OCH ₂ CF ₂ CF ₂ CF ₃ NF OCH ₂ CF ₂ CF ₂ CF ₃ N CF ₃
OCH ₂ CF ₂ CF ₂ CF ₃ CH I OCH ₂ CF ₂ CF ₂ CF ₃ N Cl OCH ₂ CF ₂ CF ₂ CF ₃ N SMe
OCH ₂ CF ₂ CHFCF ₃ CH H OCH ₂ CF ₂ CHFCF ₃ CH Me OCH ₂ CF ₂ CHFCF ₃ N Br
OCH ₂ CF ₂ CHFCF ₃ CH F OCH ₂ CF ₂ CHFCF ₃ CH CF ₃ OCH ₂ CF ₂ CHFCF ₃ NI
OCH ₂ CF ₂ CHFCF ₃ CH Cl OCH ₂ CF ₂ CHFCF ₃ NH OCH ₂ CF ₂ CHFCF ₃ N Me
OCH ₂ CF ₂ CHFCF ₃ CH Br OCH ₂ CF ₂ CHFCF ₃ NF OCH ₂ CF ₂ CHFCF ₃ N CF ₃
OCH ₂ CF ₂ CHFCF ₃ CH I OCH ₂ CF ₂ CHFCF ₃ N Cl OCH ₂ CF ₂ CHFCF ₃ N SMe
OCH ₂ CF ₂ CHF ₂ CH H OCH ₂ CF ₂ CHF ₂ CH Me OCH ₂ CF ₂ CHF ₂ N Br
OCH ₂ CF ₂ CHF ₂ CH F OCH ₂ CF ₂ CHF ₂ CH CF ₃ OCH ₂ CF ₂ CHF ₂ NI
OCH ₂ CF ₂ CHF ₂ CH Cl OCH ₂ CF ₂ CHF ₂ NH OCH ₂ CF ₂ CHF ₂ N Me
OCH ₂ CF ₂ CHF ₂ CH Br OCH ₂ CF ₂ CHF ₂ NF OCH ₂ CF ₂ CHF ₂ N CF ₃
OCH ₂ CF ₂ CHF ₂ CH I OCH ₂ CF ₂ CHF ₂ N Cl OCH ₂ CF ₂ CHF ₂ N SMe
OCH ₂ CF ₂ CF ₃ CH H OCH ₂ CF ₂ CF ₃ CH Me OCH ₂ CF ₂ CF ₃ N Br
OCH ₂ CF ₂ CF ₃ CH F OCH ₂ CF ₂ CF ₃ CH CF ₃ OCH ₂ CF ₂ CF ₃ NI
OCH ₂ CF ₂ CF ₃ CH Cl OCH ₂ CF ₂ CF ₃ NH OCH ₂ CF ₂ CF ₃ N Me
OCH ₂ CF ₂ CF ₃ CH Br OCH ₂ CF ₂ CF ₃ NF OCH ₂ CF ₂ CF ₃ N CF ₃
OCH ₂ CF ₂ CF ₃ CH I OCH ₂ CF ₂ CF ₃ N Cl OCH ₂ CF ₂ CF ₃ N SMe
OSO ₂ CF ₃ CH H OSO ₂ CF ₃ CH Me OSO ₂ CF ₃ N Br
OSO ₂ CF ₃ CH F OSO ₂ CF ₃ CH CF ₃ OSO ₂ CF ₃ NI
OSO ₂ CF ₃ CH Cl OSO ₂ CF ₃ NH OSO ₂ CF ₃ N Me
OSO ₂ CF ₃ CH Br OSO ₂ CF ₃ NF OSO ₂ CF ₃ N CF ₃
OSO ₂ CF ₃ CH I OSO ₂ CF ₃ N Cl OSO ₂ CF ₃ N SMe
―――――――――――― ――――――――――――― ――――――――――――――
[Table 6]

―――――――――――――― ――――――――――――――――――
R ² R ³ R ⁴ Y2 Y3 R ² R ³ R ⁴ Y2 Y3
―――――――――――――― ――――――――――――――――――
CF ₃ HHHH SCF ₃ HHHH
CF ₃ HH CF ₃ H SCF ₃ HH CF ₃ H
CF ₃ HHH CF ₃ SCF ₃ HHH CF ₃
H CF ₃ HHHH SCF ₃ HHH
H CF ₃ H CF ₃ HH SCF ₃ H CF ₃ H
H CF ₃ HH CF ₃ H SCF ₃ HH CF ₃
HH CF ₃ HHHH SCF ₃ HH
HH CF ₃ CF ₃ HHH SCF ₃ CF ₃ H
HH CF ₃ H CF ₃ HH SCF ₃ H CF ₃
OCF ₃ HHHH SCH ₂ CF ₃ HHHH
OCF ₃ HH CF ₃ H SCH ₂ CF ₃ HH CF ₃ H
OCF ₃ HHH CF ₃ SCH ₂ CF ₃ HHH CF ₃
H OCF ₃ HHHH SCH ₂ CF ₃ HHH
H OCF ₃ H CF ₃ HH SCH ₂ CF ₃ H CF ₃ H
H OCF ₃ HH CF ₃ H SCH ₂ CF ₃ HH CF ₃
HH OCF ₃ HHHH SCH ₂ CF ₃ HH
HH OCF ₃ CF ₃ HHH SCH ₂ CF ₃ CF ₃ H
HH OCF ₃ H CF ₃ HH SCH ₂ CF ₃ H CF ₃
FH CF ₃ HH Cl H CF ₃ HH
FH CF ₃ CF ₃ H Cl H CF ₃ CF ₃ H
FH CF ₃ H CF ₃ Cl H CF ₃ H CF ₃
―――――――――――――― ――――――――――――――――――
[Table 7]

――――――――――――― ―――――――――――――――――
R ² R ³ R ⁴ Y3 R ² R ³ R ⁴ Y3
――――――――――――― ―――――――――――――――――
CF ₃ HHH SCF ₃ HHH
CF ₃ HH CF ₃ SCF ₃ HH CF ₃
H CF ₃ HHH SCF ₃ HH
H CF ₃ H CF ₃ H SCF ₃ H CF ₃
HH CF ₃ HHH SCF ₃ H
HH CF ₃ CF ₃ HH SCF ₃ CF ₃
OCF ₃ HHH SCH ₂ CF ₃ HHH
OCF ₃ HH CF ₃ SCH ₂ CF ₃ HH CF ₃
H OCF ₃ HHH SCH ₂ CF ₃ HH
H OCF ₃ H CF ₃ H SCH ₂ CF ₃ H CF ₃
HH OCF ₃ HHH SCH ₂ CF ₃ H
HH OCF ₃ CF ₃ HH SCH ₂ CF ₃ CF ₃
FH CF ₃ H Cl H CF ₃ H
FH CF ₃ CF ₃ Cl H CF ₃ CF ₃
――――――――――――― ―――――――――――――――――
[Table 8]

――――――――――――― ―――――――――――――――――
R ² R ³ R ⁴ Y2 R ² R ³ R ⁴ Y2
――――――――――――― ―――――――――――――――――
CF ₃ HHH SCF ₃ HHH
CF ₃ HH CF ₃ SCF ₃ HH CF ₃
H CF ₃ HHH SCF ₃ HH
H CF ₃ H CF ₃ H SCF ₃ H CF ₃
HH CF ₃ HHH SCF ₃ H
HH CF ₃ CF ₃ HH SCF ₃ CF ₃
OCF ₃ HHH SCH ₂ CF ₃ HHH
OCF ₃ HH CF ₃ SCH ₂ CF ₃ HH CF ₃
H OCF ₃ HHH SCH ₂ CF ₃ HH
H OCF ₃ H CF ₃ H SCH ₂ CF ₃ H CF ₃
HH OCF ₃ HHH SCH ₂ CF ₃ H
HH OCF ₃ CF ₃ HH SCH ₂ CF ₃ CF ₃
FH CF ₃ H Cl H CF ₃ H
FH CF ₃ CF ₃ Cl H CF ₃ CF ₃
――――――――――――― ―――――――――――――――――
[Table 9]

――――――――――――――― ――――――――――――――――――――
R ² R ³ R ⁴ G ₅ Y6 R ² R ³ R ⁴ G ₅ Y6
――――――――――――――― ――――――――――――――――――――
CF ₃ HHNH SCF ₃ HHNH
CF ₃ HHN CF ₃ SCF ₃ HHN CF ₃
H CF ₃ HNHH SCF ₃ HNH
H CF ₃ HN CF ₃ H SCF ₃ HN CF ₃
HH CF ₃ NHHH SCF ₃ NH
HH CF ₃ N CF ₃ HH SCF ₃ N CF ₃
OCF ₃ HHNH SCH ₂ CF ₃ HHNH
OCF ₃ HHN CF ₃ SCH ₂ CF ₃ HHN CF ₃
H OCF ₃ HNHH SCH ₂ CF ₃ HNH
H OCF ₃ HN CF ₃ H SCH ₂ CF ₃ HN CF ₃
HH OCF ₃ NHHH SCH ₂ CF ₃ NH
HH OCF ₃ N CF ₃ HH SCH ₂ CF ₃ N CF ₃
FH CF ₃ NH Cl H CF ₃ NH
FH CF ₃ N CF ₃ Cl H CF ₃ N CF ₃
CF ₃ HH CH H SCF ₃ HH CH H
CF ₃ HH CH CF ₃ SCF ₃ HH CH CF ₃
H CF ₃ H CH HH SCF ₃ H CH H
H CF ₃ H CH CF ₃ H SCF ₃ H CH CF ₃
HH CF ₃ CH HHH SCF ₃ CH H
HH CF ₃ CH CF ₃ HH SCF ₃ CH CF ₃
OCF ₃ HH CH H SCH ₂ CF ₃ HH CH H
OCF ₃ HH CH CF ₃ SCH ₂ CF ₃ HH CH CF ₃
H OCF ₃ H CH HH SCH ₂ CF ₃ H CH H
H OCF ₃ H CH CF ₃ H SCH ₂ CF ₃ H CH CF ₃
HH OCF ₃ CH HHH SCH ₂ CF ₃ CH H
HH OCF ₃ CH CF ₃ HH SCH ₂ CF ₃ CH CF ₃
FH CF ₃ CH H Cl H CF ₃ CH H
FH CF ₃ CH CF ₃ Cl H CF ₃ CH CF ₃
――――――――――――――― ――――――――――――――――――――
The pest control agent in the present invention is the field of agriculture and horticulture or the field of livestock and hygiene (internal parasites / external parasites for domestic animals and pets, hygiene pests and unpleasant pests for domestic and commercial use) It means a pest control agent for harmful arthropods such as The agrochemical in the present invention means an insecticide / acaricide, nematicide, herbicide, fungicide, etc. in the field of agriculture and horticulture.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Spider mites such as honeybees (Varroa jacobsoni).

