JP2000198768A - 3-arylphenyl sulfide derivative and insecticide/miticide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound as a specific arylphenyl sulfide derivative, having high efficacy even at low doses, useful as an insecticide of high safety, exhibiting excellent controlling effect on insect pests including hemipteron pests, and capable of controlling resistant insect pests as well. SOLUTION: This new compound is a compound of formula I R is a 2-6C alkyl, alkenyl, or the like; (n) is 0-2; Ar is a group of formula II [Q1 to Q5 are each N, C-A1 (A1 is H, a halogen, or the like) or the like]; B0 to B3 are each H, a halogen, or the like}, e.g. 2-(2-propenylthio)-4-(4-trifluoromethylphenyl) benzonitrile. The compound of formula I is obtained by reaction of an arylphenylthiol derivative with a compound of RL1 (L1 is a halogen or the like) in the molar ratio of the latter to the former of 1-5 in 0.5-10 l of a solvent (e.g. diethyl ether) in the presence of 1-5 molar times of a base or radical initiator pref. at 0-150 deg.C for 10 min to 20 h.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel 3-arylphenyl sulfide derivative and an insecticide and acaricide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art 3-Methylthiobiphenyl derivatives are disclosed in East German Patent No. 142541, East German Patent No. 142542, Japanese Patent Laid-Open No. 7-2655.
And Tetrahedron (Tetrahedr)
on), Vol. 39, p. 2289 (1983), tetrahedron letter (Tetrahed).
ron Lett. ), Vol. 25, No. 44, No. 509
5 (1984) and the like, and 3-pyridylphenyl sulfide derivatives are disclosed in German Patent No. 4323.
No. 916 specification and international application WO95 / 02580
However, there is no description about insecticides and acaricides. Further, regarding 3-azolylphenyl sulfide derivatives, International Application WO 96/0683
No. 0, Japanese Patent Application Laid-Open No. 2-184675, Japanese Patent Application Laid-Open No. 60-233061, European Patent No. 152890, South African Patent 68008
It is known from the specifications of JP-A-55-55 and DE-A-3316300, but there is no description about insecticides and acaricides. On the other hand, the 4-biphenyl sulfide derivative can be used as an insecticide, for example,
Although reported in U.S. Pat. No. 3,424,955, the 3-arylphenyl sulfide derivative of the present invention has not yet been known.

[0003]

In recent years, the use of existing commercially available insecticides has been restricted due to problems such as residue, accumulation, environmental pollution, etc., and some of them have become less effective due to the development of resistant pests by long-term use. Is out. Therefore, development of an insecticide having high efficacy at a low dose and excellent in safety has been desired.

[0004]

Means for Solving the Problems In view of such circumstances, the present inventors have synthesized various 3-arylphenyl sulfide derivatives and have studied the physiological activities thereof. As a result, the compound of the present invention is a variety of pests, especially agricultural and horticultural pests, spider mite, Kanzawa spider mite, mites spider mite, mites, konaga, nicame, lepidopteran pests represented by scotch and the like, brown planthopper, leafhopper, The present invention has been found to exhibit excellent effects on Hemiptera pests represented by cotton aphids and the like and Coleoptera pests represented by Azuki weevil and the like, thereby completing the present invention.

That is, the present invention relates to (1) a compound represented by the general formula [I]:

[0006]

Embedded image

In the formula, R is a C ₂ -C ₆ alkyl group (the group may be mono- or poly-substituted by a halogen atom or a cyano group), or a C ₂ -C ₆ alkenyl group (the group is halogen may be mono- or polysubstituted by atoms or a cyano group), an alkynyl group of C ₂ -C ₆ (which may be mono-substituted or poly-substituted by halogen atoms or a cyano group), C ₃ -C ₆ cycloalkyl groups which may be mono- or polysubstituted by halogen atoms or cyano groups or C ₄ -C ₉ cycloalkylalkyl groups wherein said groups are mono-substituted or poly-substituted by halogen atoms or cyano groups. May be substituted), and n represents an integer of 0 to 2,
The Ar group has the general formula:

[0008]

Embedded image

And a group represented by the formula:₁,
Q_Two, Q_Three, Q_FourAnd Q_FiveIs a nitrogen atom or C-
A₁, A nitrogen atom or CA_Two, A nitrogen atom or CA_Three,
Elementary atom or CA_FourAnd a nitrogen atom or CA_FiveAnd Q
₆Represents an oxygen atom or a sulfur atom;₇Is a nitrogen atom or C
-A₇And Q₈Is a nitrogen atom or CA₈And A₁,
A_Five, A₇, A₁₁And B₀Represents a hydrogen atom, a halogen atom,
Mino group, cyano group, nitro group, C₁~ C₆An alkyl group of
C₁~ C_FourHaloalkyl group of C₁~ C₆Alkylthio group of
(The group is mono- or poly-substituted by a halogen atom.
Or C) ₁~ C₆Represents an alkoxy group of_Two,
A_Three, A_Four, A₆, A₉, B₁, B_TwoAnd B_ThreeIs a hydrogen atom,
Logen atom, cyano group, nitro group, C₁~ C₆The alkyl of
Groups (the groups are halogen, hydroxyl, cyano, C_Two~ C₇
An alkoxycarbonyl group or C₁~ C₆An alkoxy group
May be mono- or poly-substituted), C_Two~ C₆
Alkenyl group (the group is a halogen atom or a cyano group)
Mono- or poly-substituted), C_Two~ C₆No
Alkynyl group (the group is a halogen atom or a cyano group;
Substituted or poly-substituted), C₁~ C₆Arco
A xy group (the group is a halogen atom, a cyano group,_Two~ C_FiveNo
Alkoxycarbonyl group or C₁~ C_ThreeBy the alkoxy group of
Mono- or poly-substituted), C₁~ C₆No
Alkylthio group (the group is a halogen atom or C₁~ C_ThreeAl
Mono- or poly-substituted by a Coxy group),
C₁~ C₆An alkylsulfinyl group (the group is a halogen atom)
Child or C ₁~ C_ThreeMono-substituted or poly-substituted by an alkoxy group
May be substituted), C₁~ C₆Alkylsulfonyl group of
(The group is a halogen atom or C₁~ C_ThreeBy the alkoxy group of
Mono- or poly-substituted), C₁~ C₇No
Sil group, C_Two~ C_FiveHaloalkylcarbonyl group, carbo
Xyl group, C_Two~ C₇An alkoxycarbonyl group or NR
₁R_Two[Wherein, R₁And R_TwoAre each independently a hydrogen atom,
C₁~ C₆An alkyl group of which is a halogen atom, cyano
Group, hydroxyl group, C₁~ C₆An alkoxy group or C₁
~ C₆Mono- or poly-substituted by the alkylthio group of
Or C) _Two~ C₆An alkenyl group of the formula
Mono- or poly-substituted by
Or C)_Two~ C₆An alkynyl group, which is a halogen atom
Mono- or poly-substituted by a substituent or a cyano group
I), C₁~ C₇An acyl group or C_Two~ C₇Alkoxyka
Represents a rubonyl group. R₁And R_TwoIs the combined nitrogen
It may form a 5- to 6-membered ring with the atoms. ]
A₈Represents a hydrogen atom, a halogen atom, a cyano group, C₁~ C₆of
An alkyl group, which is a halogen atom or C₁~ C_ThreeArco
Mono- or poly-substituted by an xy group), C
₁~ C₆An alkoxy group represented by a halogen atom or C₁~
C_ThreeMono- or poly-substituted by an alkoxy group of
Or C)₁~ C₇An acyl group of C_Two~ C_FiveHalo archi
Carbonyl group or NR₁R_Two(Where R₁And R_TwoIs
Has the same meaning as ) And A_TenIs a hydrogen atom, C₁~
C₆(The group is a halogen atom or C₁~ C_Threeof
Mono- or poly-substituted by an alkoxy group
I), C₁~ C₇An acyl group of C_Two~ C_FiveHaloalkyl mosquito
Rubonyl group, carboxyl group or C_Two~ C₇The alkoxy of
A carbonyl group, provided that the Ar group is represented by the general formula [Ar-
1] and [Ar-2], Q₁~ Q_FiveIs up to 2
Can be a nitrogen atom, and the Ar group further has a general formula [Ar-1]
And Q_FiveIf only nitrogen atom, A₁Is a hydrogen atom,
Further, when the Ar group is represented by Q in the general formula [Ar-1]₁, Q_Two, Q_Three, Q_Four
And Q_Five, Respectively, CA₁, CA_Two, CA_Three, C
-A_FourAnd CA_FiveIn the case of A_Two, A_Three, A_FourAnd B_TwoBut at the same time
Is not a hydrogen atom.₁From A_FiveAll are hydrogen sources
B for a child_TwoIs a methyl group and R is an isopropyl group
Except for certain compounds, the Ar group is represented by the general formula [Ar-4]₈
Is CA₈Then R is C_Two~ C₆An alkyl group of the formula
Mono- or poly-substituted by halogen atom
I), C_Three~ C₆A cycloalkyl group (the group is a halogen atom)
May be monosubstituted or polysubstituted) or C_Four
~ C₉A cycloalkylalkyl group (the group is a halogen atom)
May be mono-substituted or poly-substituted)
You. Induction of 3-arylphenyl sulfide represented by｝
Conductor and insecticide and miticide containing it as an active ingredient
The agent is provided.

The terms used in this specification are defined below.

The halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The alkyl group means a linear or branched alkyl group having 1 to 6 carbon atoms, unless otherwise specified.
Examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and the like.

The term "cycloalkyl group" means a cycloalkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.

The cycloalkylalkyl group is a cycloalkylalkyl group having 1 to 3 carbon atoms substituted by a cycloalkyl group having 3 to 6 carbon atoms.
And 3 represents an alkyl group, for example, a cyclopropylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group and the like.

The alkenyl group is a linear or branched alkenyl group having 2 to 6 carbon atoms, such as an ethenyl group,
Examples thereof include a 2-propenyl group.

The alkynyl group means a linear or branched alkynyl group having 2 to 6 carbon atoms, such as an ethynyl group,
Examples thereof include a 2-propynyl group.

The term "haloalkyl group" means a linear or branched alkyl group having 1 to 4 carbon atoms and substituted by the same or different halogen atoms 1 to 9 unless otherwise specified. Examples thereof include a trifluoromethyl group and a tetrafluoroethyl group.

The term "alkoxy group" means a (alkyl) -O- group in which the alkyl moiety has the above-mentioned meaning, and examples thereof include a methoxy group and an ethoxy group.

The term "alkoxyalkyl group" means (alkyl) -O- (alkyl)-wherein the alkyl moiety is as defined above.
A methoxymethyl group, an ethoxymethyl group and the like.

An alkoxyalkoxy group is (alkyl) -O- (alkyl) in which the alkyl moiety has the above-mentioned meaning.
Represents an -O- group, and examples thereof include a methoxymethoxy group and an ethoxymethoxy group.

The haloalkoxy group is a (haloalkyl) -O- group in which the haloalkyl moiety is as defined above,
For example, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, etc. can be mentioned.

The alkylthio group, alkylsulfinyl group and alkylsulfonyl group are (alkyl) -S-group and (alkyl) -SO
- group, (alkyl) -SO ₂ - can be given a group, such as methylthio, ethylthio group, methylsulfinyl group, ethylsulfinyl group, methylsulfonyl group, ethylsulfonyl group.

The haloalkylthio group, haloalkylsulfinyl group and haloalkylsulfonyl group have the above-mentioned meaning (haloalkyl) -S-
Group, (haloalkyl) -SO- group, (haloalkyl)-
An SO ₂ — group, for example, a trifluoromethylthio group,
Dichlorofluoromethylthio group, trifluoromethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group, trifluoromethylsulfonyl group, 2,2,2
Examples thereof include a 2-trifluoroethylsulfonyl group.

The acyl group is a formyl group or an (alkyl) -CO- group in which the alkyl moiety has the above-mentioned meaning.
Examples include an acetyl group and a propionyl group.

The haloalkylcarbonyl group and the alkoxycarbonyl group mean a (haloalkyl) -CO- group or a (alkoxy) -CO- group in which the haloalkyl or alkoxy moiety is as defined above, for example, a trifluoroacetyl group, a methoxycarbonyl group. And the like.

In the above general formula [I], a preferable compound group includes a group in which the Ar group is the general formula [Ar-1] or the general formula [Ar-4] and R is a 2,2,2-trifluoroethyl group. , N-propyl group, 2,2,3,3-tetrafluoropropyl group or cyclopropylmethyl group,
Is a group of compounds represented by 0 or 1.

In a further preferred group of compounds, R is 2,
2,2-trifluoroethyl group, n-propyl group, 2,
A 2,3,3-tetrafluoropropyl group or a cyclopropylmethyl group, wherein the Ar group is such that A ₁ and A ₅ are hydrogen atoms and A ₃ or A ₂ is a halogen atom, a difluoromethoxy group,
A phenyl group that is a trifluoromethoxy group or a trifluoromethyl group, B ₀ is a hydrogen atom, a methyl group, or a halogen atom; B ₂ is a halogen atom, a cyano group, an alkyl group, or a haloalkyl group; Or a compound group represented by 1.

[0028]

Next, typical specific examples of the compound of the present invention represented by the general formula [I] are shown in Tables 1 to 60.
The compound numbers will be referred to in the following description.

The following notations in the tables in the present specification represent the corresponding groups as follows.

Me: methyl group, Et: ethyl group, Pr: n-propyl group, Pr-i: isopropyl group, Pr-c: cyclopropyl group, Bu: n-butyl group, Bu-i: isobutyl group, Bu -S: sec-butyl group, Bu-t: tert-butyl group, Bu-c: cyclobutyl group, Pen: n-pentyl group, Pen-i: isopentyl group, Pen-c: cyclopentyl group, Hex-c: cyclohexyl Group,

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

[Table 6]

[0037]

[Table 7]

[0038]

[Table 8]

[0039]

[Table 9]

[0040]

[Table 10]

[0041]

[Table 11]

[0042]

[Table 12]

[0043]

[Table 13]

[0044]

[Table 14]

[0045]

[Table 15]

[0046]

[Table 16]

[0047]

[Table 17]

[0048]

[Table 18]

[0049]

[Table 19]

[0050]

[Table 20]

[0051]

[Table 21]

[0052]

[Table 22]

[0053]

[Table 23]

[0054]

[Table 24]

[0055]

[Table 25]

[0056]

[Table 26]

[0057]

[Table 27]

[0058]

[Table 28]

[0059]

[Table 29]

[0060]

[Table 30]

[0061]

[Table 31]

[0062]

[Table 32]

[0063]

[Table 33]

[0064]

[Table 34]

[0065]

[Table 35]

[0066]

[Table 36]

[0067]

[Table 37]

[0068]

[Table 38]

[0069]

[Table 39]

[0070]

[Table 40]

[0071]

[Table 41]

[0072]

[Table 42]

[0073]

[Table 43]

[0074]

[Table 44]

[0075]

[Table 45]

[0076]

[Table 46]

[0077]

[Table 47]

[0078]

[Table 48]

[0079]

[Table 49]

[0080]

[Table 50]

[0081]

[Table 51]

[0082]

[Table 52]

[0083]

[Table 53]

[0084]

[Table 54]

[0085]

[Table 55]

[0086]

[Table 56]

[0087]

[Table 57]

[0088]

[Table 58]

[0089]

[Table 59]

[0090]

[Table 60]

The compound of the present invention represented by the general formula [I]
It can be manufactured according to the following manufacturing methods, but is not limited to these methods.

<Production Method 1> The phenyl group of the compound of the present invention represented by the general formula [I] is always substituted with an RS (O) _n group. Can be used.

[0093]

Embedded image

Wherein L ₁ represents a halogen atom, an alkylsulfonyloxy group, a phenylsulfonyloxy group or SO ₂ M, M represents an alkali metal or an alkaline earth metal [preferably sodium or potassium],
r, B _{0 to} B ₃ and R have the same meanings as described above. That is, based on 1 mol of the compound represented by the general formula [II],
By reacting 1 to 5 moles of the compound represented by the general formula [III] in 0.5 to 10 l of a solvent in the presence of 1 to 5 moles of a base or 1 to 5 moles of a radical initiator, The target 3-arylphenyl sulfide derivative represented by the formula [I-1] can be obtained.

Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; , N
Aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide and sulfolane; alcohols such as methanol, ethanol and isopropyl alcohol; nitriles such as acetonitrile and propionitrile And esters such as ethyl acetate or ethyl propionate; aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane; pyridines such as pyridine or picoline; and water or a mixed solvent thereof.

As the base, for example, sodium hydroxide,
Hydroxides of alkali metals such as potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, carbonates of alkali metals such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate Inorganic bases such as bicarbonates of alkali metals; metal hydrides such as sodium hydride and potassium hydride; metal salts of alcohols such as sodium methoxide, sodium ethoxide, potassium tert-butoxide or triethylamine; N , N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like.