  Tick (Boophilus microplus), Thip tick (Haemaphysaliscampanulata), Tick tick (Haemaphysaliscampanulata), Tick tick (Ixo tus tick) spp.), ticks such as Dermacentor spp.

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

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

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

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

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

  Crustaceans such as Armadillidium vulgare.

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

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

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

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

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

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

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

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

  Dracunculidae nematodes, such as the genus Deacunculus.

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

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

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

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

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

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

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

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

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

Examples of liquid carriers include aromatic hydrocarbons such as xylene, alkyl (C ₉ or C ₁₀ etc.) benzene, phenyl xylyl ethane, alkyl (C ₁ or C ₃ etc.) naphthalene; machine oil, normal paraffin, isoparaffin Aliphatic hydrocarbons such as naphthene, aromatic hydrocarbons such as kerosene and aliphatic hydrocarbons; alcohols such as ethanol, isopropanol, cyclohexanol, phenoxyethanol, benzyl alcohol; ethylene glycol, propylene glycol, diethylene glycol, hexylene Polyhydric alcohols such as glycol, polyethylene glycol, polypropylene glycol; propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl Ethers such as ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether; ketones such as acetophenone, cyclohexanone, and γ-butyrolactone; fatty acid methyl esters, succinic acid dialkyl esters, glutamic acid dialkyl esters, adipic acid dialkyl esters , Esters such as dialkyl phthalate; acid amides such as N-alkyl (C1, C8 or C12) pyrrolidone; fats and oils such as soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil, castor oil; dimethyl sulfoxide, water And the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Next, formulation examples of the preparation when the compound of the present invention is used are shown. However, the formulation examples of the present invention are not limited to these. In the following formulation examples, “parts” means parts by mass.

[Wettable powder]
Compound of the present invention 0.1-80 parts Solid carrier 5-98.9 parts Surfactant 1-10 parts Others 0-5 parts Others include, for example, anti-caking agents and decomposition inhibitors.

〔emulsion〕
Compound of the present invention 0.1-30 parts Liquid carrier 45-95 parts Surfactant 4.9-15 parts Others 0-10 parts Others include, for example, spreading agents, decomposition inhibitors and the like.

[Suspension]
Compounds of the present invention 0.1 to 70 parts Liquid carrier 15 to 98.89 parts Surfactant 1 to 12 parts Others 0.01 to 30 parts Others include, for example, antifreezing agents and thickeners.

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

[Liquid]
Compound of the present invention 0.01 to 70 parts Liquid carrier 20 to 99.99 parts Others 0 to 10 parts Others include, for example, antifreezing agents and spreading agents.

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

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

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

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

[Formulation Example 1] Wetting Agent Compound No. 1-001a 20 parts Pyrophyllite 74 parts Solpol 5039 4 parts (trade name, mixture of nonionic surfactant and anionic surfactant: manufactured by Toho Chemical Industry Co., Ltd.)
Carplex # 80D 2 parts (trade name, synthetic hydrous silicic acid: manufactured by Shionogi & Co.)
The above is uniformly mixed and ground to obtain a wettable powder.

[Formulation Example 2] Emulsion Compound No. 1-001a 5 parts xylene 75 parts N-methylpyrrolidone 15 parts Solpol 2680 5 parts (trade name, mixture of nonionic surfactant and anionic surfactant: manufactured by Toho Chemical Industries)
The above is uniformly mixed to obtain an emulsion.

[Formulation Example 3] Suspending Agent Compound No. 1-001a 25 parts Agrisol S-710 10 parts (trade name, nonionic surfactant: manufactured by Kao Corporation)
Lnox 1000C 0.5 part (trade name, anionic surfactant: manufactured by Toho Chemical Industry Co., Ltd.)
Xanthan gum 0.2 parts Water 64.3 parts After uniformly mixing the above, wet pulverize to make a suspension.

[Formulation Example 4] Granule wettable powder of the present compound No. 1-001a 75 parts Hightenol NE-15 5 parts (trade name, anionic surfactant: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Vanillex N 10 parts (trade name, anionic surfactant: manufactured by Nippon Paper Industries Co., Ltd.)
Carplex # 80D 10 parts (trade name, synthetic hydrous silicic acid: manufactured by Shionogi & Co.)
After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to obtain a granulated wettable powder.

[Formulation Example 5] Granules of the present compound No. 1-001a 5 parts Bentonite 50 parts Talc 45 parts After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to form granules.

[Composition Example 6] Powder This invention compound No. 1-001a 3 parts Carplex # 80D 0.5 part (trade name, synthetic hydrous silicic acid: manufactured by Shionogi & Co.)
Kaolinite 95 parts Diisopropyl phosphate 1.5 parts or more uniformly mixed and pulverized to obtain a powder.

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

[Formulation 7] wettable powder preparation Compound No. 1-001a 25 parts sodium diisobutylnaphthalenesulfonate 1 part calcium n-dodecylbenzenesulfonate 10 parts alkylaryl polyglycol ether 12 parts sodium salt of naphthalenesulfonic acid formalin condensate 3 parts emulsion type silicone 1 part silicon dioxide 3 parts kaolin 45 Part [Formulation Example 8] Water-soluble thickener preparation 1-001a 20 parts polyoxyethylene lauryl ether 3 parts sodium dioctylsulfosuccinate 3.5 parts dimethyl sulfoxide 37 parts 2-propanol 36.5 parts [Formulation Example 9] Spraying solution 1-001a 2 parts dimethyl sulfoxide 10 parts 2-propanol 35 parts acetone 53 parts [Formulation Example 10] Solution for transdermal administration Compound No. 1-001a 5 parts Hexylene glycol 50 parts Isopropanol 45 parts [Formulation Example 11] Solution for transdermal administration Compound No. of the present invention 1-001a 5 parts propylene glycol monomethyl ether 50 parts dipropylene glycol 45 parts [Formulation Example 12] Solution for transdermal administration (dropping) The present compound No. 1 1-001a 2 parts light liquid paraffin 98 parts [Formulation Example 13] Solution for transdermal administration (dropping) The present compound No. 1 1-001a 2 parts light liquid paraffin 58 parts olive oil 30 parts ODO-H 9 parts Shin-Etsu silicone 1 part In addition, when the compound of the present invention is used as an agrochemical, other types of herbicidal substances are formulated or sprayed as necessary. You may mix and apply with an agent, various insecticides, an acaricide, a nematicide, a fungicide, a plant growth regulator, a synergist, a fertilizer, a soil conditioner, etc.

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

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

  Bactericides: acibenzolar-S-methyl, acylaminobenzamide, acypetacs, aldimorph, ametoctradin, aminopyrifen, amisulbrom, Amobam, ampropyfos, anilazine, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M (Benalaxyl-M), benodanil, benomyl, benquinox, bentaluron, benthiavalicarb-isopropyl, benthiazole, benzamacryl acril), benzamorf, benzovindiflupyr, bethoxazine, binapacryl, biphenyl, bitertanol, blasticidin-S (blasticidin-S), bixafen ( bixafen, bordeaux mixture, boscalid, bromuconazole, bupirimate, buthiobate, calcium polysulfide, calcium polysulfide, captaphor (Captafol), captan, carpropamid, carbamorph, carbendazim, carboxin, carvone, cheshunt mixture, chinomethionat, Robbenthiazone, chloraniformethane, chloranil, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chloroquinox, clozoline ( chlozolinate, climbazole, clotrimazole, copper acetate, copper carbonate, basic, copper hydroxide, copper naphthenate ), Copper oleate, copper oxychloride, copper sulfate, copper sulfate, basic, copper zinc chromate, cufraneb ), Coumoxystrobin, cuprobam ), Cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazol, cyprodinil, proflam cyprofuram, dazomet, debacarb, decafentin, dehydroacetic acid, diclobentiazox, dichlofluanid, dichlone, dichlorophen (Dichlorophen), dichlozoline, diclobutrazol, diclocymet, diclomedine, dicloran, etc.

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

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

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

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

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

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

    Insecticides: abamectin, acephate, acetamipirid, afidopyropen, afoxolaner, alanycarb, aldicarb, alesphos, amethphos, azaphos Ethyl (azinphos-ethyl), azinphos-methyl, bacillus thuringiensis, bendiocarb, benfluthrin, benfuracarb, bensultap, benspyrimoxane (Benzpyrimoxan), bifenthrin, bioallethrin, bioresmethrin, bistrifluron, broflanilide, buprofezin, buprofezin Carboxy (butocarboxim), carbaryl, carbofuran, carbofuran, carbosulfan, cartap, chlorantraniliprole, chlorethxyfos, chlorfenapyr, chlor Chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin , Cyanophos, cyantraniliprole, cyclaniliprole, cycloprothrin, cyflumetofen, cyfluthrin, Ter-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin (alpha) -cypermethrin), beta-cypermethrin, zeta-cypermethrin, cyphenothrin, cyromazine, deltamethrin, diacloden, diafenthiuron ( diafenthiuron, diazinon, dichlorolorzozotiaz, dichlorvos, diflubenzuron, dimefluthrin, dimethylvinphos, dinotefuran, diofenolan , Disulfoton, dimethoate, emamectin-benzoate, empenthrin, endosulfan, alpha-endosulfan, EP-N, EPN, esfenvalerate, Ethiofencarb, ethiprole, etofenprox, etrimfos, fenitrothion, fenobucarb, phenoxycarb, fenpropathrin, fenthion, fenthion Fenvalerate, fipronil, flonicamid, fluazuron, flubendiamide, flucycloxuron Flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrimin, fluralaner, fluvalinate, tau-fulvali Such as tau-fluvalinate, fonophos, formetanate, formothion, furathiocarb, flufiprole, fluhexafon, flupyradifurone, flometoquin, etc.