Examples of the radical initiator include sulfurous acid,
Examples thereof include sulfites and sulfurous acid adducts such as Rongalite (sodium / formaldehyde / sulfoxylate). Further, a base and a radical initiator may be used in combination.

The reaction is carried out at any temperature from -30 ° C to the reflux temperature in the reaction system, preferably from 0 ° C to 15 ° C.
The temperature range is 0 ° C.
It ends in 0 minutes to 20 hours.

<Production Method 2> The starting material for the compound of the present invention represented by the general formula [I-1] is an oxidative dimer of the compound represented by the general formula [II] used in the production method 1. A compound represented by a certain general formula [IV] can also be used.

[0100]

Embedded image

(In the formula, L ₂ represents a halogen atom or a sulfinic acid salt, and Ar, B _{0 to} B ₃ and R have the same meanings as described above.) That is, the compound 1 represented by the general formula [IV] For moles,
Reaction of 1 to 5 moles of the compound represented by the general formula [V] in a solvent of 0.5 to 10 l in the presence of 1 to 5 moles of a radical initiator (same as described in Production Method 1) By doing so, the desired 3-arylphenyl sulfide derivative represented by the general formula [I-1] can be obtained.

Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. N-methyl-2-
Aprotic polar solvents such as pyrrolidone, dimethylsulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate or ethyl propionate; aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane; Examples thereof include pyridines such as pyridine and picoline and water or a mixed solvent thereof.

Further, the base exemplified in Production Method 1 may be used in combination with the radical initiator.

The reaction is carried out at any temperature from -30 ° C to the reflux temperature in the reaction system, preferably from 0 ° C to 15 ° C.
The temperature range is 0 ° C.
It ends in 0 minutes to 20 hours.

<Production Method 3>

[0106]

Embedded image

(Wherein L ₃ represents a halogen atom;
The group represents a general formula [Ar-1] or a general formula [Ar-3], and B _{0 to} B ₃ , R and n have the same meanings as described above. That is, a metal (lithium, magnesium, zinc, or the like can be exemplified) or an organometallic compound (n-butyllithium, or the like can be exemplified with respect to 1 mol of the compound represented by the general formula [VI] or [VII]. ) Is reacted in a solvent of 0.5 to 10 l, and then the other compound represented by the general formula [VI] or [VII] is reacted with a 1 to 5 mol of a transition metal catalyst. By reacting in the presence or absence of 0.01 to 1 mole, the desired 3-arylphenyl sulfide derivative represented by the general formula [I] can be obtained.

Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, and aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane. And pyridines such as pyridine and picoline or a mixed solvent thereof.

As the transition metal catalyst, palladium acetate,
Dichlorobis (triphenylphosphine) palladium,
Examples include palladium compounds such as tetrakis (triphenylphosphine) palladium and tris (dibenzalacetone) palladium, and nickel compounds such as bis (triphenylphosphine) nickel chloride and tetrakis (triphenylphosphine) nickel.

The reaction is carried out at any temperature from -90 ° C to the reflux temperature in the reaction system, preferably from -78 ° C to
The temperature range is 60 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

The above L ₃ is generally preferably a bromine atom or an iodine atom, but after reacting the compound represented by the general formula [VII] with a metal or organometallic compound, A ₁ and A ₅ are not hydrogen. The general formula [V
When reacting the compound of I), L ₃ is preferably a fluorine atom.

<Production Method 4>

[0113]

Embedded image

Wherein Z is a trialkylstannyl group [preferably a trimethylstannyl group], a dihydroxyboranyl group or a dialkoxyboranyl group [1,3-dioxoborolan-2-yl group or a dimethoxyboranyl group. Preferred], the Ar group represents the general formula [Ar-1] or the general formula [Ar-3], and B _{0 to} B ₃ , L ₃ [preferably a bromine or iodine atom], R and n are the same as those described above. That is, the compound represented by the general formula [VIII] or [IX] is used in an amount of 1 to 5 times the amount of the compound represented by the general formula [VI] or [VII] with respect to 1 mol of the compound represented by the general formula [VIII] or [IX]. 1 to 5 moles of a base (same as described in Production Method 1) and a transition metal catalyst (same as described in Production Method 3) in 0.5 to 10 l. ) Reaction in the presence of 0.01 to 1 times mole Thereby, the target 3-arylphenyl sulfide derivative represented by the general formula [I] can be obtained.

When Z is a dihydroxyboranyl group, the compound represented by the formula [VIII] or [IX] is replaced by the dehydrated trimer represented by the formula [VIII]
Boroxin represented by [-1] or [IX-1] can also be used.

[0116]

Embedded image

(In the formula, the Ar group represents the general formula [Ar-1] or the general formula [Ar-3], and B _{0 to} B ₃ , R and n have the same meanings as described above.) The reaction is carried out at an arbitrary temperature from 70 ° C. to the reflux temperature in the reaction system, preferably within a temperature range of −20 ° C. to 100 ° C., and the reaction varies depending on the compound, but it is 10 minutes to 2 hours.
It ends in 0 hours.

<Production Method 5>

[0119]

Embedded image

(In the formula, Y ₁ represents a hydrogen atom or a halogen atom, the Ar group represents a general formula [Ar-1], [Ar-3] or [Ar-4], and L ₃ , B ₀ -B ₃ , R and n have the same meanings as described above. That is, the metal (lithium or magnesium can be exemplified) or the organometallic compound (n-butyl) is used per 1 mol of the compound represented by the general formula [X]. Lithium and the like can be exemplified.) After reacting 1 to 3 moles in a solvent (the same as described in Production Method 3) in 0.5 to 10 l, the compound represented by the general formula [X
The desired 3-arylphenyl sulfide derivative represented by the general formula [I] can be obtained by reacting 1 to 5 times the mole of the compound represented by the general formula [I] or the general formula [XII].

The reaction is carried out at any temperature from -90 ° C to the reflux temperature in the reaction system, preferably from -78 ° C to
The temperature range is 70 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

<Production Method 6>

[0123]

Embedded image

(Wherein, the Ar group represents the general formula [Ar-2] or the general formula [Ar-4], and B ₄ represents an electron-withdrawing group [cyano group, nitro group or alkoxy group] in the definition of B ₂ above. And B ₀ , B ₁ , B ₃ and R have the same meanings as described above, and L ₄ represents a halogen atom, an alkylsulfonyloxy group or a phenylsulfonyloxy group.) 1 to 5 moles of the compound represented by the general formula [XIV] is mixed with 1 mole to 5 moles of the compound represented by the formula [XIII] in a solvent of 0.5 to 10 l in the form of a base (same as described in Production method 1). )) By reacting in the presence of 1 to 5 moles, the desired 3-arylphenyl sulfide derivative represented by the general formula [I-2] can be obtained.

Here, the solvent may be any solvent which does not inhibit the reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, and ethers such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane and dioxane. Ketones such as acetone, methyl ethyl ketone, etc., nitriles such as acetonitrile or propionitrile, aprotic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide and N, N-dimethylacetamide, pentane, hexane, cyclohexane and heptane And pyridines such as pyridine and picoline or a mixed solvent thereof.

The reaction is carried out at any temperature from -70 ° C to the reflux temperature in the reaction system, preferably from -20 ° C to
The temperature range is 150 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

<Production Method 7>

[0128]

Embedded image

(Wherein, the Ar group represents the general formula [Ar-2] or [Ar-4], and B _{0 to} B ₃ , R and n have the same meanings as described above). The compound represented by the general formula [XV] and an anhydrous copper salt (for example, anhydrous copper acetate and the like can be exemplified) in an amount of 1 to 5 moles per 1 mol of the compound represented by [XIII],
An organic base (for example, triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylamino) in the presence or absence of 5 to 50 g of 3 to 4 molecular sieves in a solvent of 0.5 to 10 l Pyridine, 1,8
-Diazabicyclo [5.4.0] -7-undecene and the like. ) By reacting in the presence of 1 to 5 moles, the desired 3-arylphenyl sulfide derivative represented by the general formula [I] can be obtained.

Here, the solvent may be any solvent which does not inhibit the reaction, for example, halogenated alkanes such as chloroform and dichloromethane, aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, tetrahydrofuran, 1,1 Ethers such as 2-dimethoxyethane and dioxane, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, N, N-dimethylformamide and N, N
Aprotic polar solvents such as N-dimethylacetamide,
Examples thereof include aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, and a mixed solvent thereof.

The reaction is carried out at any temperature from -70 ° C to the reflux temperature in the reaction system, preferably from -20 ° C to
The temperature range is 150 ° C., and the reaction is completed in 10 minutes to 72 hours, depending on the compound.

<Production Method 8>

[0133]

Embedded image

(Wherein the Ar group is a group represented by the general formula [Ar-1]
[Ar-4], B _{0 to} B ₃ and R have the same meanings as described above, and L ₅ represents a halogen atom, an alkylsulfonyloxy group, a phenylsulfonyloxy group, an alkylsulfonyl group, a phenylsulfonyl group or a nitro group. Show. That is, 1 mole of the compound represented by the general formula [XVI] is added to the compound represented by the general formula [XVII] (an isothiourea mineral salt in which a sulfur atom is substituted by an R group and an alkali hydroxide or It can also be generated from an alkali carbonate.) By reacting 1 to 5 moles in a solvent of 0.5 to 10 l in the presence of 1 to 5 moles of a base, a compound represented by the general formula [I-1] is obtained. The desired 3-arylphenyl sulfide derivative can be obtained.

Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. N-methyl-2-
Aprotic polar solvents such as pyrrolidone, dimethyl sulfoxide and sulfolane; alcohols such as methanol, ethanol and methyl cellosolve; aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane; pyridines such as pyridine or picoline; and water. Alternatively, a mixed solvent thereof can be exemplified.

As the base, the base exemplified in Production Method 1, copper monoxide and the like can be used.

The reaction is carried out at any temperature from -70 ° C to the reflux temperature in the reaction system, preferably from 0 ° C to 15 ° C.
The temperature range is 0 ° C.
It ends in 0 minutes to 20 hours.

<Production Method 9>

[0139]

Embedded image

(Wherein, Ar, B ₀ -B ₃ , R and M have the same meaning as described above, and m represents 0 or 2.) That is, 1 mol of the compound represented by the general formula [XVIII] is used. , Solvent (same as described in Production method 1) 0.5 to 1
In 0 l, a conventional method [mineral acid (hydrochloric acid, sulfuric acid, etc. can be exemplified)
And a method of using a nitrite or an alkyl nitrite] to obtain a diazonium salt, and then a mercaptan salt or a sulfinic acid salt represented by the general formula [XIX] or a disulfide compound 1 represented by the general formula [XX] The desired 3-arylphenyl sulfide derivative represented by the general formula [I-3] can be obtained by reacting the compound with a 5- to 5-fold molar amount.

The reaction is carried out at any temperature from -30 ° C to the reflux temperature in the reaction system, preferably from -10 ° C to
The temperature is 100 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

<Production Method 10>

[0143]

Embedded image

(Wherein, X ₁ represents a halogen atom, an alkoxy group, an acyloxy group, an alkylsulfonyloxy group, or a phenylsulfonyloxy group, Y ₂ represents an alkoxy group or an alkylthio group, and L ₆ represents a halogen atom, an acyloxy group. , Alkylsulfonyloxy group, phenylsulfonyloxy group, R ₁ represents an alkyl group,
L ₃ , A ₈ , A ₁₀ , A ₁₁ , B _{0 to} B ₃ , R and n have the same meaning as described above. The compound of the present invention represented by the general formula [I-4] can be produced by a general 1,3-dipolar cycloaddition reaction (for example, see JP-A-63-28).
No. 7768 or Comprehensive Heterocyclic Chemistry (Comprehens)
live Heterocyclic Chemistr
y) the method described in Volume 5, page 283, etc.), and the compound of the present invention represented by the general formula [I-5] can be produced by a cyclization reaction with a nitrile derivative (for example, Japanese Patent Application Laid-Open No. 1-230562 or Comprehensive heterocyclic chemistry (Comp
rehensive Heterocyclic Ch
chemistry), the method described in Vol. 5, p. 769).

That is, the compound represented by the general formula [XXII] or the general formula [X
XIII] or the compound 1 represented by the general formula [XIV]
Five-fold moles of the solvent were used (the same as described in Production Method 1).
By reacting in 0.5 to 10 l in the presence of 1 to 5 moles of a base (same as described in Production method 1),
The desired pyrazolylphenyl sulfide derivative represented by the general formula [I-4] can be obtained.

Compound 1 represented by the general formula [XXI]
The compound represented by the general formula [XXV-1] or the compound represented by the general formula [XXV-2] is used in an amount of 1 to 5 moles per mole of the solvent (same as described in Production method 1). 0.5-1
In 0 l, bases (same as described in Production method 1) 1 to 5
By reacting in the presence of a 2-fold molar amount, the compound represented by the general formula [I-
5] The desired triazolylphenyl sulfide derivative represented by the formula [5] can be obtained.

As an alternative method, 1 mol of the compound represented by the general formula [XXI] is converted to amidrazone [XXI-1] with 1 to 3 moles of aqueous ammonia to prepare a solvent (the same as described in Production Method 1). ) Of 0.5 to 10 l, to which the general formula [XX
V-3] is reacted in the presence of 1 to 5 moles of a base (same as described in Production method 1), or represented by general formula [XXV-4]. The orthoester is reacted with 1 to 5 moles in the presence of an acid catalyst (for example, a sulfonic acid such as p-toluenesulfonic acid or a Lewis acid such as titanium tetrachloride) to obtain a compound represented by the general formula [I- 5] can be obtained as the target triazolylphenyl sulfide derivative.

The reaction is carried out at any temperature from -30 ° C to the reflux temperature in the reaction system, preferably from -10 ° C to
The temperature is 100 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

<Production Method 11>

[0150]

Embedded image

(Wherein L ₆ , R ₁ , X ₁ , A ₈ , A ₁₀ ,
A ₁₁ , B _{0 to} B ₃ , R and n have the same meaning as described above. That is, 1 to 5 moles of the compound represented by the general formula [XXVII-1] or the compound represented by the general formula [XXVII-2] is added to 1 mol of the compound represented by the general formula [XXVI], Solvent (same as described in Production Method 1) 0.5 to 1
In 0 l, bases (same as described in Production method 1) 1 to 5
By reacting in the presence of a 2-fold molar amount, the compound represented by the general formula [I-
4] to obtain the desired 3-pyrazolylphenyl sulfide derivative.

The compound represented by the general formula [XXVIII] or a mineral acid salt thereof and the compound represented by the general formula [XXIX] are 1 to 5 times relative to 1 mol of the compound represented by the general formula [XXVI]. The reaction is carried out in a solvent (similar to the description of the production method 1) in a solvent of 0.5 to 10 l in the presence of 1 to 5 times mol of the base (same as the description of the production method 1). The target 3-triazolylphenyl sulfide derivative represented by the general formula [I-5] can be obtained.

The reaction is carried out at any temperature from -30 ° C to the reflux temperature in the reaction system, preferably from -10 ° C to
The temperature is 100 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

<Production Method 12>

[0155]

Embedded image

(Wherein R ₁ , X ₁ , A ₂ -A ₅ , B ₀ -B ₃ ,
R and n have the same meaning as described above. ) That is, the general formula [X
XX] and 1 mole of the compound represented by the general formula [XXV]
II-3] or a compound represented by the general formula [XXVII-
1] to 5-fold molar amount of the compound represented by the formula (4)
Is the same as described above. ) In 0.5 to 10 l, the reaction was carried out in the presence of 1 to 5 moles of a base (same as described in Production method 1) to obtain the desired 3- (3-cyclopentadiene) represented by the general formula [I-6]. (2-oxopyrimidinyl) phenyl sulfide derivative can be obtained.

Further, the compound represented by the general formula [XXXII-1] or the compound 1 represented by the general formula [XXXII-2] is added to 1 mol of the compound represented by the general formula [XXXI].
Up to 5 times the molar amount of a solvent (same as described in Production method 1)
By reacting in 0.5 to 10 l in the presence of 1 to 5 moles of a base (same as described in Production method 1),
The target 3- (6-oxopyrimidinyl) phenyl sulfide derivative represented by the general formula [I-7] can be obtained.

The reaction is carried out at any temperature from -30 ° C to the reflux temperature in the reaction system, preferably from -10 ° C to
The temperature is 100 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

<Production Method 13>

[0160]

Embedded image

(Wherein, Ar, B _{0 to} B ₃ and R have the same meanings as described above, and q represents 1 or 2.) That is, the compound 1 of the present invention represented by the general formula [I-1] By oxidizing the mol with 1 to 6 times the molar amount of the oxidizing agent in 0.5 to 10 l of the solvent, the objective 3 represented by the general formula [I-8] is obtained.
-Arylphenyl sulfide derivatives can be obtained. Here, a catalyst (for example, sodium tungstate can be exemplified) may be added in an amount of 0.01 to 1 mole in some cases.