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

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

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

The chemical shift value of the proton nuclear magnetic resonance spectrum described below (hereinafter referred to as ¹ H-NMR) is 300 MHz in deuterated chloroform solvent using Me ₄ Si (tetramethylsilane) as a reference substance. (Model: JNM-ECX300 or JNM-ECP300, manufactured by JEOL).

The symbol in the chemical shift value of ¹ H-NMR represents the following meaning.
s: singlet, d: doublet, dd: double doublet, t: triplet, tt: triple triplet, q: quartet, m: multiplet, brs: broad singlet Synthesis Example 1: 3- (ethylthio) -7- (trifluoro Synthesis of methyl) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine (the present compound No. 1-001b) 3-iodo-7- (trifluoromethyl) ) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine (370 mg) and 1,4-dioxane (5 ml) in a mixed solution at room temperature with diisopropylethylamine (314 mg, 4,5). -Bis (diphenylphosphino) -9,9-dimethylxanthene 67 mg, Tris (dibenzylidene Acetone) were sequentially added dipalladium (0 valence) 37 mg and ethanethiol 71 mg. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, and then stirred for 1 hour under heating and reflux. After completion of the reaction, the reaction mixture was filtered through celite at room temperature, and the celite was washed with 20 ml of chloroform. The obtained filtrate and washing solution were combined and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography [gradient of n-hexane: ethyl acetate = 100: 0 to 0: 100 (volume ratio, the same applies hereinafter)] to obtain 295 mg of the desired product. Obtained as a white solid.
Melting point: 90-92 ° C
Synthesis Example 2: 3- (Ethylsulfonyl) -7- (trifluoromethyl) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine (present compound No. 1) Synthesis of 1-001a) of 215 mg 3- (ethylthio) -7- (trifluoromethyl) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine and 5 ml chloroform To the mixed solution, 335 mg of 65% by mass metachloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd .; containing about 30% by mass of water; the same applies hereinafter) was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours. After completion of the reaction, 3 ml of a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, followed by extraction with chloroform (5 ml × 2). The obtained organic layer was washed with 5 ml of 1 mol / L sodium hydroxide aqueous solution, dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 0: 100) to obtain 108 mg of the desired product as a white solid.
Melting point: 180-182 ° C
Synthesis Example 3: 3- (Ethylsulfinyl) -7- (trifluoromethyl) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine (present compound No. 1) 1-001c) Synthesis of 3- (ethylthio) -7- (trifluoromethyl) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine 40 mg and chloroform 5 ml To the mixed solution, 19 mg of 65% by mass metachloroperbenzoic acid was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours. After completion of the reaction, 3 ml of a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, followed by extraction with chloroform (5 ml × 2). The obtained organic layer was washed with 5 ml of 1 mol / L sodium hydroxide aqueous solution, dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 0: 100) to obtain 29 mg of the desired product as a white solid.
Melting point: 165-166 ° C
Synthesis Example 4: 3- (Ethylsulfonyl) -7- (trifluoromethyl) -2- [3- (trifluoromethyl) phenyl] imidazo [1,2-a] pyridine (present compound No. 1-004a) Synthesis of 2-bromo-3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine 107 mg, water 0.2 ml and 1,4-dioxane 0.8 ml at room temperature In this manner, 62 mg of potassium carbonate, 25 mg of [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct and 68 mg of 3- (trifluoromethyl) phenylboronic acid were sequentially added. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, followed by stirring at 80 ° C. for 3 hours. After completion of the reaction, 5 ml of water was added to the reaction mixture at room temperature, followed by extraction with ethyl acetate (5 ml × 2). The obtained organic layer was dehydrated and dried with saturated brine and then anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (n-hexane: ethyl acetate = 95: 5 to 50:50 gradient) to obtain the desired product (95 mg) as a pale yellow solid.
Melting point: 109-111 ° C
Synthesis Example 5: 3- (Ethylthio) -2- [5- (2,2,2-trifluoroethoxy) pyridin-2-yl] -7- (trifluoromethyl) imidazo [1,2-a] pyridine ( Synthesis of the present compound No. 1-006b) To a mixed solution of 2-bromo-3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine 2.9 mg and tetrahydrofuran 1.8 ml, -20 0.6 ml of 1.3 mol / L isopropylmagnesium chloride-lithium chloride complex tetrahydrofuran solution was added at ° C. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, and then stirred at −20 ° C. for 10 minutes. After completion of stirring, the reaction solution was added with 2-bromo-5- (2,2,2-trifluoroethoxy) pyridine 150 mg, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane addition. To a mixed solution of 24 mg of the product and 2.9 ml of tetrahydrofuran was added at 0 ° C. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, followed by stirring at room temperature for 2 hours. After completion of the reaction, 5 ml of water was added to the reaction mixture and extracted with ethyl acetate (5 ml × 2). The obtained organic layer was dehydrated and dried with saturated brine and then anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 70:30) to obtain 20 mg of the desired product as a colorless oil.
¹ H-NMR (CDCl ₃ ): δ8.69 (d, J = 7.5Hz, 1H), 8.55 (d, J = 3.0Hz, 1H), 8.39 (d, J = 8.7Hz, 1H), 7.97 (s , 1H), 7.45-7.35 (m, 1H), 7.15-7.05 (m, 1H), 4.49 (q, J = 7.8Hz, 2H), 2.90 (q, J = 7.5Hz, 2H), 1.15 (t, J = 7.5Hz, 3H).
Synthesis Example 6: 3- (Ethylthio) -6-iodo-2- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] imidazo [1,2-a] pyridine (present invention) Synthesis of Compound No. 1-021b) 400 mg 2-bromo-2- (ethylthio) -1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethane-1-one and To a mixed solution of 10 ml of acetonitrile, 227 mg of 5-iodo-2-aminopyridine was added at room temperature. The mixture was stirred for 2.5 hours under heating to reflux. After completion of the reaction, the solvent was distilled off under reduced pressure. 10 ml of water was added to the obtained residue, and the mixture was extracted with chloroform (20 ml × 2). The obtained organic layer was washed with 1 mol / L hydrochloric acid. The organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (n-hexane: ethyl acetate = 100: 0 to 50:50 gradient) to obtain 295 mg of the desired product as a brown solid.
Melting point: 140-142 ° C
¹ H-NMR (CDCl ₃ ): δ8.85-8.75 (m, 1H), 8.52 (d, J = 2.7Hz, 1H), 8.36 (d, J = 8.4Hz, 1H), 7.50-7.45 (m, 2H), 7.40-7.30 (m, 1H), 6.07 (tt, J = 52.8, 4.2Hz, 1H), 4.47 (t, J = 11.7Hz, 2H), 2.85 (q, J = 7.5Hz, 2H), 1.14 (t, J = 7.5Hz, 3H).
Synthesis Example 7: 3- (Ethylsulfonyl) -6-iodo-2- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] imidazo [1,2-a] pyridine (present) Invention compounds No. 1-021a) and 2- [3- (ethylsulfonyl) -6-iodoimidazo [1,2-a] pyridin-2-yl] -5- (2,2,3,3-tetrafluoro) Synthesis of propoxy) pyridine 1-oxide (the present compound No. 1-035a) 3- (ethylthio) -6-iodo-2- [5- (2,2,3,3) synthesized by the method described in Synthesis Example 6 To a mixed solution of 265 mg of 3-tetrafluoropropoxy) pyridin-2-yl] imidazo [1,2-a] pyridine and 5 ml of chloroform, 316 mg of 65 wt% metachloroperbenzoic acid was added under ice cooling. The mixture was stirred at room temperature for 3.5 hours. After 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). The obtained organic layer was washed with a 1 mol / L aqueous sodium hydroxide solution. The organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (n-hexane: ethyl acetate = 100: 0 to 50:50 gradient). No. 1-021a, 44 mg of brown solid No. 91 mg of 1-035a was obtained.
No. 1-021a
Melting point: 142-144 ° C
¹ H-NMR (CDCl ₃ ): δ9.50-9.45 (m, 1H), 8.42 (d, J = 2.7Hz, 1H), 8.06 (d, J = 9.0Hz, 1H), 7.70-7.60 (m, 1H), 7.52 (d, J = 9.3Hz, 1H), 7.38 (dd, J = 9.0, 2.4Hz, 1H), 6.07 (tt, J = 52.8, 4.2Hz, 1H), 4.47 (t, J = 11.7 Hz, 2H), 3.94 (q, J = 7.2Hz, 2H), 1.40 (t, J = 7.2Hz, 3H).
No. 1-035a
¹ H-NMR (CDCl ₃ ): δ9.12 (s, 1H), 8.09 (d, J = 2.4Hz, 1H), 7.67 (dd, J = 9.6, 1.5Hz, 1H), 7.60-7.50 (m, 2H), 7.01 (dd, J = 9.0, 2.4Hz, 1H), 6.02 (tt, J = 53.1, 4.5Hz, 1H), 4.44 (t, J = 11.4Hz, 2H), 3.75 (q, J = 7.5 Hz, 2H), 1.46 (t, J = 7.5Hz, 3H).
Synthesis Example 8 6-cyclopropyl-3- (ethylsulfonyl) -2- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] imidazo [1,2-a] pyridine ( Synthesis of the present compound No. 1-022a) 6-bromo-3- (ethylsulfonyl) -2- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] imidazo [1, 2-a] To a mixed solution of 80 mg of pyridine, 0.2 ml of water and 0.8 ml of 1,4-dioxane at room temperature, 102 mg of potassium phosphate, 53 mg of cyclopropylboronic acid and [1,1′-bis (diphenylphosphino) ) Ferrocene] palladium (II) dichloride 20 mg of dichloromethane adduct was added sequentially. After replacing the inside of the reaction vessel with nitrogen gas, the mixture was stirred at 90 ° C. for 1 hour. After completion of the reaction, 5 ml of water was added to the reaction mixture and extracted with chloroform (5 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 50:50) to obtain 17 mg of the desired product as a pale yellow solid.
Melting point: 110-111 ° C
¹ H-NMR (CDCl ₃ ): δ9.05-9.00 (m, 1H), 8.43 (d, J = 2.7Hz, 1H), 8.04 (d, J = 9.3Hz, 1H), 7.64 (d, J = 9.3Hz, 1H), 7.37 (dd, J = 9.3, 3.0Hz, 1H), 7.17 (dd, J = 9.3, 2.1Hz, 1H), 6.08 (tt, J = 53.4, 4.5Hz, 1H), 4.55- 4.40 (m, 2H), 3.89 (q, J = 7.2Hz, 2H), 2.05-1.95 (m, 1H), 1.39 (t, J = 7.2Hz, 3H), 1.10-1.00 (m, 2H), 0.80 -0.70 (m, 2H).
Synthesis Example 9 6- [3- (Ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridin-2-yl] pyridin-3-yl trifluoromethanesulfonate (present compound No. 1) Synthesis of 1-011a) To a mixed solution of 6 mg of 6- [3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridin-2-yl] pyridin-3-ol and 3 ml of dichloromethane Under ice cooling, 23 mg of 2,6-lutidine and 36 mg of trifluoromethanesulfonic anhydride were sequentially added. The reaction mixture was stirred at room temperature for 4 hours. To the reaction mixture, 23 mg of 2,6-lutidine and 36 mg of trifluoromethanesulfonic anhydride were sequentially added under ice cooling. The mixture was stirred at room temperature for 30 minutes. After completion of the reaction, 5 ml of water was added to the reaction mixture and extracted with chloroform (5 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0-50: 50) to obtain 34 mg of the desired product as a white solid.
Melting point: 143-145 ° C
¹ H-NMR (CDCl ₃ ): δ9.42 (d, J = 7.8Hz, 1H), 8.69 (d, J = 2.7Hz, 1H), 8.26 (d, J = 9.0Hz, 1H), 8.10-8.05 (m, 1H), 7.81 (dd, J = 9.0, 2.7Hz, 1H), 7.24 (dd, J = 7.8, 1.8Hz, 1H), 3.98 (q, J = 7.5Hz, 2H), 1.42 (t, J = 7.5Hz, 3H).
Synthesis Example 10 6-bromo-3- (ethylthio) -2- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] imidazo [1,2-a] pyrazine (present invention) Synthesis of Compound No. 1-038b) 2-bromo-2- (ethylthio) -1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethane-1-one 300 mg and To a mixed solution of 5 ml of acetonitrile, 154 mg of 5-bromopyrazin-2-amine was added at room temperature. The reaction mixture was stirred for 2 hours under heating to reflux. After completion of the reaction, the solvent was distilled off under reduced pressure. 10 ml of water was added to the obtained residue, and the mixture was extracted with chloroform (20 ml × 2). The obtained organic layer was washed with 1 mol / L hydrochloric acid. The organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 50:50) to obtain 76 mg of the desired product as a yellow solid.
¹ H-NMR (CDCl ₃ ): δ8.91 (d, J = 1.2Hz, 1H), 8.63 (s, 1H), 8.57-8.51 (m, 1H), 8.40-8.34 (m, 1H), 7.39 ( dd, J = 8.4, 2.7Hz, 1H), 6.08 (tt, J = 53.4, 4.2Hz, 1H), 4.54-4.44 (m, 2H), 2.96 (q, J = 7.5Hz, 2H), 1.17 (t , J = 7.5Hz, 3H).
Synthesis Example 11 6-Bromo-3- (ethylsulfonyl) -2- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] imidazo [1,2-a] pyrazine (present) Synthesis of Invention Compound No. 1-038a) 6-Bromo-3- (ethylthio) -2- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl obtained in Synthesis Example 10 ] To a mixed solution of 76 mg of imidazo [1,2-a] pyrazine and 1 ml of acetic acid, 5 mg of sodium tungstate dihydrate and 74 mg of 30% by mass hydrogen peroxide were sequentially added under ice cooling. The reaction mixture was stirred at room temperature for 7 hours. After completion of the reaction, 5 ml of a saturated aqueous sodium thiosulfate solution was added to the reaction mixture and extracted with chloroform (10 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 50:50) to obtain 44 mg of the desired product as a white solid.
Melting point: 189-191 ° C
¹ H-NMR (CDCl ₃ ): δ9.38-9.34 (m, 1H), 9.04 (d, J = 1.5Hz, 1H), 8.45 (d, J = 2.7Hz, 1H), 8.16 (d, J = 9.0Hz, 1H), 7.43 (dd, J = 9.0, 2.7Hz, 1H), 6.07 (tt, J = 53.1, 3.6Hz, 1H), 4.56-4.44 (m, 2H), 4.05 (q, J = 7.5 Hz, 2H), 1.43 (t, 7.5Hz, 3H).
The synthetic intermediate used in Synthesis Examples 1 to 11 can be produced by the following method.