Here, examples of the oxidizing agent include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, and oxone (OXONE, trade name of E.I.
Containing potassium hydrogen peroxosulfate), N-chlorosuccinimide, N-bromosuccinimide, hypochlorous acid
Examples include tert-butyl or sodium hypochlorite.

As the solvent, for example, diethyl ether,
Ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; N, N-dimethylformamide;
Aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide and sulfolane; alcohols such as methanol, ethanol and isopropyl alcohol; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane;
Examples thereof include aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid and water, or a mixed solvent thereof.

The reaction is carried out at any temperature from -30 ° C to the reflux temperature in the reaction system, preferably from -10 ° C to
The temperature is 100 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

The compound of the present invention represented by the general formula [I]
Similarly to Production Method 13, the compound of the present invention can be produced using the compound itself as a raw material. That is, a compound of the present invention represented by a new general formula [I] can be obtained from a compound of the present invention by introducing a functional group or converting a functional group by a generally known method (Examples 13 to 13). 17 but is not limited to these.)

Next, a method for synthesizing an intermediate for producing the compound of the present invention will be described in detail.

<Production Method 14> The general formulas [II] and [I
Synthesis of Production Intermediate Represented by V] The compounds represented by the general formulas [II] and [IV] can be synthesized as follows, but can be mutually converted by an oxidation-reduction reaction. The compound represented by the general formula [II] is easily oxidized by oxygen in the air, and may become a compound represented by the general formula [IV].

[0168]

Embedded image

(Wherein, R ₂ represents a methyl group or a trifluoromethyl group, and Ar, B ₀ -B ₃ and Y ₁ have the same meanings as described above). One mole of the compound was dissolved in a solvent (the same as described in Production Method 13) in an amount of 0.5 to 0.5.
Oxidizing agent in 10 l (same as described in Production Method 13)
It is oxidized with 1 to 3 moles to obtain methyl sulfoxide, and then treated with 1 to 5 moles of acetic anhydride or trifluoroacetic anhydride to carry out a Pummeler rearrangement reaction to obtain a corresponding acyloxymethyl sulfide [XXIV], which is hydrolyzed. Thereby, the target compound represented by the general formula [II] or [IV] can be obtained.

Alternatively, 1 mol of the compound represented by the general formula [XXXV] is treated with 1 to 5 moles of chlorosulfonic acid to give a sulfonyl chloride [XXXVI], which is then treated with lithium aluminum hydride, zinc and an acid. Reduction by using tin and an acid or red phosphorus and iodine in a molar amount of 1 to 5 times enables to obtain a synthetic intermediate represented by the general formula [II].

Alternatively, 1 mol of the compound represented by the general formula [XXXV] is dissolved in an inert solvent such as carbon disulfide, nitrobenzene or o-dichlorobenzene in 0.5 to 10 l of a Lewis acid such as aluminum chloride. By reacting with 0.4 to 1.0 mole of sulfur monochloride in the presence of up to 2.0 mole, a synthetic intermediate represented by the general formula [IV] can be obtained.

Alternatively, 1 mol of the compound represented by the general formula [X] is added to a solvent (same as described in Production Method 3) in an amount of 0.5 to 0.5.
After treating with 1 to 3 moles of a metal or organometallic compound (same as described in Production method 3) in 10 l, sulfur 1 to 5
The target compound represented by the general formula [II] can be obtained by reacting twice as many moles.

Alternatively, 1 mol of the compound represented by the general formula [XVIII] is converted into a diazonium salt in the same manner as in Production Method 9, and then reacted with 1 to 3 times the molar amount of a xanthate or a thiocyanate. By subjecting the product to alkaline hydrolysis, the target compound represented by the general formula [II] can be obtained.

The reaction is carried out at any reaction temperature from -70 ° C to the reflux temperature in the reaction system, preferably in the temperature range of -20 ° C to 100 ° C. It ends in ~ 20 hours.

Further, when B ₂ is an electron-withdrawing group B ₄ , a synthetic intermediate represented by the general formula [II-1] can be obtained by a substitution reaction.

[0176]

Embedded image

(In the formula, Ar, L ₅ and B _{0 to} B ₄ have the same meanings as described above.) That is, 1 mol of the compound represented by the general formula [XXXVII] is added to sodium sulfide [XXXVIII] 1 to Three-fold molar reaction was carried out in the presence of a base (similar to the description of the production method 1) 1 to 5 molar times in 0.5 to 10 l of a solvent (same as described in the production method 1). Thereafter, the target 3-arylphenylthiol derivative represented by the general formula [II-1] can be obtained by neutralization with a mineral acid or the like.

The reaction is carried out at any temperature from -30 ° C to the reflux temperature in the reaction system, preferably from -20 ° C to
The temperature is 100 ° C., and the reaction is completed in 10 minutes to 20 hours, depending on the compound.

The above formulas [X], [XVIII],
[XXXIII], [XXXV] and [XXXVII]
Are represented by the following Production Method 3, Production Method 4, Production Method 6,
It can be obtained by a synthesis method according to Production method 7, Production method 10, Production method 11, or Production method 12. When Y ₁ is a halogen atom among the compounds represented by the general formula [X], the corresponding compound is used. It can also be synthesized by halogenating a compound in which Y ₁ is a hydrogen atom.

<Production Method 15> Synthesis of Production Intermediate Represented by General Formula [XIII]

[0181]

Embedded image

(In the formula, R ₃ represents a hydrogen atom or an alkyl group, and A _{2 to} A ₁₁ , R ₁ , X ₁ and L ₆ have the same meanings as described above.) That is, a compound represented by the general formula [XXXIX] 1 mol of the pyridine compound is added to a solvent (same as described in Production Method 13) in 0.5.
In 10 to 10 l of peracid (eg, m-chloroperbenzoic acid, peroxysulfuric acid, etc.) can be oxidized with 1 to 3 moles to give N-oxide [XL], and then acid halides (acetyl chloride, oxychloride, etc.). Examples thereof include phosphorus chloride.)
The resulting product is further hydrolyzed under alkaline conditions or acidic conditions to obtain the target synthetic intermediate represented by the general formula [XIII-1].

The formula [X] is used per mole of urea [XLI].
XVII-3] or a compound represented by the general formula [XXVI]
0.5 to 5 times the molar amount of the compound represented by I-4] in a solvent (the same as described in Production Method 1) in 0.5 to 10 L.
By reacting in the presence of a base (same as described in Production method 1) in an amount of 0.5 to 5 moles, a compound represented by the general formula [XIII]
-2] can be obtained.

The compound represented by the general formula [XXXII-1] or the compound 1-5 represented by the general formula [XXXII-2] is added to 1 mol of the compound represented by the general formula [XLII].
The molar amount of the solvent was changed to 0.
Base in 5 to 10 l (same as described in Production Method 1)
By reacting in the presence of 1 to 5 moles, the desired synthetic intermediate represented by the general formula [XIII-3] can be obtained.

The compound represented by the formula [XLIV] is used in an amount of 0.5 to 5 moles per 1 mole of the hydrazine hydrate [XLIII], and the solvent is 0.5 (the same as described in the production method 1).
By reacting in the following general formula [XIII
-4] can be obtained.

The compound represented by the general formula [XXVII-1] or the compound represented by the general formula [XXVII-2] is used in an amount of 0.5 to 1 mol per 1 mol of the hydrazine hydrate [XLIII].
Five-fold moles of the solvent were used (the same as described in Production Method 1).
The desired synthesis represented by the general formula [XIII-5] is performed by reacting in 0.5 to 10 l in the presence of 0.5 to 5 moles of a base (same as described in Production method 1). An intermediate can be obtained.

Further, the compound represented by the general formula [XXVIII] or its mineral acid salt or the compound represented by the general formula [XXIX] is 0.5 to 5 moles per 1 mol of the hydrazine hydrate [XLIII]. By reacting in 0.5 to 10 l of a solvent (same as described in Production method 1) in the presence of 1 to 5 times mol of a base (same as described in Production method 1), The desired synthetic intermediate represented by [XIII-6] can be obtained.

The reaction is carried out at any reaction temperature from -70 ° C to the reflux temperature in the reaction system, and preferably in the temperature range of -20 ° C to 100 ° C. It ends in ~ 20 hours.

<Production Method 16> Synthesis of Production Intermediate Represented by General Formula [XXI]

[0190]

Embedded image

(In the formula, L ₃ , L ₆ , A ₁₀ , B _{0 to} B ₃ , R and n have the same meanings as described above.) That is, 1 mol of a phenylhydrazine derivative represented by the general formula [XLV] Is represented by the general formula [XLVI] in the presence of 1 to 5 moles of a base (same as described in Preparation method 1) in 0.5 to 10 l of a solvent (same as described in Preparation method 1).
After acylating the compound represented by the formula 1 to 5 times by mol to obtain a compound represented by the general formula [XLVII], a halogenating agent (for example, phosphorus trichloride, phosphorus tribromide, thionyl chloride, phosphorus oxychloride, Phosphorus pentachloride, triphenylphosphine /
Examples thereof include carbon tetrachloride and triphenylphosphine / carbon tetrabromide. ) By treating with 1 to 5 times mol
The target compound represented by the general formula [XXI] can be obtained.

Alternatively, 1 mol of the phenylhydrazine derivative represented by the general formula [XLV] is mixed with 0.5 to 10 l of an acid catalyst (for example, p-
Examples thereof include sulfonic acids such as toluenesulfonic acid and Lewis acids such as titanium tetrachloride. ) In the presence or absence of
After reacting with an aldehyde derivative represented by the general formula [XLVIII] or a compound in which a lower alcohol is added to an aldehyde (aldehyde hemiacetal) in an amount of 1 to 5 times, to obtain a phenylhydrazone derivative represented by the general formula [XLIX], Halogenating agent (for example, chlorine, N-chlorosuccinimide, N-bromosuccinimide or hypochlorous acid)
Tert-butyl and the like can be exemplified. ) The target compound represented by the general formula [XXI] can be obtained by treating with 1 to 5 moles.

The reaction is carried out at any reaction temperature from -70 ° C to the reflux temperature in the reaction system, preferably in the temperature range of -20 ° C to 150 ° C. It ends in ~ 20 hours.

[0194]

The production method, formulation method and use of the compound of the present invention will be specifically described below with reference to examples. The method for producing the synthetic intermediate of the compound of the present invention is also described.

Example 1 (1) Production of 2- (2-propenylthio) -4- (4-trifluoromethylphenyl) benzonitrile (Compound No. 1-42 of the present invention) 2-mercapto-4- ( 1.0 g (3.6 mmol) of 4-trifluoromethylphenyl) benzonitrile, 0.45 g (4.0 mmol) of potassium tert-butoxide and 0.5 g (4.1 mmol) of propenyl bromide were added to N, 20 ml of N-dimethylformamide,
Stirred at room temperature for 1 hour. The reaction mixture was poured into 200 ml of water and extracted twice with 50 ml of ethyl acetate. The ethyl acetate layer was washed twice with 50 ml of water, and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 2- (2-propenylthio) as yellow crystals (melting point: 89 to 90 ° C).
0.5 g of 4- (4-trifluoromethylphenyl) benzonitrile was obtained (yield: 43.0%). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 3.73 (2H, d) 5.16 (1H, d) 5.20 (1H, d) 5.90 (1H, m) 7.48 (1H, d) 7.50-7.76 (value) 6H, m)

(2) 2-cyclobutylmethylthio-4-
Production of (3-trifluoromethylpyrazolyl) benzonitrile (Compound No. V-33 of the present invention) 2-mercapto-4- (3-trifluoromethylpyrazolyl) benzonitrile 0.9 g (3.3 mmol), cyclobutylmethyl 0.5 g (3.3 mmol) of bromide and 0.55 g (4.0 mmol) of potassium carbonate were added to 5 ml of N, N-dimethylformamide, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into 50 ml of water, and the organic matter was extracted twice with 20 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 30 ml of water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 2-cyclobutylmethylthio-4- (3-trifluoromethylpyrazolyl) as a pale yellow powder (melting point: 102 to 103 ° C). 0.24 g of benzonitrile (21.2% yield)
I got ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.84 to 2.00 (4H, m) 2.10 to 2.24 (2H, m) 2.57 to 2.67 (1H, m) 3.18 (2H, d) 6.79 ( 1H, d) 7.53 (1H, dd) 7.71 (1H, d) 7.79 (1H, d) 8.02 (1H, dd)

Example 2 (1) Production of [5- (2,6-dichloro-4-trifluoromethylphenyl) -2-methylphenyl] isopropylsulfide (Compound No. I-55 of the present invention) 1,1 '-Thiodi- [5- (2,6-dichloro-4-trifluoromethylphenyl) -2-methylbenzene]
3.3 g (4.9 mmol), Rongalite 3.0 g
(19.5 mmol) and 3.0 g of isopropyl iodide
(17.6 mmol) was added to 30 ml of N, N-dimethylformamide and stirred at room temperature for 3 hours. The reaction mixture was poured into 300 ml of water and extracted twice with 50 ml of ethyl acetate. The ethyl acetate layer was washed twice with 50 ml of water, and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain yellow candy (n _D ²⁰ 1.5462) [5- (2,6-dichloro-4-trifluoromethylphenyl)]. Thus, 1.4 g (yield: 38.0%) of [-2-methylphenyl] isopropyl sulfide was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.33 (6H, d) 2.46 (3H, s) 3.35-3.44 (1H, m) 6.98-7.02 (1H, dd) 7.20 (1H, d) 7.31 (1H, d) 7.67 (2H, s)

(2) [2-ethoxymethoxy-5- (4
-Trifluoromethylphenyl) phenyl] 2,2,2
-Trifluoroethyl sulfide (Compound No. I of the present invention)
Production of 1,1′-thiodi- [2-ethoxymethoxy-5- (4
-Trifluoromethylphenyl) benzene] 3.3 g
(5.0 mmol), Rongalite 3.0 g (19.5)
Mmol), 3.0 g (21.7 mmol) of potassium carbonate and 2,2,2-trifluoroethyl iodide 3.2
g (17.6 mmol) was added to 50 ml of N, N-dimethylformamide and stirred at room temperature for 3 hours. The reaction mixture was poured into 300 ml of water and extracted twice with 50 ml of ethyl acetate. The ethyl acetate layer was washed twice with 50 ml of water, and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain [2-ethoxymethoxy-5- (4-trifluoromethylphenyl)] as a pale yellow viscous liquid (n _D ²⁰ 1.5213). Phenyl] 2,2,2-trifluoroethyl sulfide (3.1 g, yield 75.6%) was obtained.

(3) Preparation of 2- (2,2,2-trifluoroethylthio) -4- (3-trifluoromethylpyrazolyl) benzonitrile (Compound No. V-27 of the present invention) -[2-cyano-5- (3-trifluoromethylpyrazolyl) benzene] 2.7 g (5.0 mmol), Rongalite 3.0 g (19.5 mmol), potassium carbonate 3.0 g (21.7 mmol) And 6.1 g of 2,2,2-trifluoroethyl iodide (2
9.0 mmol) with N, N-dimethylformamide 50
Then, the mixture was stirred at room temperature for 3 hours. Reaction mixture
The mixture was poured into 00 ml of water and extracted twice with 50 ml of ethyl acetate. The ethyl acetate layer was washed twice with 50 ml of water, and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 2- (2,2,2) as a brown solid (melting point 65-67 ° C).
2.5 g of 2-trifluoroethylthio) -4- (3-trifluoromethylpyrazolyl) benzonitrile (yield 7
1.4%).