Intermediate Production Example 1: Synthesis of 3-iodo-7- (trifluoromethyl) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine Step 1: 7- Synthesis of (trifluoromethyl) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine 2-bromo-1- [5- (trifluoromethyl) pyridine-2 -Il] To a mixed solution of 2.45 g of ethane-1-one and 10 ml of ethanol, 800 mg of 4- (trifluoromethyl) pyridin-2-amine and 622 mg of sodium bicarbonate were sequentially added at room temperature. After completion of the addition, the reaction mixture was stirred for 1 hour under heating to reflux. After completion of the reaction, 20 ml of water was added to the reaction mixture at room temperature, followed by extraction with ethyl acetate (20 ml × 2). The obtained organic layer was dehydrated and dried with saturated brine and then anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The precipitated solid was separated by filtration. The obtained solid was washed with diisopropyl ether to obtain 1.30 g of the desired product as a brown solid.
Melting point: 160-170 ° C
Step 2: Synthesis of 3-iodo-7- (trifluoromethyl) -2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine 7- (trifluoromethyl)- To a mixed solution of 2- [5- (trifluoromethyl) pyridin-2-yl] imidazo [1,2-a] pyridine 500 mg and N, N-dimethylformamide 10 ml, 509 mg of N-iodosuccinimide was added at room temperature. . After the addition was complete, the reaction mixture was stirred at room temperature for 40 minutes. After completion of the reaction, 20 ml of water was added to the reaction mixture, and the precipitated solid was separated by filtration to obtain 412 mg of the desired product as a brown solid.
Melting point: 200-205 ° C
Intermediate Production Example 2: Synthesis of 2-bromo-3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine Step 1: 3-iodo-7- (trifluoromethyl) imidazo Synthesis of ethyl [1,2-a] pyridine-2-carboxylate of 3.73 g of ethyl 7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylate and 20 ml of N, N-dimethylformamide. To the mixed solution, 6.5 g of N-iodosuccinimide was added at room temperature. After completion of the addition, the reaction mixture was stirred at 80 ° C. for 5 hours. After completion of the reaction, water was added to the reaction mixture at room temperature, and the precipitated solid was separated by filtration. The obtained solid was dissolved in 20 ml of chloroform and washed with a saturated aqueous sodium thiosulfate solution and then with saturated sodium bicarbonate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 5.08 g of the desired product as a skin-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 2: Synthesis of ethyl 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylate 3-Iodo-7- (trifluoromethyl) imidazo [1,2- a] To a mixed solution of 5.73 g of ethyl pyridine-2-carboxylate and 40 ml of 1,4-dioxane, 5.79 g of diisopropylethylamine, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene at room temperature 862 mg, tris (dibenzylideneacetone) dipalladium (zero valent) 682 mg and ethanethiol 1.85 g were sequentially added. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, and then stirred for 2 hours under heating and reflux. After completion of the reaction, the reaction mixture was filtered through celite at room temperature, and the celite was washed with 30 ml of chloroform. The obtained filtrate and washing solution were combined and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0-50: 50) to obtain 5.58 g of the desired product as a brown solid.
Melting point: 50-52 ° C
¹ H-NMR (CDCl ₃ ): δ 8.67 (d, J = 7.4Hz, 1H), 8.02-8.00 (m, 1H), 7.15 (dd, J = 7.4, 1.8Hz, 1H), 4.52 (q, J = 7.0Hz, 2H), 2.98 (q, J = 7.5Hz, 2H), 1.48 (t, J = 7.0Hz, 3H), 1.20 (t, J = 7.5Hz, 3H).
Step 3: Synthesis of 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylic acid 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2 -A] To a mixed solution of 5.58 g of ethyl pyridine-2-carboxylate, 60 ml of ethanol and 30 ml of tetrahydrofuran, 10 ml of a 3 mol / L aqueous sodium hydroxide solution was added at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. A 1 mol / L aqueous hydrochloric acid solution was added to the obtained residue to adjust the pH of the aqueous layer to 2, and the mixture was extracted with ethyl acetate (20 ml × 2). The obtained organic layer was dehydrated and dried with saturated brine and then anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 3.40 g of the desired product as a yellow solid.
Melting point: 163-171 ° C
¹ H-NMR (CDCl ₃ ): δ 8.69 (d, J = 7.2Hz, 1H), 8.19 (s, 1H), 7.22 (dd, J = 7.2, 1.4Hz, 1H), 3.06 (q, J = (7.4Hz, 2H), 1.23 (t, J = 7.4Hz, 3H) (CO ₂ H proton peak could not be observed).
Step 4: Synthesis of 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine- To a mixed solution of 10.0 g of ethyl 2-carboxylate and 114 ml of ethylene glycol, 108 mg of copper was added at room temperature. After the addition was complete, the reaction mixture was stirred at 200 ° C. for 3 hours. After completion of the reaction, 300 ml of water was added to the reaction mixture at room temperature, followed by extraction with chloroform (250 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 11.37 g of the desired product as a brown oil.