(4) [2-chloro-4-fluoro-5-
(3-trifluoromethyltriazolyl) phenyl]
Production of 2,2,2-trifluoroethyl sulfide (Compound No. VI-291 of the present invention) 1,1′-thiodi- [2-chloro-4-fluoro-5-
(3-trifluoromethyltriazolyl) benzene]
1.8 g (3.0 mmol), Rongalit 2.0 g
(13.0 mmol), 2.0 g of potassium carbonate (14.
5 mmol) and 3.2 g (17.6 mmol) of 2,2,2-trifluoroethyl iodide were reacted in the same manner as in Example 2, (3) to give white crystals (melting point 56 to 58 ° C) [ 2-chloro-4-fluoro-5 (3-trifluoromethyltriazolyl) phenyl] 1,2,2,2-trifluoroethyl sulfide (1.1 g, yield 47.8%) was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 3.30 (2H, q) 7.76 (1Hdd) 7.50 (1H, d) 8.18 (1H, d) 8.72 (1H, s)

Example 3 Production of [3- (2,6-dichloro-4-trifluoromethylphenyl) phenyl] isopropyl sulfide (Compound No. I-73 of the present invention) 1.0 g of 3-iodophenylisopropyl sulfide
(3.6 mmol) was added to 10 ml of dry benzene, and 2.8 ml of an n-butyllithium hexane solution (1.56 mol / l) was added dropwise while stirring at room temperature under a nitrogen stream. After further stirring at room temperature for 2 hours, the mixture was cooled to 10 ° C., and 1.0 g (4.3 mmol) of 3,5-dichloro-4-fluorobenzotrifluoride in diethyl ether 5
0 ml solution was added dropwise. After stirring at room temperature for further 12 hours, the reaction mixture was poured into 100 ml of water and separated. The organic layer was washed twice with 50 ml of water and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a colorless liquid (n
_D ²⁰ 1.5675) [3- (2,6-dichloro-4-
0.5 g (yield 38.0%) of trifluoromethylphenyl) phenyl] isopropylsulfide was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.32 (6H, d) 3.33 to 3.48 (1H, m) 7.11 to 7.12 (1H, m) 7.26 to 7.27 (1H, d) 7.40 to 7.49 (2H, m) 7.67 (2H, s)

Example 4 [3- (4-trifluoromethylphenyl) phenyl]
Cyclopentyl sulfide (Compound No. I-6 of the present invention)
Preparation of 7) 1.0 g of 4-trifluoromethylphenylboronic acid
(5.2 mmol), 1.4 g (5.4 mmol) of 3-bromophenylcyclopentyl sulfide, 1.6 g (15.0 mmol) of sodium carbonate and 0.8 g (0.7 mmol) of palladium tetrakis (triphenylphosphine) ) Was added to a mixed solvent of 50 ml of toluene, 25 ml of ethanol and 25 ml of water, and the mixture was stirred under heating and reflux for 2 hours. The reaction mixture was poured into ice water and extracted with toluene. After the toluene layer was washed twice with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a colorless liquid (n
_D ²⁰ 1.5732) [3- (4-Trifluoromethylphenyl) phenyl] cyclopentyl sulfide 1.3
g (78.0% yield). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.54 to 1.75 (4H, m) 1.76 to 1.85 (2H, m) 2.03 to 2.14 (2H, m) 3.61 to 3.87 (1H, m) 7.38 to 7.96 (8H, m)

Example 5 Preparation of [5- (4-trifluoromethylphenyl) -2-ethoxymethoxyphenyl] propyl sulfide (Compound No. I-212 of the present invention) 4- (4-trifluoromethylphenyl) phenyl 3.0 g (10.1 mmol) of ethoxymethyl ether was dissolved in 30 ml of diethyl ether, and stirred at −20 ° C. while n-butyllithium hexane solution (1.56 m
ol / l) 7.8 ml was added dropwise. After further stirring at room temperature for 2 hours, the mixture was cooled to 0 ° C., and 1.8 g (12.0 mmol) of dipropyl disulfide was added dropwise. After further stirring at room temperature for 2 hours, the reaction mixture was poured into ice water, the ether layer was washed twice with water, and then dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography, a yellow viscous liquid (n _D ²⁰
1.5491) [5- (4-trifluoromethylphenyl) -2-ethoxymethoxyphenyl] propyl sulfide (2.6 g, yield 69.5%).

Example 6 2-propylthio-4- (3-trifluoromethyl-1
Preparation of (H-triazolyl) benzonitrile (Compound No. VI-1 of the present invention) 3-trifluoromethyl-1H-triazole 1.06
g (7.7 mmol), 1.38 g (6.5 mmol) of 4-chloro-2-n-propylthiobenzonitrile, and 1.07 g (7.7 mmol) of potassium carbonate in 10 ml of N, N-dimethylformamide. The mixture was stirred at 150 ° C. for 2 hours. After cooling to room temperature, the reaction mixture was poured into 100 ml of water, and the organic matter was extracted twice with 50 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 50 ml of water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give a milky white powder (melting point: 143 to 144)
0.78 g of 2-propylthio-4- (3-trifluoromethyl-1H-triazolyl) benzonitrile
(38.2% yield). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.84 to 2.00 (4H, m) 1.12 (3H, t) 1.80 (2H, h) 3.11 (2H, t) 7.53 (1Hdd) 7.75 (1H, d) 7.77 (1H, d) 8.69 (1H, s)

Example 7 Production of [4-fluoro-2-methyl-5- (3-trifluoromethylpyrazolyl) phenyl] 2,2,2 trifluoroethyl sulfide (Compound No. V-613 of the present invention) 0.34 g of 3-trifluoromethylpyrazole
(2.49 mmol), 2-fluoro-4-methyl-5
1.34 g (5.0 mmol) of-(2,2,2 trifluoroethylthio) benzeneboronic acid, 0.39 g of pyridine
(4.98 mmol), 0.68 g of copper (II) acetate
(3.74 mmol), 4 mol molecular sieve 0.
1 g was added to methylene chloride (20 ml) and stirred at room temperature for 2 days. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to give a pale yellow liquid (n _D ²⁰ 1.49).
98) of [4-fluoro-2-methyl-5- (3-trifluoromethylpyrazolyl) phenyl] 2,2,2 trifluoroethyl sulfide 0.09 g (yield 10.0%)
I got ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 2.52 (3H, s) 3.43 (2H, q) 6.74 (1H, d) 7.15 (1H, d) 7.99 (1H, bs) 8.05 (1H, d)

Example 8 (1) Production of 4- (2,4-dichlorophenyl) -2-ethylthiobenzonitrile (Compound No. I-62 of the present invention) 0.12 g of 60% sodium hydride (3.0) Mmol)
Was added to 30 ml of N, N-dimethylformamide, and 0.2 g (3.2 mmol) of ethanethiol was added dropwise with stirring at room temperature. After the generation of hydrogen was completed, 0.7 g (2.6 mmol) of 2-fluoro-4- (2,4-dichlorophenyl) benzonitrile was added, and the mixture was heated at 60 ° C for 6 hours.
Stirred for hours. The reaction mixture was poured into about 100 ml of ice water and extracted twice with 50 ml of ethyl acetate. The ethyl acetate layer was washed twice with 50 ml of water, and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography. (Yield 8
8.0%). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
(Value) 1.38 (3H, t) 3.07 (2H, q) 7.25 to 7.42 (3H, m) 7.49 (1H, dd) 7.52 (1H, dd) 7.76 ( 1H, d)

(2) Production of [5- (2,6-dichloro-4-trifluoromethylphenyl) -2-nitrophenyl] isopropylsulfide (Compound No. I-56 of the present invention) 0.33 g of 60% sodium hydride (8.3 mmol)
Was added to 50 ml of N, N-dimethylformamide, and while stirring at room temperature, 0.7 g of isopropyl mercaptan was added.
(9.2 mmol) was added dropwise. After completion of hydrogen generation, 3.0 g of 1-chloro-5- (2,6-dichloro-4-trifluoromethylphenyl) -2-nitrobenzene.
(8.1 mmol) and stirred at room temperature for 12 hours. The reaction mixture was poured into about 200 ml of ice water and extracted twice with 50 ml of ethyl acetate. The ethyl acetate was washed twice with 100 ml of water and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain yellow candy (n _D
²⁰ 1.5881) [5- (2,6-dichloro-4-trifluoromethylphenyl) -2-nitrophenyl] isopropyl sulfide (3.0 g, yield 90.0%). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.40 (6H, d) 3.50 to 3.59 (1H, m) 7.12 to 7.13 (1H, dd) 7.31 (1H, d) 7.67 (2H, s) 8.25 (1H, d)

(3) [4-Fluoro-2-nitro-5-
Preparation of (4-trifluoromethylphenyl) phenyl] propyl sulfide (Compound No. I-221 of the present invention) 1.4 g (12.5 mmol) of potassium tert-butoxide was added to 100 ml of tetrahydrofuran, and n-propanethiol was added at room temperature. 0.9 g (11.8 mmol) was added dropwise, and the mixture was stirred at the same temperature for 10 minutes. 4- (4
-Trifluoromethylphenyl) -2,5-difluoronitrobenzene 3.5 g (11.6 mmol) were added,
Stirred at room temperature for another 2 hours. Tetrahydrofuran was distilled off under reduced pressure, 200 ml of ice water was added, and the organic matter was extracted twice with 50 ml of ethyl acetate. Combine the ethyl acetate layers and add 1
After washing twice with 00 ml of water, it was dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography.
3.8 g (yield 90%) of (4-trifluoromethylphenyl) phenyl] propyl sulfide was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.11 (3H, t) 1.81 (2H, m) 2.97 (2H, t) 7.42 (1H, d) 7.56 (2H, d) 7.81 (2H, d) 8.08 (1H, d)

(4) 2-cyclopropylmethylthio-4
Production of-(5-trifluoromethylpyridin-2-yl) benzonitrile (Compound No. II-5 of the present invention) 4- (5-trifluoromethylpyridin-2-yl)-
1.8 g (6.8 mmol) of 2-fluorobenzonitrile, 1.6 g (7.6 mmol) of S-cyclopropylmethylisothiourea hydrobromide and 50 ml of N, N-dimethylformamide were placed in a round bottom flask. And 1.6 g (8 mmol) of a 20% aqueous sodium hydroxide solution, and the mixture was stirred overnight. The solvent was distilled off under reduced pressure.
0 ml was added and the layers were separated. The organic layer was washed twice with 50 ml of water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain pale yellow feather-like crystals (melting point: 135 to 136).
C), 2.2 g (96% yield) of 2-cyclopropylmethylthio-4- (5-trifluoromethylpyridin-2-yl) benzonitrile. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 0.29 to 0.35 (2H, m) 0.61 to 0.68 (2H, m) 1.07 to 1.20 (1H, m) 3.07 (2H, d) 7.75 ( 1H, d) 7.85 to 7.90 (2H, m) 8.05 (1H, dd) 8.19 (1H, d) 8.99 (1H, dd)

(5) 4- (6-oxo-4-trifluoromethyl-1,6-dihydropyrimidin-1-yl)-
2-propylthiobenzonitrile (Compound No. II of the present invention)
Production of I-9) 4- (6-oxo-4-trifluoromethyl-1,6-
1.1 g (3.9 mmol) of dihydropyrimidin-1-yl) -2-fluorobenzonitrile was dissolved in 50 ml of dimethyl sulfoxide, and 1.0 g of potassium carbonate (7.
2 mmol) and 0.3 g (3.9 mmol) of propanethiol were added and reacted at 100 ° C. for 2 hours. The solvent was distilled off under reduced pressure, 50 ml of water and 50 ml of ethyl acetate were added, and the layers were separated. The organic layer was washed twice with 50 ml of water, dried over anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a white powder (melting point: 157 to 158 ° C). 4-
0.7 g (54% yield) of (6-oxo-4-trifluoromethyl-1,6-dihydropyrimidin-1-yl) -2-propylthiobenzonitrile was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.09 (3H, t) 1.77 (2H, m) 3.03 (2H, t) 6.96 (1H, s) 7.22 (1H, dd) 7.35 (1H, d) 7.79 (1H, d) 8.25 (1H, s)

(6) 4- (5-chlorothiophen-2-
Preparation of yl) -2-cyclopropylmethylthiobenzonitrile (Compound No. IV-5 of the present invention) Similarly to (4) of Example 8, 4- (5-chlorothiophen-2-yl) -2-fluorobenzo Nitrile 0.
9 g (4.0 mmol) was reacted with 0.9 g (4.3 mmol) of S-cyclopropylmethylisothiourea hydrobromide, and the obtained crude product was purified by silica gel column chromatography to give a yellow feather Crystals (melting point 123-1)
24 [deg.] C) 4- (5-chlorothiophen-2-yl)-
1.1 g of 2-cyclopropylmethylthiobenzonitrile
(91% yield). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 0.28 to 0.33 (2H, m) 0.61 to 0.67 (2H, m) 1.07 to 1.15 (1H, m) 3.00 (2H, d) 6.95 ( 1H, d) 7.19 (1H, d) 7.36 (1H, dd) 7.54 (1H, d) 7.60 (1H, dd)

(7) Preparation of [2-nitro-5- (3-trifluoromethylpyrazolyl) phenyl] propyl sulfide (Compound No. V-166 of the present invention) 1- (3-chloro-4-nitrophenyl) -3 0.8 g (2.7 mmol) of trifluoromethylpyrazole,
0.25 g (3.3 mmol) of 1-propanethiol,
0.57 g (4.1 mmol) of potassium carbonate was added to N, N-
The mixture was added to 5 ml of dimethylformamide and stirred at room temperature for 2 hours. The reaction mixture was poured into 50 ml of water, and the organic matter was extracted twice with 20 ml of ethyl acetate. Combine the ethyl acetate layers,
After washing twice with 30 ml of water, it was dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain [2-nitro-5] as an amber viscous liquid (n _D ²⁰ 1.5741).
0.31 g (yield 34.4%) of-(3-trifluoromethylpyrazolyl) phenyl] propyl sulfide was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.08 (3H, t) 1.75 (2H, h) 3.02 (2H, t) 6.74 (1H, d) 7.37 to 7.40 (2H, m) 7.72 ( 1Hdd) 7.97 (1H, d)

(8) Production of 2- (2,2,2-trifluoroethylthio) -4- (4-trifluoromethylpyrazolyl) benzonitrile (Compound No. V-639 of the present invention) 2-chloro-4- 0.64 g (2.4 mmol) of (4-trifluoromethylpyrazolyl) benzonitrile,
0.33 g of 2,2,2-trifluoroethanethiol
(2.9 mmol), 0.40 g of potassium carbonate (2.9
(Mmol) was added to 5 ml of N, N-dimethylformamide and stirred at room temperature overnight. The reaction mixture was poured into 50 ml of water, and the organic matter was extracted twice with 20 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 30 ml of water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain a milky white powder (melting point: 90 to 91 ° C.).
(2,2,2-trifluoroethylthio) -4- (4-
Trifluoromethylpyrazolyl) benzonitrile 0.4
8 g (57.1% yield) was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 3.67 (2H, q) 7.76 (1Hdd) 7.83 (1H, d) 7.79 (1H, s) 8.08 (1H, d) 8.28 (1H, s)

(9) Production of 4- (4-methyl-3-trifluoromethylpyrazolyl) -2-propylthiobenzaldehyde (Compound No. V-381 of the present invention) 2-chloro-4- (4-methyl-3-) 5.77 g (trifluoromethylpyrazolyl) benzaldehyde (20.0 g)
Mmol), 1.83 g of 1-propanethiol (23.
9 mmol) and 3.31 g (24.0 mmol) of potassium carbonate were added to 20 ml of N, N-dimethylformamide, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into 200 ml of water, and the organic matter was extracted twice with 100 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 100 ml of water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give a yellow liquid (n _D ²⁰ 1.572).
6) 4- (4-methyl-3-trifluoromethylpyrazolyl) -2-propylthiobenzaldehyde 3.07
g (46.8% yield). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.11 (3H, t) 1.79 (2H, h) 2.26 (3H, s) 3.03 (2H, t) 7.51 (1H, dd) 7.79 (1H, d) 7.83 (1H, s) 7.92 (1H, d) 10.35 (1H, s)

(10) Preparation of methyl 2-propylthio-4- (3-trifluoromethylpyrazolyl) benzoate (Compound No. V-175 of the present invention) 2-chloro-4- (3-trifluoromethylpyrazolyl) benzoic acid 1.52 g (5.0 mmol) of methyl, 1
-0.66 g (8.6 mmol) of propanethiol and 0.83 g (6.0 mmol) of potassium carbonate were added to 5 ml of N, N-dimethylformamide, and the mixture was stirred at 60 ° C for 24 hours. The reaction mixture was poured into 50 ml of water, and the organic matter was extracted twice with 20 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 30 ml of water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was purified by thin-layer chromatography to obtain 2-propylthio-4- (3- (3-methylthiophene) as a white powder (melting point: 114 to 116 ° C).
Trifluoromethylpyrazolyl) methyl benzoate 0.3
1 g (18.0% yield) was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.14 (3H, t) 1.83 (2H, h) 3.00 (2H, t) 3.94 (3H, s) 6.77 (1H, d) 7.40 (1H, dd) 7.73 (1H, d) 8.01 (1H, bs) 8.10 (1H, d)

Example 9 Production of [3- (2,4-dichlorophenyl) phenyl] isopropylsulfide (Compound No. I-71 of the present invention) 3- (2,4-dichlorophenyl) aniline 0.9 g
(3.8 mmol) and 0.6 g (4.0 mmol) of diisopropyl disulfide in 20 ml of acetonitrile
And tert-butyl nitrite 0.4 g at 60 ° C.
(4.0 mmol) was added dropwise. After stirring at the same temperature for 1 hour, low-boiling substances were distilled off under reduced pressure, and water and ethyl acetate were added to carry out liquid separation. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain [3- (2,4) as a colorless liquid (n _D ²⁰ 1.6143).
[Dichlorophenyl) phenyl] isopropyl sulfide (0.25 g, yield 31.0%) was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.35 (6H, d) 3.35 to 3.49 (1H, m) 7.19 to 7.52 (7H, m)