Step 5: Synthesis of 2-bromo-3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2- a] To a mixed solution of 11.37 g of pyridine and 70 ml of dichloromethane, 6.74 g of N-bromosuccinimide was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 16 hours. After completion of the stirring, 6.74 g of N-bromosuccinimide was added to the reaction mixture under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 95: 5 to 75:25) to obtain 3.72 g of the desired product as a pale pink solid.
Melting point: 242-245 ° C
Step 6: Synthesis of 2-bromo-3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine 2-bromo-3- (ethylthio) -7- (trifluoromethyl) imidazo To a mixed solution of 808 mg of [1,2-a] pyridine and 10 ml of chloroform, 1.31 g of 65% by mass metachloroperbenzoic acid (including about 30% by mass water) was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 3 hours. After completion of the reaction, 3 ml of a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, followed by extraction with chloroform (10 ml × 2). The obtained organic layer was washed with 5 ml of 2 mol / L sodium hydroxide aqueous solution, dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The precipitated solid was separated by filtration. The obtained solid was washed with diisopropyl ether to obtain 807 mg of the desired product as a white solid.
¹ H-NMR (CDCl ₃ ): δ9.18 (d, J = 7.5Hz, 1H), 8.00-7.95 (m, 1H), 7.30-7.20 (m, 1H), 3.39 (q, J = 7.5Hz, 2H), 1.35 (t, J = 7.5Hz, 3H).
Intermediate Production Example 3: Synthesis of 2-bromo-2- (ethylthio) -1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethan-1-one Step 1: Synthesis of 1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethane-1-one 5- (2,2,3,3-tetrafluoropropoxy) picolinonitrile 6 To a mixed solution of .38 g and 90 ml of tetrahydrofuran was added 10.9 ml of a diethyl ether solution (manufactured by Tokyo Chemical Industry Co., Ltd.) of about 3 mol / L methylmagnesium bromide under ice cooling. After replacing the inside of the reaction vessel with nitrogen gas, the mixture was stirred for 1.5 hours under ice cooling. After completion of the reaction, the reaction mixture was added dropwise to 20 ml of 3 mol / L hydrochloric acid under ice cooling. Under ice-cooling, a 10 mol / L aqueous sodium hydroxide solution was added to the mixture to adjust the pH of the aqueous layer to 9 to 10, followed by extraction with chloroform (20 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 6.8 g of the desired product as a brown oil.
¹ H-NMR (CDCl ₃ ): δ 8.38 (d, J = 3.3Hz, 1H), 8.08 (d, J = 8.4Hz, 1H), 7.33 (dd, J = 8.4, 3.3Hz, 1H), 6.06 (tt, J = 53.4, 4.2Hz, 1H), 4.49 (t, J = 11.7Hz, 2H), 2.70 (s, 3H).
Step 2: Synthesis of 2-bromo-1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethane-1-one 1- [5- ( 2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethane-1-one and a mixed solution of 90 ml of dichloromethane and 2.99 g of triethylamine and trimethylsilyl trifluoromethanesulfonate 6 under ice-cooling. .28 g was added sequentially. The reaction mixture was stirred for 1 hour under ice cooling. To the reaction mixture, 10.1 g of trimethylphenylammonium tribromide was added under ice cooling. The reaction mixture was stirred for 1.5 hours under ice cooling. After completion of the reaction, 50 ml of water was added to the reaction mixture and extracted with chloroform (50 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 9.46 g of the desired crude product as a brown oil.
¹ H-NMR (CDCl ₃ ): δ8.38 (d, J = 2.7Hz, 1H), 8.13 (d, J = 8.7Hz, 1H), 7.40-7.20 (m, 1H), 6.04 (tt, J = 53.4, 4.2Hz, 1H), 4.79 (s, 2H), 4.49 (t, J = 11.4Hz, 2H).
Step 3: Synthesis of 2- (ethylthio) -1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethan-1-one 2-Bromo- obtained in Step 2 To a mixed solution of 9.46 g of a crude product of 1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethan-1-one and 50 ml of N, N-dimethylformamide was added ice. Under cooling, 2.01 g of ethanethiol and 2.71 g of sodium bicarbonate were sequentially added. The reaction mixture was stirred at room temperature for 16 hours. After completion of the reaction, 100 ml of water was added to the reaction mixture and extracted with ethyl acetate (100 ml × 2). The obtained organic layer was dehydrated and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 7.72 g of the desired product as a yellow oil.
¹ H-NMR (CDCl ₃ ): δ 8.38 (d, J = 3.0Hz, 1H), 8.13 (d, J = 8.4Hz, 1H), 7.35 (dd, J = 8.4, 3.0Hz, 1H), 6.06 (tt, J = 53.1, 4.2Hz, 1H), 4.49 (t, J = 12.0Hz, 2H), 4.02 (s, 2H), 2.63 (q, J = 7.5Hz, 2H), 1.28 (t, J = 7.5Hz, 3H).
Step 4: Synthesis of 2-bromo-2- (ethylthio) -1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethan-1-one obtained in step 3 To a mixed solution of 2- (ethylthio) -1- [5- (2,2,3,3-tetrafluoropropoxy) pyridin-2-yl] ethane-1-one 5.52 g and dichloromethane 60 ml, ice-cooled. Then, 1.97 g of triethylamine and 4.32 g of trimethylsilyl trifluoromethanesulfonate were sequentially added. The reaction mixture was stirred for 30 minutes under ice cooling. 6.65 g of trimethylphenylammonium tribromide was added to the reaction mixture under ice cooling. The reaction mixture was stirred for 1 hour under ice cooling. After completion of the reaction, 50 ml of water was added to the reaction mixture and extracted with chloroform (50 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 6.9 g of the desired product as a brown oil.
¹ H-NMR (CDCl ₃ ): δ 8.39 (d, J = 2.7Hz, 1H), 8.19 (d, J = 9.0Hz, 1H), 7.38 (dd, J = 9.0, 2.7Hz, 1H), 7.23 (s, 1H), 6.06 (tt, J = 53.1, 4.2Hz, 1H), 4.51 (t, J = 12.0Hz, 2H), 3.00-2.75 (m, 2H), 1.36 (t, J = 7.5Hz, 3H).
Intermediate Production Example 4: Synthesis of 6- [3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridin-2-yl] pyridin-3-ol Step 1: 1- [ Synthesis of 5- (benzyloxy) pyridin-2-yl] -2- (ethylthio) ethane-1-one 1- [5- (Benzyloxy) pyridin-2-yl] -2-bromoethane-1-one To a mixed solution of 12 g and 15 ml of N, N-dimethylformamide, 250 mg of ethanethiol and 340 mg of sodium bicarbonate were sequentially added under ice cooling. The reaction mixture was stirred at room temperature for 16 hours. After completion of the reaction, 20 ml of water was added to the reaction mixture and extracted with ethyl acetate (20 ml × 2). The obtained organic layer was dehydrated and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 990 mg of the desired product as a pale yellow oil.
¹ H-NMR (CDCl ₃ ): δ 8.39 (d, J = 3.3Hz, 1H), 8.08 (d, J = 9.0Hz, 1H), 7.45-7.35 (m, 5H), 7.34 (dd, J = 9.0, 3.3Hz, 1H), 5.19 (s, 2H), 4.02 (s, 2H), 2.61 (q, J = 7.2Hz, 2H), 1.28 (t, J = 7.2Hz, 3H).
Step 2: Synthesis of 1- [5- (benzyloxy) pyridin-2-yl] -2-bromo-2- (ethylthio) ethan-1-one 1- [5- (benzyloxy) synthesized by the method of Step 1 ) Pyridin-2-yl] -2- (ethylthio) ethane-1-one 1.25 g and dichloromethane 15 ml were mixed with 484 mg of triethylamine and 1.02 g of trimethylsilyl trifluoromethanesulfonate under ice cooling. The reaction mixture was stirred for 2 hours under ice cooling. To the reaction mixture, 1.64 g of trimethylphenylammonium tribromide was added under ice cooling. The reaction mixture was stirred for 30 minutes under ice cooling. After completion of the reaction, 20 ml of water was added to the reaction mixture and extracted with chloroform (20 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.55 g of the desired product as a brown oil.
¹ H-NMR (CDCl ₃ ): δ 8.39 (d, J = 2.7Hz, 1H), 8.14 (d, J = 9.3Hz, 1H), 7.45-7.35 (m, 5H), 7.35 (dd, J = 9.3, 2.7Hz, 1H), 7.26 (s, 1H), 5.21 (s, 2H), 3.00-2.75 (m, 2H), 1.36 (t, J = 7.5Hz, 3H).
Step 3: Synthesis of 2- [5- (benzyloxy) pyridin-2-yl] -3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine 1 obtained in Step 2 -To a mixed solution of 1.5-g of [5- (benzyloxy) pyridin-2-yl] -2-bromo-2- (ethylthio) ethan-1-one and 20 ml of acetonitrile at room temperature, 2-amino-4- ( 823 mg of (trifluoromethyl) pyridine was added. The reaction mixture was stirred at room temperature for 1 hour. 20 ml of a saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with chloroform (20 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. To the obtained residue, 20 ml of 1,4-dioxane and 80 mg of p-toluenesulfonic acid monohydrate were added and stirred at 80 ° C. for 3 hours. After completion of the reaction, 20 ml of saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with chloroform (20 ml × 2). The obtained residue was purified by medium pressure preparative liquid chromatography (n-hexane: ethyl acetate = 100: 0 to 50:50 gradient) to obtain 1.37 g of the desired product as a brown oil.
¹ H-NMR (CDCl ₃ ): δ8.67 (d, J = 7.2Hz, 1H), 8.58 (d, J = 2.7Hz, 1H), 8.34 (d, J = 8.7Hz, 1H), 7.96 (s , 1H), 7.50-7.35 (m, 6H), 7.09 (dd, J = 7.2, 1.8Hz, 1H), 5.20 (s, 2H), 2.90 (q, J = 7.8Hz, 2H), 1.15 (t, J = 7.8Hz, 3H).
Step 4: Synthesis of 2- [5- (benzyloxy) pyridin-2-yl] -3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine Obtained in Step 3. To a mixed solution of 2- [5- (benzyloxy) pyridin-2-yl] -3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine and 15 ml of chloroform was added ice. Under cooling, 1.60 g of 65% by weight metachloroperbenzoic acid was added. The reaction mixture was stirred at room temperature for 3 hours. After 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 obtained organic layer was washed with a 1 mol / L aqueous sodium hydroxide solution. The organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 50:50) to obtain 790 mg of the desired product as a yellow solid.
Melting point: 144-146 ° C
Step 5: Synthesis of 6- [3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridin-2-yl] pyridin-3-ol 2- [obtained in Step 4 5- (Benzyloxy) pyridin-2-yl] -3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine 755 mg, ethanol 3 ml, ethyl acetate 3 ml and tetrahydrofuran 6 ml mixed solution 378 mg of 5 mass% palladium-carbon (water-containing product, STD type, manufactured by N.E. Chemcat Co.) at room temperature was added. After replacing the inside of the reaction vessel with hydrogen gas, the mixture was stirred at room temperature for 16 hours. After completion of the reaction, palladium-carbon was removed from the reaction mixture by celite filtration. Celite was washed with 20 ml of ethyl acetate. The obtained filtrate and washing solution were combined and the solvent was distilled off under reduced pressure to obtain 602 mg of the desired product as a white solid.
Melting point: 245-247 ° C
The compound of the present invention can be synthesized according to the above production method and synthesis examples. Examples of condensed heterocyclic compounds produced in the same manner as in Synthetic Examples 1 to 11 are shown in Tables 10 to 12. However, the condensed heterocyclic compounds and their production intermediates included in the present invention are limited to these. It is not limited.