Example 10 Production of [2-methyl-5- (3-trifluoromethylpyrazolyl) phenyl] propyl sulfide (Compound No. V-176 of the present invention) N ′-(4-methyl-3-n- Propylthiophenyl)
1.0 g of trifluoroacetohydrazideyl chloride
(3.2 mmol) in N, N-dimethylformamide 5
and stirred at 0 ° C. Next, 0.72 g (7.1 mmol) of triethylamine and 1.
7 g (15.9 mmol) were added, and the mixture was added at 0 ° C to room temperature for 2 hours.
Stir for 4 hours. The reaction mixture was poured into 50 ml of water, and the organic matter was extracted twice with 20 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 30 ml of water, and dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure, the resulting residue was purified by silica gel column chromatography, a colorless liquid (n _D ²⁰ not measurable) [2-methyl-5
0.22 g (yield 22.7%) of-(3-trifluoromethylpyrazolyl) phenyl] propyl sulfide was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.08 (3H, t) 1.75 (2H, h) 2.38 (3H, s) 2.97 (2H, t) 6.71 (1H, d) 7.23 (1H, d) 7.32 (1H, dd) 7.57 (1H, d) 7.89 (1H, bs)

Example 11 2-propylthio-4- (5-trifluoromethylpyrazolyl) benzonitrile (Compound No. V-15 of the present invention)
Preparation of 3) 1.7 g (10.1 mmol) of 4-ethoxy-1,1,1-trifluoro-3-buten-2-one and 2.1 g of 4-hydrazino-2-propylthiobenzonitrile (1
(0.1 mmol) was added to 50 ml of ethanol, and the mixture was stirred under reflux for 2 hours. After distilling off ethanol under reduced pressure, acetic acid (60 ml) was added, and the mixture was further stirred for 6 hours while heating under reflux. After distilling off acetic acid under reduced pressure, ethyl acetate and water were added to carry out liquid separation, and the organic layer was washed twice with water. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to give a yellow-brown viscous liquid (n _D ²⁰ 1.
5562) of 2-propylthio-4- (5-trifluoromethylpyrazolyl) benzonitrile (1.2 g, yield 3)
8.7%). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.08 (3H, t) 1.70 to 1.82 (2H, m) 3.03 (2H, t) 6.90 (1H, d) 7.39 (1H, dd) 7.52 ( 1H, d) 7.72 (1H, d) 7.78 (1H, d)

Example 12 (1) [3- (2,4-dichlorophenyl) phenyl]
Isopropyl sulfoxide (Compound No. I-7 of the present invention)
Preparation of 2) 1.0 g (3.4 mmol) of [3- (2,4-dichlorophenyl) phenyl] isopropyl sulfide was dissolved in 50 ml of chloroform, and m-
0.7 g (4.1 mmol) of chloroperbenzoic acid was added and stirred for 2 hours. After stirring at room temperature for another 12 hours,
A 5% aqueous solution of sodium bicarbonate was added to carry out liquid separation. The chloroform layer was washed with a 5% aqueous sodium sulfite solution and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.9 g of [3- (2,4-dichlorophenyl) phenyl] isopropylsulfoxide as a colorless candy (n _D ²⁰ 1.6169).
(85.0% yield). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.22 (6H, dd) 2.79 to 2.96 (1H, m) 7.26 to 7.65 (7H, m)

(2) [2-Difluoromethyl-5- (3
-Trifluoromethylpyrazolyl) phenyl] 2,2
Production of 2-trifluoroethyl sulfoxide (Compound No. V-324 of the present invention) [2-Difluoromethyl-5- (3-trifluoromethylpyrazolyl) phenyl] 2,2,2-trifluoroethyl sulfide (Compound No. of the present invention) V-295) 0.3
7 g (1.0 mmol) was added to 5 ml of chloroform,
With stirring at 0 ° C, m-chloroperbenzoic acid 0.25
g (1.5 mmol) was added and stirred at 0 ° C. for 1 hour. 10 ml of 10% aqueous sodium sulfite solution
After stirring at room temperature for 10 minutes, 20 ml of chloroform was further added. The chloroform layer was washed three times with 20 ml of a saturated aqueous solution of sodium hydrogen carbonate and dried over anhydrous magnesium sulfate. Chloroform is distilled off under reduced pressure,
Yellow syrupy substance (n _D ²⁰ 1.4909) of [2-difluoromethyl-5- (3-trifluoromethyl-pyrazolyl) phenyl] 2,2,2-trifluoroethyl sulfoxide 0.38 g (yield: 97.4 %). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
3.48-3.67 (2H, m) 6.82 (1H, d) 6.96 (1H, t) 7.81 (1H, dd) 8.15 (1H, d) 8.16 (value) 1H, d) 8.51 (1H, d)

(3) [2-Methyl-5- (3-trifur
Oromethylpyrazolyl) phenyl] 2,2,2-trif
Fluoroethyl sulfoxide (Compound No. V-32 of the present invention)
Production of 1) [2-methyl-5- (3-trifluoromethylpyrazoli
Ru) phenyl] 2,2,2-trifluoroethylsulfur
(Compound No. V-292 of the present invention) 1.68 g (4.
9 mmol) in 10 ml of chloroform and at 0 ° C.
While stirring, 1.02 g of m-chloroperbenzoic acid (5.
1 mmol) and stirred at 0 ° C. for 1 hour. Reaction
Add 10 ml of a 10% aqueous sodium sulfite solution to the solution, and add
After stirring at room temperature for 10 minutes, further chloroform 20 ml
Was added. Chloroform layer is saturated aqueous sodium bicarbonate
After washing three times with 20 ml of the solution, anhydrous magnesium sulfate
And dried. Chloroform is distilled off under reduced pressure to give a pale yellow solid.
(Melting point 109-110 ° C) [2-methyl-5- (3-
Trifluoromethylpyrazolyl) phenyl] 2,2,2
-Trifluoroethylsulfoxide 0.65 g (yield 3
7.1%). ¹ H-NMR data (300 MHz, CDCl_ThreeSolvent, δ
Value) 2.44 (3H, s) 3.46 to 3.50 (2H, m) 6.76 (1H, d) 7.41 (1H, d) 7.94 (1H, dd) 8.07 ( 1H, d) 8.25 (1H, d)

Example 13 Production of 4- (2,6-dichloro-4-trifluoromethylphenyl) -2-isopropylthioaniline (Compound No. I-57 of the present invention) 3.5 g (63.6) of iron powder Mmol), water (10 ml) and acetic acid (1 ml) were added to toluene (20 ml), and the mixture was stirred at 60 ° C. for 30 minutes, and then [5- (2,6-dichloro-4-trifluoromethylphenyl) -2-nitrophenyl] isopropylsulfide ( A solution of 3.0 g (7.3 mmol) of the compound prepared in (2) of Example 8 in 10 ml of toluene was added dropwise. After further reacting for 3 hours under heating reflux,
The reaction mixture was cooled to room temperature. The insoluble material was separated by filtration, water and toluene were added to the filtrate, and the mixture was separated. The toluene layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain pale yellow candy (n _D ²⁰ 1.5782).
1.0 g of-(2,6-dichloro-4-trifluoromethylphenyl) -2-isopropylthioaniline (yield 3
6.0%). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.27 (6H, d) 3.20 to 3.34 (1H, m) 6.82 (1H, d) 7.00 to 7.04 (1H, dd) 7.27 (1H, d) 7.67 (2H, s)

Example 14 Production of [5- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromophenyl] isopropyl sulfide (Compound No. I-58 of the present invention) 5- (2,6) 0.7 g (1.8 mmol) of -dichloro-4-trifluoromethylphenyl) -2-isopropylthioaniline (the compound prepared in Example 9) and 0.5 g (3.5 mmol) of copper bromide in 20 ml of acetonitrile
And 0.2 g of tert-butyl nitrite at 60 ° C.
(2.0 mmol) was added dropwise. After stirring at the same temperature for 1 hour, low-boiling substances were distilled off under reduced pressure, and water and ethyl acetate were added to carry out liquid separation. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, a colorless liquid ^{_{(n D 20 1.5642) [5-}} (2,6
-Dichloro-4-trifluoromethylphenyl) -2-
Bromophenyl] isopropyl sulfide 0.25g
(31.0% yield). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.37 (6H, d) 3.49 (1H, q) 6.93 (1H, dd) 7.18 (1H, d) 7.68 (2H, s) 7.69 (1H, d)

Example 15 Production of [2-methyl-5- (3-trifluoromethylpyrazolyl) phenyl] propyl sulfide (Compound No. V-176 of the present invention) 0.98 g of 2-propylthio-4- (3-trifluoromethylpyrazolyl) benzaldehyde (Compound No. V-159 of the present invention) obtained
(3.1 mmol) in 10 ml of methylene chloride,
1.44 g (12.4 mmol) of triethylsilane and 0.63 ml of boron trifluoride diethyl ether complex
(6.8 mmol) and stirred at room temperature for 22 hours.
The reaction mixture was poured into 50 ml of ice water, and methylene chloride 20
ml was added. The methylene chloride layer was separated, washed twice with 30 ml of water, and dried over anhydrous magnesium sulfate. The methylene chloride was distilled off under reduced pressure, the resulting residue was purified by silica gel column chromatography, a colorless liquid (n _D ²⁰
[Measurable]) [2-methyl-5- (3-trifluoromethylpyrazolyl) phenyl] propyl sulfide 0.1
8 g (19.3% yield) was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 1.08 (3H, t) 1.75 (2H, h) 2.38 (3H, s) 2.97 (2H, t) 6.71 (1H, d) 7.23 (1H, d) 7.32 (1H, dd) 7.57 (1H, d) 7.89 (1H, bs)

Example 16 Preparation of [2-difluoromethyl-5- (3-trifluoromethylpyrazolyl) phenyl] 2,2,2-trifluoroethyl sulfide (Compound No. V-295 of the present invention) Example 8 2- (2,2,2) obtained in the same manner as (9)
1.0 g (2.8 mmol) of 2-trifluoroethylthio) -4- (3-trifluoromethylpyrazolyl) benzaldehyde (Compound No. V-275 of the present invention) is dissolved in 5 ml of methylene chloride, and DAST is performed under a nitrogen stream. 0.55 g of (diethylaminosulfur trifluoride) (3.
4 mmol) and stirred at room temperature for 4 hours. further,
DAST (diethylaminosulfur trifluoride)
0.14 g (0.8 mmol) was added, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into 20 ml of ice water, and 20 ml of methylene chloride was added. Separate the methylene chloride layer and add 20 ml
After washing twice with water, the extract was dried over anhydrous magnesium sulfate. The methylene chloride was distilled off under reduced pressure, and a yellow viscous liquid (n _D
²⁰ 1.4951) of [2-difluoromethyl-5- (3
-Trifluoromethylpyrazolyl) phenyl] 2,2
0.75 g of 2-trifluoroethyl sulfide (yield 7
0.8%). ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 3.50 (2H, q) 6.78 (1H, d) 7.16 (1H, t) 7.82 (2H, s) 8.02 (1H, d) 8.07 (1H, s)

Example 17 Production of [2-ethenyl-5- (3-trifluoromethylpyrazolyl) phenyl] 2,2,2-trifluoroethyl sulfide (Compound No. V-278 of the present invention) 2- (2,2,2) obtained in the same manner as (9)
2.83 g (8.0 mmol) of 2-trifluoroethylthio) -4- (3-trifluoromethylpyrazolyl) benzaldehyde (Compound No. V-275 of the present invention), 2.85 g of methyltriphenylphosphonium bromide (8.8 g).
0 mmol) and 1.38 g (10.0 mmol) of potassium carbonate were added to a mixed solvent of 20 ml of dioxane and 0.3 ml of water, and the mixture was refluxed for 5 hours. After cooling to room temperature, insolubles were removed by filtration, and dioxane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography, and [2-ethenyl-5- (3-trifluoromethylpyrazolyl) phenyl] 2,2,2-triol as a pale yellow liquid (n _D ²⁰ 1.5328) was obtained. 1.23 g (yield 43.8%) of fluoroethyl sulfide was obtained. ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 3.41 (2H, q) 5.47 (1H, dd) 5.79 (1H, dd) 6.74 (1H, d) 7.29 (1H, dd) 7.67 (2H, s) 7.91 (1H, s) 8.95 (1H, d)

(Production Example of Intermediate) Reference Example 1 Production of 2-mercapto-4- (4-trifluoromethylphenyl) benzonitrile (Compound II) (a) 2-Methylthio-4- (4-tri Production of fluoromethylphenyl) benzonitrile (compound XVII) 3.0 g (11.3 mmol) of 2-fluoro-4- (4-trifluoromethylphenyl) benzonitrile was added to 50 ml of N, N-dimethylformamide, and the mixture was cooled to room temperature. 7.0 g of a 15% aqueous solution of sodium methyl mercaptan
(15.0 mmol) was added dropwise. After stirring at 60 ° C. for 6 hours, the reaction mixture was poured into about 200 ml of ice water and extracted twice with 100 ml of ethyl acetate. 1 layer of ethyl acetate
After washing twice with 00 ml of water, it was dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 2.5 g of 2-methylthio-4- (4-trifluoromethylphenyl) benzonitrile as white crystals (melting point: 128 to 129 ° C).
(Yield 75.0%).

(B) 2-methylsulfinyl-4- (4
Preparation of -trifluoromethylphenyl) benzonitrile 2.5 g (8.5 mmol) of the methylthio form obtained in (a) was dissolved in 50 ml of chloroform, and m-chloroperbenzoic acid 1 was stirred at 0 ° C while stirring. A solution of 7.7 g (9.9 mmol) in chloroform was added dropwise and stirred for 1 hour. 5%
Aqueous sodium bicarbonate was added and the layers were separated. The chloroform layer was washed with a 5% aqueous sodium sulfite solution and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain yellow-brown crystals (melting point 127).
2.2 g) of 2-methylsulfinyl-4- (4-trifluoromethylphenyl) benzonitrile.
(84.0% yield).

(C) 2-mercapto-4- (4-trifluoromethylphenyl) benzonitrile (compound II)
2-methylsulfinyl-4- (4- (4-) obtained in (b)
2.2 g of trifluoromethylphenyl) benzonitrile
(7.1 mmol) was added to 15 ml of trifluoroacetic anhydride, and the mixture was stirred at room temperature for 12 hours. Then, low-boiling substances were distilled off under reduced pressure, and 50 ml of methanol and 3 g of 20% aqueous potassium hydroxide solution were added to the residue. The reaction was performed for 1 hour. The solvent was distilled off under reduced pressure, 5% aqueous sulfuric acid was added, and the mixture was extracted with ethyl acetate.
After drying the ethyl acetate layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 1.0 g of 2-mercapto-4- (4-trifluoromethylphenyl) benzonitrile was obtained (yield 5).
1.0%). This was used as a raw material of (1) of Example 1.

Reference Example 2 1,1′-thiodi- [5- (2,6-dichloro-4-trifluoromethylphenyl) -2-methylbenzene]
Preparation of (Compound IV) (a) Preparation of 4- (2,6-dichloro-4-trifluoromethylphenyl) toluene (Compound X) 5.7 g (26.1 mmol) of 4-iodotoluene was added to 30 ml of dry benzene. In addition, an n-butyllithium hexane solution (1.60) was stirred under a nitrogen stream at room temperature.
(mol / l) 17.0 ml was added dropwise. After stirring at room temperature for 2 hours, a solution of 6.0 g (25.8 mmol) of 3,5-dichloro-4-fluorobenzotrifluoride in 10 ml of diethyl ether was added dropwise at 10 ° C. After stirring at room temperature for further 12 hours, the reaction mixture was poured into 100 ml of water and separated. The organic layer was washed twice with 50 ml of water and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and 6.7 g of colorless liquid 4- (2,6-dichloro-4-trifluoromethylphenyl) toluene (yield 8)
5.0%).

(B) Production of 5- (2,6-dichloro-4-trifluoromethylphenyl) -2-methylbenzenesulfonyl chloride 6.7 g (22.0 mmol) of (fluoromethylphenyl) toluene was dissolved in 50 ml of chloroform, and 3.8 g (32.6 mmol) of chlorosulfonic acid was added dropwise at 0 ° C. while stirring. After stirring at room temperature for another 3 hours, the reaction mixture was poured into about 200 ml of ice water and separated. The organic layer was washed twice with water and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure to obtain 7.2 g of 5- (2,6-dichloro-4-trifluoromethylphenyl) -2-methylbenzenesulfonyl chloride (yield: 81.0%).