In the table, “Me” represents a methyl group, “Et” represents an ethyl group, and “ ^c Pr” represents a cyclopropyl group. The description of V2-3a in the table represents the following ring structure.

  Further, “* 1” in the table represents that the compound is a solid, “* 2” represents that the compound is an oily substance, and “mp” represents a melting point (unit: ° C.).

  [Table 10]

――――――――――――――――――――――――――――――――――――――
No. A ² R ³ R ⁴ R ⁵ Y2 Y3 Y4 n mp
――――――――――――――――――――――――――――――――――――――
1-001a NH CF ₃ HH CF ₃ H 2 180-182
1-001b NH CF ₃ HH CF ₃ H 0 90-92
1-001c NH CF ₃ HH CF ₃ H 1 165-166
1-002a CH H CF ₃ HH CF ₃ H 2 174-177
1-003a CH H OCF ₃ HH CF ₃ H 2 134-136
1-004a CH HH CF ₃ H CF ₃ H 2 109-111
1-005a CF H CF ₃ HH CF ₃ H 2 163-166
1-006a NH OCH ₂ CF ₃ HH CF ₃ H 2 152-155
1-006b NH OCH ₂ CF ₃ HH CF ₃ H 0 * 2
1-007a NH OCH ₂ CF ₂ CF ₃ HH CF ₃ H 2 155-158
1-008a NH OCH ₂ CF ₂ CF ₂ CF ₃ HH CF ₃ H 2 140-143
1-009a NH OCH ₂ CF ₂ CHFCF ₃ HH CF ₃ H 2 126-128
1-010a NH OCH ₂ CHF ₂ HH CF ₃ H 2 161-162
1-011a NH OSO ₂ CF ₃ HH CF ₃ H 2 143-145
1-012a NH OSO ₂ CH ₂ CF ₃ HH CF ₃ H 2 179-183
1-013a NH OCH ₂ CF ₂ CHF ₂ HH CF ₃ H 2 148-150
1-014a NH OCH ₂ CF ₂ CHF ₂ HH Cl H 2 177-179
1-014b NH OCH ₂ CF ₂ CHF ₂ HH Cl H 0 100-101
1-015a NH OCH ₂ CF ₂ CHF ₂ HH Br H 2 155-157
1-016a NH OCH ₂ CF ₂ CHF ₂ HHIH 2 155-156
1-017a NH OCH ₂ CF ₂ CHF ₂ HH ^c Pr H 2 * 2
1-018a NH OCH ₂ CF ₂ CHF ₂ H CF ₃ HH 2 157-160
1-018b NH OCH ₂ CF ₂ CHF ₂ H CF ₃ HH 0 86-89
1-019a NH OCH ₂ CF ₂ CHF ₂ H Cl HH 2 143-146
1-019b NH OCH ₂ CF ₂ CHF ₂ H Cl HH 0 137-138
1-020a NH OCH ₂ CF ₂ CHF ₂ H Br HH 2 178-180
1-021a NH OCH ₂ CF ₂ CHF ₂ HIHH 2 142-144
1-021b NH OCH ₂ CF ₂ CHF ₂ HIHH 0 140-142
1-022a NH OCH ₂ CF ₂ CHF ₂ H ^c Pr HH 2 110-111
1-023a NH OCH ₂ CF ₂ CHF ₂ HHHH 2 85-88
1-023b NH OCH ₂ CF ₂ CHF ₂ HHHH 0 * 2
1-024a NH OCH ₂ CF ₂ CHF ₂ H Cl H Cl 2 207-208
1-024b NH OCH ₂ CF ₂ CHF ₂ H Cl H Cl 0 115-117
1-025a NH OCH ₂ CF ₂ CHF ₂ H Br H Br 2 214-216
1-025b NH OCH ₂ CF ₂ CHF ₂ H Br H Br 0 109-112
1-026a NH OCH ₂ CF ₂ CHF ₂ HHFH 2 146-148
1-027a NH OCH ₂ CF ₂ CHF ₂ HH CN H 2 161-162
1-028a NH OCH ₂ CF ₂ CHF ₂ HH SMe H 2 50-52
1-029a NH OCH ₂ CF ₂ CHF ₂ HH V2-3a H 2 223-224
1-030a NH OCH ₂ CF ₂ CHF ₂ HIFH 2 193-195
1-031a NH OCH ₂ CF ₂ CHF ₂ HIHF 2 173-175
1-032a CH H SCH ₂ CF ₃ HH CF ₃ H 2 120-122
1-033a CH SCH ₂ CF ₃ HHH CF ₃ H 2 145-147
――――――――――――――――――――――――――――――――――――――
[Table 11]

―――――――――――――――――――――――
No. R ⁴ Y2 Y3 n mp
―――――――――――――――――――――――
1-034a OCH ₂ CF ₂ CHF ₂ Cl H 2 * 2
1-035a OCH ₂ CF ₂ CHF ₂ IH 2 * 1
―――――――――――――――――――――――
[Table 12]

――――――――――――――――――――――
No. R ⁴ Y2 n mp
――――――――――――――――――――――
1-036a OCH ₂ CF ₃ H 2 154-156
1-037a OCH ₂ CF ₂ CHF ₂ H 2 143-146
1-038a OCH ₂ CF ₂ CHF ₂ Br 2 189-191
1-038b OCH ₂ CF ₂ CHF ₂ Br 0 * 1
1-039a OCH ₂ CF ₂ CHF ₂ ^c Pr 2 * 1
――――――――――――――――――――――
Of the compounds of the present invention shown in Tables 10 to 12, ¹ H-NMR data of compounds with no melting point are shown in Table 13.

[Table 13]
―――――――――――――――――――――――――――――――――――――――
No. ¹ H NMR (CDCl ₃ , Me ₄ Si, 300 MHz).
―――――――――――――――――――――――――――――――――――――――
1-006b δ8.69 (d, J = 7.5Hz, 1H), 8.55 (d, J = 3.0Hz, 1H),
8.39 (d, J = 8.7Hz, 1H), 7.97 (s, 1H), 7.45-7.35 (m, 1H),
7.15-7.05 (m, 1H), 4.49 (q, J = 7.8Hz, 2H), 2.90 (q, J = 7.5Hz, 2H),
1.15 (t, J = 7.5Hz, 3H).
1-017a δ9.08 (d, J = 8.4Hz, 1H), 8.42 (d, J = 2.4Hz, 1H),
8.05 (d, J = 9.0Hz, 1H), 7.39 (s, 1H),
7.37 (dd, J = 9.0, 2.4Hz, 1H), 6.72 (dd, J = 7.2, 2.1Hz, 1H),
6.08 (tt, J = 53.1, 4.5Hz, 1H), 4.55-4.40 (m, 2H),
3.89 (q, J = 7.5Hz, 2H), 2.05-1.95 (m, 1H),
1.37 (t, J = 7.5Hz, 3H), 1.20-1.10 (m, 2H), 0.90-0.80 (m, 2H).
1-023b δ8.57 (d, J = 6.9Hz, 1H), 8.54 (d, J = 2.1Hz, 1H),
8.40 (d, J = 9.0Hz, 1H), 7.68 (d, J = 9.3Hz, 1H),
7.37 (dd, J = 9.0, 3.0Hz, 1H), 7.35-7.25 (m, 1H),
7.00-6.90 (m, 1H), 6.10 (tt, J = 53.4, 4.8Hz, 1H),
4.55-4.40 (m, 2H), 2.85 (q, J = 7.5Hz, 2H), 1.15 (t, J = 7.5Hz, 3H).
1-034a δ8.96 (s, 1H), 8.10 (d, J = 2.4Hz, 1H), 7.73 (d, J = 9.6Hz, 1H),
7.56 (d, J = 9.0Hz, 1H), 7.48 (dd, J = 9.6, 1.8Hz, 1H),
7.03 (dd, J = 9.0, 2.4Hz, 1H), 6.03 (tt, J = 53.1, 4.2Hz, 1H),
4.45 (t, J = 11.7Hz, 2H), 3.78 (q, J = 7.2Hz, 2H),
1.48 (t, J = 7.2Hz, 3H).
1-035a δ9.12 (s, 1H), 8.09 (d, J = 2.4Hz, 1H), 7.67 (dd, J = 9.6, 1.5Hz, 1H),
7.60-7.50 (m, 2H), 7.01 (dd, J = 9.0, 2.4Hz, 1H),
6.02 (tt, J = 53.1, 4.5Hz, 1H), 4.44 (t, J = 11.4Hz, 2H),
3.75 (q, J = 7.5Hz, 2H), 1.46 (t, J = 7.5Hz, 3H).
1-038b δ8.91 (d, J = 1.2Hz, 1H), 8.63 (s, 1H), 8.57-8.51 (m, 1H),
8.40-8.34 (m, 1H), 7.39 (dd, J = 8.4, 2.7Hz, 1H),
6.08 (tt, J = 53.4, 4.2Hz, 1H), 4.54-4.44 (m, 2H),
2.96 (q, J = 7.5Hz, 2H), 1.17 (t, J = 7.5Hz, 3H).
1-039a δ9.09 (d, J = 1.8Hz, 1H), 9.02 (d, J = 1.8Hz, 1H),
8.44 (d, J = 3.3Hz, 1H), 8.11 (d, J = 9.0Hz, 1H),
7.40 (dd, J = 9.0, 3.3Hz, 1H), 6.08 (tt, J = 53.1, 4.8Hz, 1H),
4.55-4.45 (m, 2H), 4.00 (q, J = 7.5Hz, 2H), 2.14-2.02 (m, 1H),
1.42 (t, J = 7.5Hz, 3H), 1.12-1.02 (m, 2H), 0.54-0.44 (m, 2H).
―――――――――――――――――――――――――――――――――――――――
Next, the usefulness of the compound of the present invention as a pest control agent will be specifically described in the following test examples, but the present invention is not limited thereto.

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

(Calculation formula) Death rate (%) = (Number of dead insects / Number of test insects) × 100
As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-001a, 1-001b, 1-006a, 1-007a, 1-008a, 1-009a, 1-010a, 1-011a, 1-013a, 1-014a, 1-016a, 1-016a 017a, 1-018a, 1-019a, 1-020a, 1-021a, 1-022a, 1-023a, 1-028a, 1-031a, 1-034a, 1-035a, 1-039a.

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

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-001a, 1-001b, 1-001c, 1-002a, 1-004a, 1-005a, 1-006a, 1-007a, 1-008a, 1-009a, 1-010a, 1- 011a, 1-012a, 1-013a, 1-014a, 1-014b, 1-015b, 1-015a, 1-016a, 1-017a, 1-018a, 1-018b, 1-019a, 1-019b, 1-020a, 1-021a, 1-021b, 1-022a, 1-023a, 1-024a, 1-024b, 1-025a, 1-025b, 1-026a, 1-027a, 1-028a, 1-029a, 1- 030a, 1-031a, 1-032a, 1-034a, 1-035a, 1-037a, 1-038a, 1-039a.

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

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-1-001a, 1-001b, 1-001c, 1-002a, 1-003a, 1-006a, 1-007a, 1-008a, 1-009a, 1-010a, 1-011a, 1-012a, 1-013a, 1-014a, 1-014b, 1-015a, 1-016a, 1-017a, 1-018a, 1-018b, 1-019a, 1-019b, 1-020a, 1- 021a, 1-021b, 1-022a, 1-024a, 1-024b, 1-025a, 1-025b, 1-030a, 1-031a, 1-034a, 1-035a, 1-038a, 1-039a.

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

  1: 0-20% damage, 2: 20-50% damage, 3: 50-70% damage, 4: 70% or more damage.

As a result, among the compounds tested, the following compounds showed a mortality rate of 50% or more and a food damage level of 2 or 1.
Compounds of the present invention: 1-001b, 1-003a, 1-004a, 1-005a, 1-017a, 1-020a, 1-021a, 1-021b, 1-022a, 1-028a, 1-031a, 1- 034a, 1-035a.

Test Example 5: Insecticidal test against peach aphid Placed wet cotton wool on a glass petri dish with an inner diameter of 3 cm, placed kanran leaves cut into the same diameter on it, and released 4 adult mosquito aphids (Myzus persicae) Insects. One day later, a 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder was tested) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 500 ppm. The prepared chemical solution was sprayed (2.5 mg / cm ² ) in a rotary spray tower, covered, and stored in a thermostatic chamber at 25 ° C. Six days after housing, the number of dead peach aphids in the petri dish was examined, and the mortality rate was calculated from the same formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-005a, 1-006a, 1-007a, 1-008a, 1-009a, 1-010a, 1-011a, 1-013a, 1-014a, 1-014b, 1-015a, 1- 016a, 1-017a, 1-018a, 1-019a, 1-020a, 1-021a, 1-022a, 1-023a, 1-024a, 1-025a, 1-028a, 1-031a, 1-032a, 1-034a, 1-035a, 1-039a.

Test Example 6: Soil irrigation treatment test for peach aphid A 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 500 ppm. 10 ml of the above-mentioned chemical solution was irrigated to the stock soil portion of the plastic cup planted cabbage seedling (2.5 true leaf stage). After the irrigation treatment, the cabbage seedling was left in the greenhouse. One day after the irrigation treatment, 20 adult peach aphids (Myzus persicae) were released per strain. After the release, the cabbage seedling was left in the greenhouse. Six days after the release, the number of live insects of the peach aphid was investigated, and the control rate was calculated from the following formula.

Control rate (%) = [1- (Cb × Tai) / (Cai × Tb)] × 100
The characters in the formula represent the following:
Cb: Number of insects before treatment in the untreated plot, Cai: Number of live insects at the final survey in the untreated plot, Tb: Number of insects before treatment in the treated plot, Tai: Live insect at the final survey in the treated plot As a result, the following compounds showed a control rate of 90% or more.
Compounds of the present invention: 1-009a, 1-014a.

Test Example 7: Osmotic transfer test against brown planthopper A 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 20 ppm, and the roots of rice cell seedlings (two leaves) were immersed in the chemical solution. Seven days later, the rice was cut out and placed in a test tube, in which 5 third-instar larvae of the green planthopper (Nilaparvata lugens) were released per test tube, covered with a sponge and housed in a thermostatic chamber at 25 ° C. . Six days after the release, the number of dead planthoppers was examined, and the death rate was calculated from the same calculation formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-001a, 1-006a, 1-007a, 1-008a, 1-010a, 1-011a, 1-012a, 1-013a, 1-014a, 1-017a, 1-019a, 1- 020a, 1-022a, 1-028a, 1-031a, 1-036a, 1-037a, 1-039a.

Test Example 8: Soil irrigation treatment test for diamondback moth 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 500 ppm. 10 ml of the above-mentioned chemical solution was irrigated to the stock soil portion of a plastic cup planted cabbage seedling (2.5 true leaf stage). After the irrigation treatment, the cabbage seedling was left in the greenhouse. Five days after the irrigation treatment, the kanran leaves were cut out and placed in a petri dish. In this, 5 third-instar larvae of Plutella xylostella were released per petri dish, covered, and housed in a thermostatic chamber at 25 ° C. Six days after housing, the number of dead moths in petri dishes was examined, and the mortality rate was calculated from the same calculation formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a control value of 90% or more.
Compounds of the present invention: 1-001a, 1-006a, 1-013a, 1-014a, 1-019a, 1-024a, 1-031a.

Test Example 9: 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. Four soybean seeds were put into a plastic tube having a capacity of 50 ml, and the whole amount of the diluted solution was poured from above. The acetone was completely evaporated while stirring so that the compound was evenly attached to the seeds. Four treated seeds were planted in a plastic pot and left in the greenhouse. After the development of the primary leaves, two adult Aphis glycines were released per strain. The number of live worms 7 days after the release was examined, and the control rate was calculated from the same calculation formula as in Test Example 6.

As a result, the following compounds showed a control rate of 90% or more.
The compound of the present invention: 1-104a.

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

As a result, among the compounds tested, the following compounds showed a death rate of 50% or more.
Compounds of the present invention: 1-001b, 1-002a, 1-003a, 1-005a, 1-006a, 1-007a, 1-010a, 1-013a, 1-016a, 1-021a, 1-023a, 1- 026a, 1-032a, 1-033a, 1-034a, 1-036a.

Test Example 11: Effect test on cat fleas 3.5 mg of the compound of the present invention was dissolved in 3.5 ml of acetone to prepare a chemical solution having a concentration of 1000 ppm. After 350 μl of the chemical solution was applied to the bottom and side surfaces of a glass container having an inner wall surface area of 35 cm ² , acetone was volatilized to produce a thin film of the compound on the glass container inner wall. The inner wall of the glass container used is 35 cm ² , and the treatment drug amount is 10 μg / cm ² . Five adult cat fleas (mixed male and female) (mixed male and female) were released into the treated glass container, covered, and housed in a thermostatic chamber at 25 ° C. Four days after releasing, the number of dead fleas was investigated, and the death rate was calculated from the same calculation formula as in Test Example 1.

As a result, among the compounds tested, the following compounds showed a death rate of 50% or more.
Compounds of the present invention: 1-001b, 1-001c, 1-006a, 1-007a, 1-010a, 1-011a, 1-013a, 1-014a, 1-018a, 1-020a, 1-021a, 1- 021b, 1-022a, 1-024b, 1-025a, 1-028a, 1-030a, 1-031a, 1-034a, 1-035a.

Test Example 12: Insecticidal test against housefly 2 mg of the compound of the present invention was dissolved in 1 ml of acetone to prepare a drug solution having a concentration of 2 μg / μl. After letting female Musca domestica females sleep in carbon dioxide, 1 μl of the drug solution was applied to the back side of the chest of the pests using a topical application device (Burkard Scientific). After the chemical treatment, the treated pests were transferred to a plastic cup with a lid having an inner diameter of 7.5 cm and a height of 4 cm, and managed in a 25 ° C. constant temperature room. Three days after treatment with the drug, the number of dead insects was examined, and the dead insect ratio was calculated from the same formula as in Test Example 1. In addition, the test was performed by 5 heads and 2 repetitions.

As a result, the following compounds showed a death rate of 70% or more.
Compounds of the present invention: 1-007a, 1-008a, 1-015a, 1-016a, 1-020a, 1-021a, 1-025a.

Test Example 13: Insecticidal test against German cockroaches 2 mg of the compound of the present invention was dissolved in 0.2 ml of acetone to prepare a drug solution having a concentration of 10 μg / μl. After letting male adult cockroaches (Blattela germanica) sleep with carbon dioxide, the drug solution was applied to the abdomen of the pest at 1 μl per head using a topical application device (Burkard Scientific). After the chemical treatment, the sample was transferred to a waist-high petri dish having an inner diameter of 6 cm and a height of 6 cm, and managed in a constant temperature room at 25 ° C. Three days after the treatment of the drug, the number of bitter worms and the number of dead worms were investigated, and the bitter mortality rate was calculated from the following formula. In addition, the test was performed by 4 repetitions of 5 animals.

Bitter mortality rate (%) = (bitter worm count + dead worm count) / test insect count x 100
As a result, the following compounds showed an agony rate of 70% or more.
Compounds of the present invention: 1-015a, 1-016a, 1-018a, 1-020a, 1-021a, 1-024a.