(C) 1,1′-thiodi- [5- (2,6
-Dichloro-4-trifluoromethylphenyl) -2-
Preparation of methylbenzene] (compound IV) 0.7 g (18.4 mmol) of lithium aluminum hydride was added to 30 ml of diethyl ether, and the mixture was added at -10 ° C with 5- (2,6-dichloro-4-trifluoromethylphenyl). -2-methylbenzenesulfonyl chloride 7.2
g (17.8 mmol) in 30 ml of diethyl ether was added dropwise. After stirring at room temperature for 12 hours, the reaction mixture was poured into 100 ml of 1N hydrochloric acid and separated. 50 organic layers
After washing twice with ml of water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a pale yellow candy (n _D
²⁰ 1.6066) of 1,1'-thiodi- [5- (2,6
-Dichloro-4-trifluoromethylphenyl) -2-
Methylbenzene] (4.3 g, yield 75.0%).
This was used as a raw material of (1) of Example 2.

Reference Example 3 Preparation of 2-mercapto-4- (3-trifluoromethylpyrazolyl) benzonitrile (Compound II-1) 2-Chloro-4- (3-trifluoromethylpyrazolyl) benzonitrile 0 g (18.4 mmol)
It was dissolved in 20 ml of N, N-dimethylformamide, and 1.86 g (23.9 mmol) of sodium sulfide was added.
Stirred at 20 ° C. for 30 minutes. After cooling to room temperature, water 100
The mixture was washed with 30 ml of ethyl acetate, the aqueous phase was adjusted to pH 5 to 6 with citric acid, and extracted twice with 50 ml of ethyl acetate. Combine the ethyl acetate layers and add 2
After washing twice, it was dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain 2-mercapto-4 as a pale yellow powder.
-(3-Trifluoromethylpyrazolyl) benzonitrile (97.6% yield) was obtained. This is referred to as (2) of Example 1.
Used as raw material for ¹ H-NMR data (300 MHz, CDCl ₃ solvent, δ
Value) 4.28 (1H, bs) 6.79 (1H, d) 7.56 (1H, dd) 7.71 (1H, d) 7.87 (1H, d) 8.01 (1H, d)

Reference Example 4 1,1′-thiodi- [2-ethoxymethoxy-5- (4
-Trifluoromethylphenyl) benzene] (compound I
Production of V) [4- (4-trifluoromethylphenyl) phenyl]
3.0 g (10.1 mmol) of ethoxymethyl ether
Was dissolved in 30 ml of diethyl ether, and stirred at −20 ° C. with n-butyllithium hexane solution (1.56
(mol / l) 7.8 ml was added dropwise. 2 more at room temperature
After stirring for an hour, the mixture was cooled to 0 ° C and powdered sulfur 0.6 g
(18.8 mmol) was added. After further stirring at room temperature for 2 hours, the reaction mixture was poured into dilute hydrochloric acid, and the ether layer was washed twice with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, 20 ml of dimethylsulfoxide was added to the residue, and the mixture was reacted at 80 ° C. for 12 hours.
Extracted twice with ml. The organic layer was washed twice with water and dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure,
1,1′-thiodi- as a yellow solid (melting point 61-62 ° C.)
1.6 g (yield 48.5%) of [2-ethoxymethoxy-5- (4-trifluoromethylphenyl) benzene] was obtained. This was used as a raw material of Example 2 (2).

Reference Example 5 (1) 1,1′-thiodi- [2-cyano-5- (3-trifluoromethylpyrazolyl) benzene] (compound I
Preparation of V) 3.0 g (11.1 mmol) of 2-mercapto-4- (3-trifluoromethylpyrazolyl) benzonitrile
Was added to 5 ml of dimethyl sulfoxide, and the mixture was stirred at 50 ° C. for 2 hours. After cooling to room temperature, the reaction mixture was poured into 50 ml of water, and the organic matter was extracted twice with 20 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 30 ml of water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 1,1′-thiodi-
1.3 g (yield 42.4%) of [2-cyano-5- (3-trifluoromethylpyrazolyl) benzene] was obtained. This was used as a raw material for (3) of Example 2.

(2) 1,1′-thiodi- [2-chloro-
Preparation of 4-fluoro-5- (3-trifluoromethyltriazolyl) benzene] (compound IV) [2-Chloro-4-fluoro-5 (3-trifluoromethyltriazolyl) phenyl] methyl sulfide 2. 2
g (7.1 mmol) as 2-chloro-4-fluoro-5 (3-trifluoromethyltriazolyl) thiophenol in the same manner as in Reference Example 1, and then in the same manner as in Reference Example 5 (1). Thus, 1.8 g (yield 85.7%) of 1,1′-thiodi- [2-chloro-4-fluoro-5- (3-trifluoromethyltriazolyl) benzene] was obtained. This was used as a raw material for (4) of Example 2.

Reference Example 6 Production of 4-methyl-3-trifluoromethylpyrazole (Compound XIII) 4-ethoxy-3-methyl-1,1,1-trifluoro-3-buten-2-one 7 g (10.1 mmol)
Then, 0.6 g (12.0 mmol) of hydrazine hydrate was added to 50 ml of ethanol, and the mixture was stirred at room temperature for 2 hours. After distilling off ethanol under reduced pressure, ethyl acetate and water were added to carry out liquid separation, and the organic layer was washed twice with water. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 1.3 g of 4-methyl-3-trifluoromethylpyrazole (86.7% yield).
I got

Reference Example 7 Production of 4-trifluoromethyl-1,6-dihydropyrimidine-6-oxide (Compound XIII) 6.9 g (48.6 mmol) of ethyl trifluoroacetate and 5 g of formamidine acetate (48 .1 mmol) and 5.1 g (48.1 mmol) of sodium carbonate were refluxed in 50 ml of methanol for 6 hours. After methanol was distilled off under reduced pressure, water and dilute hydrochloric acid were added, and the precipitated crystals were separated by filtration, dried and 5.3 g of 4-trifluoromethyl-1,6-dihydropyrimidine-6-oxide (yield 89.9).
%).

Reference Example 8 N '-(4-methyl-3-n-propylthiophenyl)
Trifluoroacetohydrazideyl chloride (compound X
Preparation of XI) 2.0 g (10 mmol) of 4-methyl-3-n-propylthiophenylhydrazine was added to 15 ml of pyridine,
Stirred at 0 ° C. 2.1 g of trifluoroacetic anhydride (10
Mmol) and the mixture was stirred at room temperature overnight. Pyridine was distilled off from the reaction mixture under reduced pressure, poured into 50 ml of water, and extracted with 30 ml of ethyl acetate. 20 ml of ethyl acetate layer
, And then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to give N '-(4-methyl-
2.3 g of (3-n-propylthiophenyl) trifluoroacetohydrazide were obtained. Next, this hydrazide 2.0
g (6.8 mmol) was dissolved in 15 ml of acetonitrile, 2.0 g (7.6 mmol) of triphenylphosphine and 5 ml of carbon tetrachloride were added, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, acetonitrile was distilled off under reduced pressure,
30 ml of toluene was added to the obtained residue, and insolubles were removed by decantation (twice). The toluene layers were combined, washed with 40 ml of water, and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography.
1.0 g of (4-methyl-3-n-propylthiophenyl) trifluoroacetohydrazideyl chloride (3.2
Mmol). This was used as a raw material in Example 10.

Reference Example 9 1-chloro-5- (2,6-dichloro-4-trifluoromethylphenyl) -2-nitrobenzene (compound XV
Preparation of I) 10.0 g (41.9) of 1-chloro-3-iodobenzene
Mmol) was added to 50 ml of dry benzene, and 32.0 ml of an n-butyllithium hexane solution (1.56 mol / l) was added dropwise while stirring at room temperature under a nitrogen stream. After stirring at room temperature for 2 hours, 9.9 g of 3,5-dichloro-4-fluorobenzotrifluoride (10
2.5 mmol) of diethyl ether in 200 ml was added dropwise. After stirring at room temperature for further 12 hours, the reaction mixture was poured into 500 ml of water and separated. 200 m of organic layer
After washing twice with 1 l of water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and 1-chloro-3- (2,6
-Dichloro-4-trifluoromethylphenyl) benzene 5.0 g (yield 35.0%) was obtained.

To 50 ml of fuming nitric acid was added dropwise 5.0 g (15.4 mmol) of 1-chloro-3- (2,6-dichloro-4-trifluoromethylphenyl) benzene at -30 ° C. After stirring at the same temperature for 15 minutes, the temperature was raised to 5 ° C, poured into about 200 ml of ice water, and diethyl ether 10
Extracted twice with 0 ml. 200 m of diethyl ether layer
After washing twice with 1 l of water, it was dried over anhydrous magnesium sulfate. The diethyl ether was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1-chloro-5- (2,6-) as a pale yellow liquid (n _D ²⁰ 1.5744).
3.0 g (yield 52.6%) of dichloro-4-trifluoromethylphenyl) -2-nitrobenzene was obtained. This was used as the raw material of (8) of Example 8.

Reference Example 10 Production of 2-fluoro-4- (2,4-dichlorophenyl) benzonitrile (Compound XVI) 1.0 g (5.2 mmol) of 2,4-dichlorophenylboronic acid, 4-bromo- 1.1 g (5.5 mmol) of 2-fluorobenzonitrile, 1.6 g of sodium carbonate
(15.0 mmol) and 0.8 g (0.7 mmol) of tetrakis (triphenylphosphine) palladium were added to a mixed solvent of 50 ml of toluene, 25 ml of ethanol and 25 ml of water, and reacted under heating and reflux for 2 hours. The reaction mixture was poured into ice water and extracted with toluene. After the toluene layer was washed twice with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 2-fluoro-4- (2,4
1.3 g of (-dichlorophenyl) benzonitrile (yield 9
3.0%). This was used as the raw material of Example 8 (1).

Reference Example 11 Production of 4- (4-trifluoromethylphenyl) -2,5-difluoronitrobenzene (Compound XVI) 2,5-Difluoro-4-bromonitrobenzene
3 g (68.5 mmol), 13.0 g (68.4 mmol) of 4-trifluoromethylphenylboronic acid, 15.0 g (141.5 mmol) of sodium carbonate and 2.0 g of tetrakis (triphenylphosphine) palladium
(1.8 mmol) was added to a mixed solvent of 200 ml of dimethoxyethane and 50 ml of water, and reacted under heating and reflux for 8 hours. Dimethoxyethane was distilled off under reduced pressure, 300 ml of ice water was added, and the organic matter was extracted twice with 100 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 200 ml of water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography.
13.5 g (yield 65.0%) of (trifluoromethylphenyl) -2,5-difluoronitrobenzene was obtained. This was used as a raw material for (8) of Example 8.

Reference Example 12 Production of 2-fluoro-4- (5-trifluoromethylpyridin-2-yl) benzonitrile (Compound XVI) 4.0 g of 2-fluoro-4-bromobenzaldehyde
(19.7 mmol), 2.0 g ethylene glycol
(32.3 mmol), p-toluenesulfonic acid 0.2
g (1.1 mmol) and 100 ml of toluene were placed in a round bottom flask and azeotropically dehydrated for 4 hours. After completion of the reaction, the organic phase was washed with aqueous sodium hydrogen carbonate and water, dried over anhydrous magnesium sulfate, and toluene was distilled off under reduced pressure to give 4.7 g of 2- (2-fluoro-4-bromophenyl) dioxolane (yield). 9
7%). This was dissolved in 50 ml of ether, and 15.0 ml of an n-butyllithium hexane solution (1.56 mol / l) was added dropwise while stirring at −60 ° C. under a nitrogen stream. After further stirring at −60 ° C. for 2 hours, a solution of 3.0 g (28.9 mmol) of trimethyl borate in 10 ml of diethyl ether was added dropwise, and the mixture was further stirred at room temperature for 12 hours. The mixture was cooled again to 0 ° C., 5 ml of dilute sulfuric acid was added, and the mixture was stirred for 1 hour. The reaction mixture was poured into 100 ml of water and separated. The organic layer was washed twice with 50 ml of water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give 4-
2.4 g (69% yield) of (dioxoborolan-2-yl) -2-fluorobenzaldehyde was obtained. This and 2-
3.5 g of bromo-5-trifluoromethylpyridine (1
4.2 mmol), 3.2 g of sodium carbonate (30.0
Mmol) and tetrakis (triphenylphosphine)
1.5 g (1.4 mmol) of palladium in toluene 10
The mixture was added to a mixed solvent of 0 ml, 40 ml of ethanol and 40 ml of water, and stirred under heating and reflux for 2 hours. The reaction mixture was poured into ice water, extracted with toluene, the toluene layer was washed twice with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to give 4- (5-trifluoromethylpyridine-
2.3 g of 2-yl) -2-fluorobenzaldehyde
(81% yield). This was dissolved in 100 ml of ethanol, and 1.0 g (14.5 g) of hydroxylamine hydrochloride was dissolved.
Mmol) and 1.0 g (10 mmol) of triethylamine, and the mixture was stirred at room temperature for 12 hours. Ethanol was distilled off under reduced pressure, and 50 ml of water and 50 ml of ethyl acetate were added to the residue.
Was added, and the mixture was separated. The organic layer was washed twice with 50 ml of water, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the obtained residue was dissolved in pyridine. 2.1 g (10 mmol) of trifluoroacetic anhydride Was added and left overnight. Pyridine was distilled off under reduced pressure, 50 ml of aqueous sodium bicarbonate and 50 ml of ethyl acetate were added, and the mixture was separated. After the organic layer was washed twice with 50 ml of water, dried over anhydrous magnesium sulfate,
The solvent was distilled off under reduced pressure to give 2-fluoro-4- (5-trifluoromethylpyridin-2-yl) benzonitrile.
8 g (81% yield) was obtained. This was used as the raw material of Example 8 (4).

Reference Example 13 Production of 2-fluoro-4- (6-oxo-4-trifluoromethyl-1,6-dihydropyrimidin-1-yl) benzonitrile (Compound XVI) 60% sodium hydride 0 0.8 g (20 mmol) were dispersed in 100 ml of N, N-dimethylformamide and, with stirring, 3.3-trifluoromethyl-1,6-dihydropyrimidine-6-oxide 3.3 synthesized in Reference Example 7.
g (20 mmol) was added. After the generation of hydrogen gas stopped, 2.8 g of 2,4-difluorobenzonitrile (20 g
(Mmol) was added and reacted at 110 ° C for 12 hours. The solvent was distilled off under reduced pressure, and 50 ml of water and 50 ml of ethyl acetate were removed.
Was added, and the mixture was separated. The organic layer was washed twice with 50 ml of water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to give 2-fluoro-4- (6-oxo-4-trifluoromethyl-1,6- Dihydropyrimidine-1-
Il) benzonitrile 1.1 g (19% yield) was obtained.
This was used as a raw material for (8) of Example 8.

Reference Example 14 Production of 4- (5-chlorothiophen-2-yl) -2-fluorobenzonitrile (Compound XVI) As in Reference Example 11, 4- (dioxoborolan-2-yl) -2 2.0 g of fluorobenzaldehyde (10.
4 mmol) and 2-bromo-5-chlorothiophene
By coupling 2 g (11.1 mmol) and then reacting with hydroxylamine hydrochloride, 0.9 g (38% yield) of 4- (5-chlorothiophen-2-yl) -2-fluorobenzonitrile was obtained. Was. This was used as a raw material for (6) of Example 8.

Reference Example 15 Production of 2-chloro-4- (3-trifluoromethylpyrazolyl) benzaldehyde (Compound XVI) 4.08 g of 3-trifluoromethylpyrazole (30.
0 mmol), 4.75 g (30.0 mmol) of 2-chloro-4-fluorobenzaldehyde and 4.14 g (30.0 mmol) of potassium carbonate were added to 30 ml of N, N-dimethylformamide, and the mixture was stirred at 60 ° C. for 2 hours.
After cooling to room temperature, the reaction mixture was poured into 100 ml of water,
The organic matter was extracted twice with 50 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 50 ml of water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was washed with n-hexane to give a light yellow powder 2-
7.18 g (87.2% yield) of chloro-4- (3-trifluoromethylpyrazolyl) benzaldehyde was obtained.

Reference Example 16 Preparation of 2-chloro-4- (3-trifluoromethylpyrazolyl) benzonitrile (Compound XVI) 2.5 g of 3-trifluoromethylpyrazole (18.4)
mmol), 2.9 g (18.4 mmol) of 2-chloro-4-fluorobenzonitrile, 2.8 g of potassium carbonate
(20.2 mmol) was added to 20 ml of N, N-dimethylformamide and stirred at 60 ° C. for 2 hours. After cooling to room temperature, the reaction mixture was poured into 100 ml of water, and the organic matter was extracted twice with 50 ml of ethyl acetate. The ethyl acetate layers were combined, washed twice with 50 ml of water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was washed with n-hexane to give 2-chloro-4 as a white powder.
4.6 g (92.0% yield) of-(3-trifluoromethylpyrazolyl) benzonitrile was obtained. Reference Example 3
Used as raw material.

Reference Example 17 3- (2,4-dichlorophenyl) aniline (compound X
VIII) Preparation of 2.0 g (10.4) of 2,4-dichlorophenylboronic acid
Mmol), 2.4 g (11.0 mmol) of 3-iodoaniline, 3.2 g (30.0 mmol) of sodium carbonate and 1.6 g (1.4 mmol) of tetrakis (triphenylphosphine) palladium in 70 ml of toluene,
To a mixed solvent of 30 ml of ethanol and 30 ml of water,
The reaction was carried out for 2 hours under reflux. The reaction mixture was poured into ice water and extracted with toluene. After the toluene layer was washed twice with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 0.9 g of 3- (2,4-dichlorophenyl) aniline (yield: 36.0%). This was used as a raw material in Example 9.

Reference Example 18 Production of [2-chloro-4-fluoro-5- (3-trifluoromethyltriazolyl) phenyl] methyl sulfide 4-chloro-2-fluoro-5-methylthiophenylhydrazine 1 g (19.8 mmol), 2.9 g of trifluoroacetaldehyde ethyl hemiacetal (2
0.1 mmol), 0.3 g (1.5 mmol) of p-toluenesulfonic acid monohydrate and 50 ml of ethanol were placed in a round-bottomed flask, reacted for 1 hour under reflux, and then ethanol was distilled off under reduced pressure. To give N '-(4-chloro-2-fluoro-5-methylthiophenyl) trifluoroacetaldehyde hydrazone. This was dissolved in 50 ml of N, N-dimethylformamide, and 3.8 g (21.3 mmol) of N-bromosuccinimide was added at room temperature. After stirring at room temperature for another 1 hour, the solvent was distilled off under reduced pressure and 50 ml
And extracted with 30 ml of ethyl acetate. The ethyl acetate layer was washed with 20 ml of water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to give N '-(4
6.5 g of (-chloro-2-fluoro-5-methylthiophenyl) trifluoroacetohydrazideyl bromide (9
0.3%). This was dissolved in 50 ml of N, N-dimethylformamide, and 2 ml of 28% aqueous ammonia was added. After stirring at room temperature for another 1 hour, the solvent was distilled off under reduced pressure, poured into 50 ml of water, and extracted with 30 ml of ethyl acetate.
The ethyl acetate layer was washed three times with 20 ml of water, and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and 4.5 g of N '-(4-chloro-2-fluoro-5-methylthiophenyl) trifluoroacetamidine (8
(3.8%). The resulting N '-(4-chloro-2-
(Fluoro-5-methylthiophenyl) trifluoroacetamidine and p-toluenesulfonic acid monohydrate 0.3
After refluxing g (1.5 mmol) in 30 ml of trimethyl orthoformate for 6 hours, the trimethyl orthoformate was distilled off under reduced pressure, poured into 50 ml of water, and extracted with 30 ml of ethyl acetate. After washing the ethyl acetate layer twice with 20 ml of water,
It was dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain 2.2 g (47.2%) of [2-chloro-4-fluoro-5- (3-trifluoromethyltriazolyl) phenyl] methyl sulfide. This was used as a raw material for Reference Example 5 (2).

The insecticide and acaricide of the present invention has the general formula [I]
The active ingredient is a 3-arylphenyl sulfide derivative represented by

When the compound of the present invention is used as an active ingredient of a pesticidal agent, the compound of the present invention may be used as it is. And other auxiliaries, emulsions, suspensions, powders, granules, tablets, wettable powders, aqueous solvents, liquids, flowables, wettable powders, aerosols,
It can be formulated into various forms such as pastes, oils, emulsions and the like. These mixing ratios are usually 0.1% of the active ingredient.
It is 10 to 99.9 parts by weight of the pesticide adjuvant in 〜90 parts by weight.

The carriers used in the formulation are divided into solid carriers and liquid carriers. Solid carriers include, for example, starch, activated carbon, soy flour, flour, wood flour, fish flour, animal and plant powders such as milk powder, talc, kaolin,
Bentonite, calcium carbonate, zeolite, diatomaceous earth,
Mineral powders such as white carbon, clay, and alumina can be used. Examples of the liquid carrier include water; alcohols such as isopropyl alcohol and ethylene glycol;
Ketones such as cyclohexanone and methyl ethyl ketone;
Ethers such as dioxane and tetrahydrofuran; aliphatic hydrocarbons such as kerosene and light oil; aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, methylnaphthalene and solvent naphtha; halogenated hydrocarbons such as chlorobenzene; Acid amides such as dimethylacetamide; esters such as glycerin esters of fatty acids; nitriles such as acetonitrile; and sulfur-containing compounds such as dimethylsulfoxide.

Examples of the surfactant include a metal salt of alkyl benzene sulfonic acid, a metal salt of dinaphthyl methane disulfonic acid, an alcohol sulfate, an alkyl aryl sulfonate, a lignin sulfonate, a polyoxyethylene glycol ether, and a polyoxyethylene alkyl. Aryl ether, polyoxyethylene sorbitan monoalkylate and the like can be mentioned.

Examples of other auxiliary agents include fixing agents or thickeners such as carboxymethylcellulose, gum arabic, sodium alginate, guar gum, tragacanth gum, and polyvinyl alcohol; defoaming agents such as metal soaps;
A property improving agent such as a fatty acid, an alkyl phosphate, silicone, and paraffin, a coloring agent, and the like can be used.

In the actual use of these preparations, they can be used as they are or after being diluted to a predetermined concentration with a diluent such as water. The application of various preparations containing the compound of the present invention, or a dilution thereof, is carried out by a commonly used application method, that is, spraying (for example, spraying, misting, atomizing, dusting, dusting, water application, box application). Etc.), soil application (e.g., mixing, irrigation, etc.), surface application (e.g., application, dressing, coating, etc.), dipping, bait and the like. Further, it is also possible to feed the livestock with the above-mentioned active ingredient mixed with livestock to control the generation and growth of harmful insects, particularly harmful insects, in their excrement. Further, it can be applied by a so-called ultra-high concentration small amount spraying method. In this method, it is possible to contain 100% of the active ingredient.

The application of the pesticidal composition of the present invention is generally 0.1 to 50,000 ppm, preferably 1 to 10,000 ppm.
It is carried out at an active ingredient concentration of ppm.

The concentration of the active ingredient can be appropriately changed depending on the form of the preparation, the method of application, the purpose, the timing, the place and the occurrence of pests. For example, in the case of aquatic pests, even if a chemical solution having the above-mentioned concentration range is sprayed on the place of occurrence, control can be performed.
The application rate per unit area is 0.1 to 5000 g, preferably 1 to 1000 g as an active ingredient compound per ha.
Is used, but is not limited thereto.

Needless to say, the compound of the present invention alone is sufficiently effective, but if necessary, other fertilizers and agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antibacterial agents, It can be mixed with or used in combination with a virus agent, an attractant, a herbicide, a plant growth regulator, etc., and in this case, even better effects may be exhibited.

Representative examples of insecticides, fungicides, acaricides and the like which can be used by mixing with the compound of the present invention are shown below.

For example, organophosphorus and carbamate insecticides: fenthion, fenitrothion, diazinon,
Chlorpyrifos, oxydeprofos, bamidione, fentoate, dimethoate, formotion, malathion, trichlorfon, thiomethone, phosmet, dichlorvos, acephate, EPBP, methylparathion,
Oxydimetone methyl, ethione, dioxabenzophos, cyanophos, isoxathion, pyridafenthion, hosalon, methidathion, sulfophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, disulfoton, propenophos, pyraclophos, monocrotophos, Azinphos-methyl, aldicarb, mesomil, thiodicarb, carbofuran, carbosulfan, benfracarb, flatiothiocarb, propoxur, fenobcarb, metlcarb, isoprocarb, carbaryl, pirimicarb, ethiophencarb, diclofenthion, pirimiphosmethyl, quinalphos, chlorpyrifosmethyl, prothioda, MC, X Iocarb, oxamil, alanical , Such as chlorobutyl host.

Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, etocitrin Fenprox, cycloprothrin, tralomethrin, silafluofen, tefluthrin, bifenthrin, acrinatrine and the like.

Acylureas and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron,
Triflumuron, teflubenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, lufenuron, cyromazine, methoprene, endosulfan, diafenthiuron, imidacloprid, fipronil, nicotine sulfate, rotenone, methaldehyde, machine oil, BT and insects Microbial pesticides such as pathogenic viruses, phenoxycarb, cartap, thiocyclam,
Bensultap, tebufenozide, chlorfenapyr,
Emamectin benzoate, acetapride, nitenpyram, sodium oleate, rapeseed oil and the like.

Nematicides: fenamiphos, phosthiazate, etoprophos, methyl isothiocyanate, 1,3
Dichloropropene, DCIP and the like.

Acaricides: chlorbenzylate, phenisobromolate, dicofol, amitraz, propargite, benzomate, hexithiax, fenbutatin oxide, polynactin, quinomethionate, chlorfenson, tetradiphone, abamectin, milbemectin, clofentezine, pyridaben , Fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor, ethoxazole, halfenprox, bifenazate and the like.

Fungicides: thiophanate methyl, benomyl, carbendazole, thiabendazole, folpet, thiuram, ziram, zineb, maneb, polycarbamate, iprobenphos, edifenphos, fusaride, probenazole, isoprothiolane, chlorothalonil, captan, polyoxin, blasticidin S,
Kasugamycin, Streptomycin, Validamycin, Tricyclazole, Pyroquilon, Phenazine Oxide, Mepronil, Flutolanil, Penciclone, Iprodione, Himexazole, Metalaxyl, Triflumizole, Trifolin, Triadimefon, Vitertanol,
Fenarimol, propiconazole, simoxanil, prochloraz, perfurazoate, hexaconazole, microbutanil, diclomedine, teclophthalam, propineb, dithianone, fosetyl, vinclozolin, procymidone, oxadixil, guazatine, propamocarb hydrochloride, fluazinam, oxoisoliconic acid, oxoisonic acid Mepanipyrim and the like.

The compounds of the present invention can be prepared by using the compounds of the present invention: It shows an excellent control effect against pests such as sex nematodes. Examples of such pests include the following pests.

Pests of the order Hemiptera, for example, Rabbit bugs (R
iptortus clavatus, southern stink bug (Nezara viridula), white stink bug (Lygus sp.), red-winged stink bug (Blisssusleucopterus),
Nashigumbai (Stephanitis nashi)
Stink bugs (Heteroptera; HETEROPTERA), etc.
Black leafhopper (Nephotettix cinc)
ticeps), leafhoppers (Empoasca)
sp. , Erythroneura sp. , Cir
culifer sp. ), Leafhoppers (Nilaparvata lugens), staghorn planthoppers (Sogatalla furcifer)
a), Japanese brown planthopper (Laodelfax str)
hoppers such as iatellus), Psyllas
p. Lice such as lice, whitefly (Bemisi)
atabaci), whitefly (Triale)
whiteflies such as urodes vapororiorum, grapevine aphid (Viteus viti)
folii), peach aphid (Myzus pe)
rsicae) and apple aphid (Aphis po)
mi), cotton aphid (Aphis gossypi)
i), Aphis fabae, radish aphid (Rhopalosiphum pesedobras)
sicas, potato beetle aphid (Aul)
acorthum solani) and aphids such as the wheat aphid (Schizaphis graminum), and the stag beetle (Pseudoc)
occus comstocki, ruby beetles (Ceroplastes rubens), and sun horse scales (Comstockockaspis per)
niciosa) and the wild scale insect (Unaspi)
syanonensis, etc., and sea turtles (Rhodnius sp.).

Lepidopteran pests such as Chamomaki (Homo
na magnanima), Kokamon monamaki (Ad
oxophies orana), Tenguhamaki (Sp
arganothis pillariana, Nasihimesingui (Grapholitha moleest)
a), Mameshin squid (Leguminivoragl)
ycinivorella), codling moth (Laspe)
yresia pomonella), Eucosma
sp. , Lobesia botrana, and other oysters, and grape soy hamaki (Eupoecillia a
mambiguella), Bamba
lina sp. And other larvae, such as Nemopo
gon granulus, iga (Tineat)
lancelucens, etc., and the lycopodium moth moth (Lyonetia prunifoliell).
a) and the like,
Nostratum rigoniella and the like, the citrus leaf moth (Phyllocnistis)
Citrulla, etc .;
utella xylostella), Plays
stags such as citri, grape squash (Parant)
hrene regalis), Synanthesdo
n sp. Stag beetles, such as cotton beetle (Pec
tinophora gossypiella, potato moth (Phthomaimaea opercule)
lla), Stopteryx sp. And others, such as Carposina nipone
nsis), irida (Monema)
flavescens) and iraga, squid (C)
HILO Suppressalis, Kobume meiga (Cnaphalocrocis medinali)
s), Ostrinia nubilalis, Aristolochia (Ostrinia furnacalis)
, Hellula undal
is), Honey (Galleriamellone)
lla), Elasmopalpus lignose
lulus, Loxostege sticticali
s and other Japanese moths, white butterfly (Pieris ra)
pae) and white butterflies, Artemisia japonicus (Asc)
otis selenaria, etc., Paeoniae, such as Malcosoma neustria, Sponges, such as Manduca sexta, and Eupoctis pseudo.
conspersa), Gypsy moth (Lymantri)
a dispar, etc., Higtriga, such as Hyphantria cunea, and tobacco bad worm (Heliothis vir)
escens), ball worm (Helikoverp)
a zea), Spodoptera litura (Spodopte)
ra exigua) and Helicov (Helicov)
erpa armigera), Spodoptera litura (Sp)
podoptera litura) and the armyworm (Mam)
estra brassicae), Tamanayaga (Ag)
rotis ipsiron), armyworm (Pseu)
and nodules such as daleia separata and Trichoplusia ni.

Coleopteran pests, for example Douganebuui (A
Nomala cuprea), Bean beetle (Popi)
llia japonica), Japanese turtle (Anom)
ala rufocuprea), Eutheola
beetles, wireworms (Agriotes sp.), Conodeus s
p. Beetles such as beetles,
pilachna vigintiocutunct
ata), ladybug (Epilachna)
ladybirds such as Varivestis, and Tribolium castaneu.
m) and other beetles, such as beetles and beetles (Ano)
plophora malasiaca, pine beetle (Monochamus alternat)
us), beetles beetles, bean weevil (A
canthoscelides obtectus),
Adzuki beetle (Callosobruchus ch)
beetles such as C. inensis, and the colorado leaf beetle (Leptinotarsa decemlineat)
a), corn rootworm (Diabrotica s)
p. ), Olema oryzae
e), Chaetocnema
concinna), Phaedon cochlea
rias, Olema melanopus, Dic
Chrysomelidae such as Ladispa armigera, Ap
weevil weevil such as ion godmani and rice weevil (Lissorhoptrus oryz)
ophilus) and a cotton weevil (Anthonom)
weevil, etc., weevil such as Sitophilus zeamais, bark beetles, beetles, beetles, etc.

A dipteran pest, for example, Pterodactyla (T
ipra anno), rice midge (Tanytars)
us oryzae) and rice flour flies (Ors)
eolia oryzae), Mediterranean fruit fly (C
eratitis capitata), rice stalk fly (Hydrellia grisela), Drosophila suzuki (Drosophila suzu)
kii), fritz fries (Oscinella fr)
it), rice flies (Chlorops oryza)
e), haricot fly (Ophiomia ph)
aseoli), the bean leaf fly (Liriomyz)
a trifolii), red mosaic fly (Pe
gomya hyoscillami) and the fly (Hyl)
emiplatura), sorghum fry (Athe
rigona soccata, housefly (Musc)
a Domestica, Horsefly (Gastrop)
hilus sp. ), Stomflies (Stomoxys)
sp. ), Aedes aegypt
i), Culex pipiens, and Anopheles slnensi
s), Culex tritaen (Culex tritaen)
iorhynchus).

Hymenoptera pests, such as wasps (Ceph)
us sp. ), Beetles (Harmolit)
a sp. ), The wasps (Athalia s)
p. ), Wasps (Vespa sp.), Fire ant and the like.

Pests of Orthoptera, such as German cockroaches (B
ratella germanica), cockroach Periplaneta americana (Periplaneta americana)
), Kera (Grylotalpa african)
a), grasshopper (Locustamigratoria)
migratriodes), Melanoplus
sanguinipes and the like.

A termite pest such as a termite (Reticulitermesperatus),
House termites (Copttermes forms)
anus) and the like.

Thrips pests, for example, Thrips thrips dorsal
is), Thrips palmi (Thrips pa
lmi), Croton thrips (Heliothrip)
haemorrhoidalis, Frankliniella occid
entalis), Thrips palmi (Haplot)
hrips aculeatus).

Spider mites, for example, spider mites (Tetra)
nychus urticae), Kanzawa spider mite (T
etranychus kanzawai, mandarin spider mite (Panonychus citri), apple spider mite (Panyonychusulmi), yellow mite (Eotetranychus carpini),
Texas Citrus Might (Eotetranychus)
banksi), citrus red mite (Phylloco)
ptruta oleivora), Polyphagotarsonemus latu
s);
p. ), Robin mite (Rhizoglyphus r)
obini), Tyrophagus
putresentiae) and the like.