Test Example 14 Insecticidal Test for Yamato Termites A 10% emulsion of the compound of the present invention was diluted with water to prepare a chemical solution having a concentration of 100 ppm. 0.5 ml of the chemical solution was added dropwise to 10 g of river sand and mixed so that the chemical solution was uniformly dispersed in the river sand. 1% agar (2 cm square) was placed in a petri dish having an inner diameter of 4 cm, and river sand treated with the above-mentioned chemicals and a piece of filter paper serving as food were placed therein. Here, Yamato termites (Reticulitermes speratus) were released and then kept in a thermostatic chamber at 25 ° C. Ten days after the release, the number of dead insects was examined, and the death rate was calculated from the same calculation formula as in Test Example 1. The test was performed twice.

As a result, the following compounds showed a death rate of 70% or more.
Compounds of the present invention: 1-007a, 1-008a, 1-013a, 1-015a, 1-016a, 1-018a, 1-020a, 1-021a, 1-024a, 1-025a.

Test Example 15: Insecticidal test for Chikaeka 2 mg of the compound of the present invention was dissolved in 0.2 ml of dimethyl sulfoxide to prepare a 1% (w / v) dimethyl sulfoxide solution. The solution was diluted 100 times with distilled water to prepare a chemical solution having a compound concentration of 100 ppm. As a test container, a 1.9 ml plastic container (Cellstar 24 well plate, manufactured by GREINER) was used. Add 0.7 ml of water containing 10-30 larvae of Culex pipiens molestus one day after hatching to the test container and 0.2 ml of water in which the fish for appreciation fish (Tetramin, Tetra Japan) is suspended. It was. The said chemical | medical solution 0.1ml was added here and it controlled to a 25 degreeC thermostat. One day after the chemical solution was treated, the number of dead insects was investigated, and the dead insect rate was calculated from the same formula as in Test Example 1. The test was performed twice.

As a result, the following compounds showed 100% mortality.
Compounds of the present invention: 1-007a, 1-008a, 1-013a, 1-015a, 1-016a, 1-018a, 1-020a, 1-021a, 1-024a, 1-025a.

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

Claims (19)

Formula (1):

[In the formula, D substituted with —S (O) _n R ¹ represents a structure represented by D1, D2, D3, or D4;

Q represents a ring represented by Q1, Q2, Q3, Q4 or Q5;

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),
U ¹ represents N (U ^1a ), an oxygen atom or a sulfur atom,
R ¹ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylthio, halo (C ₁ -C _{6) alkylthio,} C 1 -C ₆ alkylsulfinyl, halo _(C 1 ~C _{6) alkylsulfinyl,} C 1 -C ₆ alkylsulfonyl, halo _(C 1 ~C _{6) alkylsulfonyl,} C 1 -C ₆ represents alkoxy, halo _(C 1 _{~C 6)} alkoxy, ^{-OR 10,} cyano or nitro,
R ¹⁰ represents halo (C ₁ -C ₆ ) alkylsulfonyl,
Y1, Y2, Y3 and Y4 are each independently a hydrogen atom, a halogen _atom, C 3 -C ₆ cycloalkyl, substituted with ^{Y a} _(C 3 ~C _{6) cycloalkyl,} C 1 -C ₆ alkyl, Halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkylthio, halo (C ₁ -C ₆ ) alkylthio, C ₁ -C ₆ alkyl Sulfinyl, halo (C ₁ -C ₆ ) alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, halo (C ₁ -C ₆ ) alkylsulfonyl, —NH ₂ , —NHR ^{90 g} , cyano, nitro, V 1 or V 2;
Y5 and Y6 represent independently a hydrogen atom, a halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 ~C ₆₎ alkyl or _C 1 -C ₆ alkylthio,
R ^90g is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halo ( C ₁ -C ₆ ) alkoxycarbonyl, C ₁ -C ₆ alkylsulfonyl or halo (C ₁ -C ₆ ) alkylsulfonyl,
V1 represents the structure represented by V1-1, V1-2, V1-3 or V1-4,

V2 represents the structure represented by V2-1, V2-2, V2-3 or V2-4,

Z ¹ and Z ² are each independently a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkylthio, halo _(C 1 ~C _{6) alkylthio,} C 1 -C ₆ alkylsulfinyl, halo _(C 1 ~C _{6) alkylsulfinyl,} C 1 -C ₆ alkylsulfonyl, halo _(C 1 _~C 6) When alkylsulfonyl, cyano or nitro is represented and p4, p5, q2, q3 or q4 represents an integer of 2 or more, each Z ¹ and each Z ² may be the same as or different from each other. You may,
Y ^a represents cyano, —C (O) OH or —C (O) NH ₂ ,
U ^1a represents a hydrogen atom or C ₁ -C ₆ alkyl,
p4 represents an integer of 0, 1, 2, 3 or 4;
p5 represents an integer of 0, 1, 2, 3, 4 or 5;
q2 represents an integer of 0, 1 or 2,
q3 represents an integer of 0, 1, 2, or 3,
q4 represents an integer of 0, 1, 2, 3 or 4,
r represents an integer of 0 or 1,
n represents an integer of 0, 1 or 2. ] The condensed heterocyclic compound or its salt represented by these, or those N-oxides. R ¹ represents C ₁ -C ₆ alkyl;
R ² , R ³ and R ⁵ are each independently a hydrogen atom, a halogen atom, halo (C ₁ -C ₆ ) alkyl, halo (C ₁ -C ₆ ) alkylthio or halo (C ₁ -C ₆ ) alkoxy. Represent,
R ⁴ represents a hydrogen atom, halo (C ₁ -C ₆ ) alkyl, halo (C ₁ -C ₆ ) alkylthio, halo (C ₁ -C ₆ ) alkoxy or —OR ¹⁰ ,
Y1, Y2, Y3 and Y4 are each independently a hydrogen atom, a halogen _atom, C 3 -C _{6 cycloalkyl,} C 1 -C ₆ alkyl, halo _(C 1 ~C _{6) alkyl,} C 1 -C ₆ alkoxy , Halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkylthio, halo (C ₁ -C ₆ ) alkylthio, C ₁ -C ₆ alkylsulfinyl, halo (C ₁ -C ₆ ) alkylsulfinyl, C _1- C ₆ alkylsulfonyl, halo (C ₁ -C ₆ ) alkylsulfonyl, —NH ₂ , cyano, nitro, V 1 or V ₂ ,
Y5 represents a hydrogen atom,
The fused heterocyclic compound or a salt thereof or an N-oxide thereof according to claim ^1, wherein Z ¹ and Z ² each independently represent halo (C ₁ -C ₆ ) alkyl. D substituted with —S (O) _n R ¹ represents the structure represented by D1,
G ₁ represents C (Y1),
G ₂ is represents C (Y2),
G ₃ represents C (Y3),
The condensed heterocyclic compound or a salt thereof, or an N-oxide thereof according to claim 2, wherein G ₄ represents C (Y4).   The condensed heterocyclic compound or a salt thereof, or an N-oxide thereof according to claim 3, wherein Q represents a ring represented by Q1. Y1 represents a hydrogen atom,
Y2 represents a hydrogen atom, a halogen _atom, a C 3 -C ₆ cycloalkyl or halo _(C 1 ~C ₆₎ alkyl,
Y3 represents a hydrogen atom, a halogen _atom, C 3 -C _{6 cycloalkyl,} C 1 -C ₆ alkylthio, cyano, halo _(C 1 ~C ₆₎ alkyl or V2,
Y4 represents a hydrogen atom or a halogen atom,
V2 represents the structure represented by V2-3,
The fused heterocyclic compound or a salt thereof or an N-oxide thereof according to claim 4, wherein q2 represents an integer of 0. D substituted with —S (O) _n R ¹ represents the structure represented by D1,
G ₁ represents C (Y1),
G ₂ is represents C (Y2),
G ₃ represents a nitrogen atom,
The condensed heterocyclic compound or a salt thereof, or an N-oxide thereof according to claim 2, wherein G ₄ represents C (Y4). Q represents a ring represented by Q1,
7. The condensed heterocyclic compound or a salt thereof or an N-oxide thereof according to claim 6, wherein r represents an integer of 0. R ⁴ represents halo (C ₁ -C ₆ ) alkyl or halo (C ₁ -C ₆ ) alkoxy,
Y1 and Y4 represent a hydrogen atom,
Y2 represents a hydrogen atom, a halogen atom or a _C 3 -C ₆ cycloalkyl,
n represents the integer of 0 or 2, The condensed heterocyclic compound of Claim 7 or its salt, or those N-oxides.   The condensed heterocyclic compound or a salt thereof, or an N-oxide thereof according to claim 3, wherein Q represents a ring represented by Q2. R ² represents a hydrogen atom or a halogen atom,
R ³ represents a hydrogen atom, halo (C ₁ -C ₆ ) alkyl or halo (C ₁ -C ₆ ) alkylthio,
R ⁴ represents a hydrogen atom, halo (C ₁ -C ₆ ) alkyl, halo (C ₁ -C ₆ ) alkylthio or halo (C ₁ -C ₆ ) alkoxy,
R ⁵ represents a hydrogen atom,
Y1, Y2 and Y4 represent a hydrogen atom,
Y3 is halo _(C 1 _{~C 6)} alkyl,
n represents the integer of 2, The condensed heterocyclic compound of Claim 9 or its salt, or those N-oxides.   The pest control agent which contains the 1 type (s) or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-10 as an active ingredient.   The agrochemical which contains 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-10 as an active ingredient.   Control agent for internal or ectoparasites of mammals or birds containing one or more selected from the condensed heterocyclic compound according to any one of claims 1 to 10 and a salt thereof as an active ingredient .   14. The control agent according to claim 13, wherein the ectoparasite is a flea or ticks.   The insecticide or acaricide which contains 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-10 as an active ingredient.   The soil treatment agent which contains 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-10 as an active ingredient.   The soil treatment agent according to claim 16, wherein the soil treatment is performed by a soil irrigation treatment.   The seed treatment agent which contains the 1 type (s) or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-10 as an active ingredient.   The seed treatment agent according to claim 18, wherein the seed treatment is performed by dipping treatment.