Plant parasitic nematodes, such as sweet potato nematodes (Meloidogyne incogn)
ita), nematode (Pratylench)
ussp. ), Soy cyst nematode (Hetero)
dera glycines), Rice phalaenopsis nematode (Aphelenchoides bessey)
i), pine wood nematode (Bursaphelen)
chus xylophilus) and the like.

Other pests, unpleasant animals, sanitary pests, and parasites, for example, Pomacea ca
naliculata), slugs (Inciari)
asp. ), African Maimai (Achatina f
ulica) and other gastropods (Gastropoda),
Dung beetle (Armadillidium sp.),
Isopoda, such as Warabijimushi and Centipede,
Liposcelis sp. And other beetles, C
tenolepisma sp. Such as spots, Pure
x sp. , Ctenocephalides sp.
Fleas such as Trichodictes sp. Lice such as Cimex sp. Bed lice such as bed bugs such as bed bugs, Boophilus microplu
s), Haemaphysalis
animal mites, Dermatophagoides and the like.

Further, it is also effective against pests which are resistant to organic phosphorus compounds, carbamate compounds, synthetic pyrethroid compounds, acylurea compounds or existing insecticides.

[0280]

EFFECTS OF THE INVENTION The compound of the present invention is a compound of the class of Hemiptera, Lepidoptera, Coleoptera, Diptera, Hymenoptera, Orthoptera, Termites, Thrips, Spider mites, It shows an excellent control effect on a wide range of pests such as plant parasitic nematodes, and can also control resistant pests.

Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and auxiliary agents are not limited to these, and can be changed in a wide range. In the following description,% indicates weight percentage.

Formulation Example 1 Emulsion 30% of compound (I-28), 20% of cyclohexanone,
11% polyoxyethylene alkyl aryl ether,
An emulsion was prepared by uniformly dissolving 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene. Formulation Example 2 wettable powder compound (I-28) 10%, naphthalenesulfonic acid formalin condensate sodium salt 0.5%, polyoxyethylene alkylaryl ether 0.5%, diatomaceous earth 24%,
65% clay was uniformly mixed and pulverized to obtain a wettable powder. Formulation Example 3 Dust 2% of compound (I-28), 5% of diatomaceous earth and 93% of clay
Was uniformly mixed and pulverized to obtain a powder. Formulation Example 4 Granules Compound (I-28) 5%, lauryl alcohol sulfate sodium salt 2%, lignin sulfonate sodium 5%, carboxymethyl cellulose 2% and clay 8
6% was uniformly mixed and pulverized. 20 parts by weight of water was added to 100 parts by weight of this mixture, kneaded, and the mixture was extruded using an extrusion granulator.
After processing into 4-32 mesh granules, they were dried to give granules.

Next, the effects of the pesticidal composition containing the compound of the present invention as an active ingredient will be described with reference to Test Examples. Test Example 1 Test for controlling spider mites A wettable powder prepared according to Formulation Example 2 was used as an active ingredient in an amount of 50%.
Diluted with water to a concentration of 0 ppm. A soybean seedling inoculated with an adult spider mite was immersed in the solution and air-dried. The soybean seedlings after the treatment were placed in a constant temperature room at 25 ° C., and after 13 days, the number of surviving insects was examined, and the control value was calculated by the equation (1). In this test, as a representative of the compounds that can achieve an acaricidal effect with a control value of 90 or more, I-2, I-3, I-10,
I-12, I-17, I-18, I-19, I-21, I-24, I
-26, I-27, I-28, I-29, I-32, I-35, I-
37, I-38, I-40, I-42, I-44, I-45, I-4
6, I-48, I-49, I-50, I-51, I-52, I-5
3, I-54, I-59, I-60, I-61, I-76, I-7
7, I-78, I-79, I-81, I-82, I-82, I-8
5, I-92, I-93, I-96, I-98, I-99, I-10
0, I-103, I-107, I-111, I-113, I-114, I
-118, I-119, I-120, I-122, I-123, I-12
4, I-127, I-128, I-129, I-130, I-131, I
-132, I-133, I-134, I-137, I-151, I-15
2, I-153, I-163, I-167, I-170, I-173, I
-175, I-176, I-178, I-179, I-180, I-18
1, I-183, I-184, I-185, I-186, I-187, I
-188, I-189, I-190, I-191, I-192, I-19
3, I-194, I-196, I-198, I-199, I-204, I
-205, I-206, I-207, I-208, I-209, I-21
0, I-211, I-213, I-215, I-216, I-219, I
-220, I-221, I-222, I-223, I-224, I-22
7, I-228, I-229, I-230, I-232, I-233, I
-234, I-235, I-236, I-238, I-239, I-24
4, I-245, I-248, I-249, I-250, I-251, I
-252, I-253, I-254, I-255, I-256, I-25
7, I-258, I-259, I-260, I-261, I-262, I
-263, I-264, I-265, I-266, I-267, I-27
6, I-277, I-278, I-279, I-282, I-283, I
-286, I-287, I-288, I-290, I-291, I-29
2, I-293, I-294, I-295, I-296, I-297, I
-298, I-299, I-300, I-301, I-302, I-30
3, I-304, I-305, I-306, I-307, I-308, I
-309, I-310, I-311, I-312, I-313, I-31
4, I-315, I-317, I-318, I-320, I-322, I
-324, I-325, I-328, I-329, I-330, I-33
6, I-337, I-339, I-340, I-341, I-342, I
-343, I-344, I-345, I-346, I-347, I-34
8, I-349, I-350, I-351, I-352, I-353, I
-354, I-355, I-356, I-357, I-358, I-35
9, I-360, I-361, I-362, I-364, I-366, I
-367, I-368, I-369, I-370, I-372, I-37
4, I-383, I-385, I-386, I-387, I-388, I
-403, I-405, I-406, I-407, I-408, I-41
1, I-414, I-417, I-418, I-419, I-421, I
-422, I-425, I-426, I-427, I-428, I-42
9, I-430, I-445, I-446, I-451, I-452, I
-477, I-478, I-513, I-514, I-517, I-51
8, I-535, I-571, I-572, I-573, I-575, I
-576, I-577, I-581, I-587, I-588, I-58
9, I-591, I-593, I-595, I-599, I-600, I
I-1, II-3, II-4, II-5, II-6, II-
9, II-11, II-15, II-16, II-19, II-2
0, II-27, II-28, II-39, II-40, II-4
3, II-44, II-55, II-57, II-58, II-6
1, II-62, II-77, II-78, II-81, II-8
2, II-85, II-86, II-89, II-94, II-9
5, III-10, III-14, III-15, IV-5, I
V-6, V-13, V-14, V-19, V-20, V-21, V
-27, V-32, V-33, V-36, V-37, V-38, V-
44, V-53, V-54, V-82, V-83, V-92, V-9
3, V-95, V-102, V-103, V-105, V-113, V
-114, V-116, V-120, V-121, V-124, V-15
4, V-155, V-156, V-159, V-167, V-176, V
-179, V-188, V-208, V-237, V-266, V-27
6, V-278, V-283, V-284, V-285, V-286, V
-292, V-294, V-295, V-297, V-301, V-30
2, V-305, V-307, V-312, V-321, V-323, V
-324, V-326, V-330, V-331, V-333, V-36
5, V-366, V-373, V-493, V-613, V-614, V
-635, V-636, V-639, V-640, V-645, V-64
6, V-651, V-652, V-653, V-657, V-658, V
−659, V−660, V−685, V−686, V−687, V−68
8, V-692, V-693, V-694, V-695, V-698, V
-699, V-700, V-701, V-708, V-710, V-71
7, V-718 and the like.

On the other hand, Comparative compound 1 (2-amino-6-methylthio-4-phenyl-benzene-1,3-dicaronitrile), which is the compound of Example 1 in the specification of East German Patent No. 142541, and East Germany The control value in this test of Comparative Compound 2 (2-amino-6-phenyl-4-methylthio-3-nitrobenzonitrile), which is an example compound in the specification of Japanese Patent No. 142542, was zero.

[0285]

(Equation 1)

[0286]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 43/40 101 A01N 43/40 101Q 43/54 43/54 ABF 43/56 43/56 D43 / 653 43/653 A 43/76 43/76 43/78 43/78 B C07C 317/14 C07C 317/14 317/22 317/22 317/44 317/44 321/28 321/28 323/18 323 / 18 323/22 323/22 323/35 323/35 323/41 323/41 323/43 323/43 323/62 323/62 C07D 213/57 C07D 213/57 231/12 231/12 Z 239/36 239 / 36 249/08 513 249/08 513 333/20 333/20 333/28 333/28 (72) Inventor Minoru Ito 408 Shionita, Fukuda-cho, Fukuda-machi, Iwata-gun, Shizuoka Pref. 72) Inventor Tetsuya Hiraide 408-1, Shioda, Fukuda-cho, Iwata-gun, Shizuoka Prefecture Inside the K-I Research Institute Co., Ltd. 408-1 K-I Research Institute, Inc. (72) Inventor Mitsuharu Asahida 408-1 Shi-Nitta, Fukuda-cho, Fukuda-cho, Iwata-gun, Shizuoka Prefecture (72) K-I Research Institute, Inc. (72) Inventor Yasunobu Maeda Iwata, Shizuoka Prefecture 408-1 Shioda, Fukuda-cho, Fukuda-gun, Japan In-house Research Institute, Inc. (72) Inventor Nobuhide Wada 408-1, Shioda, Fukuda-machi, Iwata-gun, Shizuoka, Japan In-house Research Institute for Keio Corporation, (72) Inventor Toyoichi Fujisawa 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Inventor Yuki 1809, Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka (72) Inventor Masaaki Komatsu 1809, Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka (72) Inventor Tada Osamu 2-4-6 Midorigaoka, Kakegawa-shi, Shizuoka Pref. AB02 AC22 AC24 AC63 BA02 BA06 BA21 BA25 BA29 BA32 BA48 BA51 BA93 BB11 BB12 BB14 BB15 BB20 BB2 1 BB22 BB25 BC10 BC19 TA03 TA04 TB02 TB03 4H011 AC01 AC02 AC04 AC05 BB07 BB09 DA02 DA15 DA16 DC06

Claims (10)

[Claims] 1. A compound of the general formula [I]Ｒwhere R is C_Two~ C₆An alkyl group of which is a halogen atom
Mono- or poly-substituted by a substituent or a cyano group
I), C_Two~ C₆An alkenyl group (the group is a halogen atom or
May be mono- or poly-substituted by a cyano group.
I), C_Two~ C₆An alkynyl group, which is a halogen atom or
May be mono- or poly-substituted by a cyano group.
I), C_Three~ C₆A cycloalkyl group (the group is a halogen atom)
Mono- or poly-substituted by a substituent or a cyano group
I) or C_Four~ C₉A cycloalkylalkyl group of the formula
Mono- or poly-substitution by halogen atom or cyano group
N is an integer of 0 to 2, and Ar
The group has the general formula:And a group represented by the formula:₁, Q_Two, Q_Three, Q_FourPassing
And Q_FiveIs a nitrogen atom or C—A, respectively.₁, Nitrogen atom or
Is CA_Two, A nitrogen atom or CA_Three, A nitrogen atom or CA
_FourAnd a nitrogen atom or CA_FiveAnd Q₆Is an oxygen atom or
Represents a sulfur atom, Q₇Is a nitrogen atom or CA₇And Q
₈Is a nitrogen atom or CA₈And A₁, A_Five, A₇, A₁₁
And B₀Is hydrogen atom, halogen atom, amino group, cyano
Group, nitro group, C₁~ C₆An alkyl group of C₁~ C_FourHalo of
Alkyl group, C₁~ C₆An alkylthio group (the group is
May be monosubstituted or polysubstituted)
C ₁~ C₆An alkoxy group of A_Two, A_Three, A_Four, A₆, A
₉, B₁, B_TwoAnd B_ThreeIs hydrogen, halogen, cyano
Group, nitro group, C₁~ C₆An alkyl group of the formula
Atom, hydroxyl group, cyano group, C_Two~ C₇The alkoxy carb
Nyl group or C₁~ C₆Mono-substituted by an alkoxy group of
May be poly-substituted), C_Two~ C₆Alkenyl group (the
Groups are mono-substituted or poly-substituted by halogen atoms or cyano groups
May be substituted), C_Two~ C₆Alkynyl group (the group is
Mono- or poly-substitution by halogen atom or cyano group
May be done), C₁~ C₆An alkoxy group of the formula
Gen atom, cyano group, C_Two~ C_FiveThe alkoxycarbonyl
Group or C₁~ C_ThreeMono-substituted or poly-substituted by an alkoxy group
May be substituted), C₁~ C₆Alkylthio group (the group
Is a halogen atom or C₁~ C_ThreeBy the alkoxy group of
Substituted or poly-substituted), C₁~ C₆The alkyl of
Sulfinyl group (the group is a halogen atom or C₁~ C_ThreeNo
It may be mono- or poly-substituted by a lucoxy group.
I), C₁~ C₆An alkylsulfonyl group of the formula
Atom or C₁~ C_ThreeMono-substituted by an alkoxy group of
May be poly-substituted), C₁~ C₇An acyl group of C_Two~
C_FiveHaloalkylcarbonyl group, carboxyl group, C_Two
~ C₇An alkoxycarbonyl group or NR₁R_Two[Where,
R₁And R_TwoAre independently a hydrogen atom, C₁~ C₆No
Alkyl group (the group is a halogen atom, a cyano group,
Group, C₁~ C₆An alkoxy group or C₁~ C₆The alkyl of
Mono- or poly-substituted by a thio group), C
_Two~ C₆An alkenyl group, which is a halogen atom or cyano
May be mono- or poly-substituted), C_Two~
C₆Alkynyl group (the group is a halogen atom or a cyano group
May be mono- or poly-substituted), C₁~ C₇
An acyl group or C_Two~ C₇Represents an alkoxycarbonyl group of
You. R₁And R_TwoIs 5 with these attached nitrogen atoms
May form a 6-membered ring. And A₈Is hydrogen field
, Halogen atom, cyano group, C₁~ C₆Alkyl group
(The group is a halogen atom or C₁~ C_ThreeBy the alkoxy group of
Mono- or poly-substituted), C₁~ C₆No
Alkoxy group (the group is a halogen atom or C₁~ C_ThreeArco
Mono- or poly-substituted by an xy group), C
₁~ C₇An acyl group of C_Two~ C_FiveHaloalkylcarbonyl
Group or NR₁R_Two(Where R₁And R_TwoHas the same meaning as above
Show. ) And A_TenIs a hydrogen atom, C₁~ C₆The alkyl of
Group (the group is a halogen atom or C₁~ C_ThreeTo the alkoxy group of
More mono- or poly-substituted), C₁~ C₇of
Acyl group, C_Two~ C_FiveHaloalkylcarbonyl group, cal
Boxyl group or C_Two~ C₇Represents an alkoxycarbonyl group of
Provided that the Ar group is represented by the general formulas [Ar-1] and [Ar-
2], Q₁~ Q_FiveMeans that up to two nitrogen atoms
And the Ar group is represented by Q in the general formula [Ar-1]._FiveOnly nitrogen
A for atoms₁Is a hydrogen atom, and an Ar group is generally
In the formula [Ar-1], Q₁, Q_Two, Q_Three, Q_FourAnd Q_FiveBut it
Each, CA₁, CA_Two, CA_Three, CA_FourAnd CA
_FiveIn the case of A_Two, A_Three, A_FourAnd B_TwoAre simultaneously hydrogen atoms
Never, A₁From A_FiveWhen all are hydrogen atoms,
B_TwoIs a methyl group and R is an isopropyl group.
And the Ar group is Q in the general formula [Ar-4].₈Is CA₈Place
If R is C_Two~ C₆Alkyl group (the group is a halogen atom
More mono- or poly-substituted), C_Three~ C₆of
Cycloalkyl groups, which are monosubstituted by halogen atoms
Or poly-substituted) or C_Four~ C₉The cycloal
A alkyl group, which is monosubstituted or substituted by a halogen atom
May be poly-substituted). 3- represented by｝
Arylphenyl sulfide derivatives. 2. A ₁ , A ₅ , A ₇ and A ₁₁ are hydrogen atoms, and R is an ethyl group (the group may be mono- or poly-substituted by a halogen atom) or an n-propyl group (the The compound according to claim 1, wherein the group is mono- or poly-substituted by a halogen atom or a cyclopropylmethyl group (the group may be mono- or poly-substituted by a halogen atom). 3. The compound according to claim 1, wherein the Ar group is represented by the general formula [Ar-1] or the general formula [Ar-4]. 4. An aryl group represented by the general formula [Ar-1]:
₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ are respectively C-A ₁ , C-
_{A 2, C-A 3,} C-A 4 and C-A ₅ The compound of claim 1, wherein shown. 5. The compound according to claim 1, wherein the Ar group has the general formula [Ar-4]. 6. An insecticide and acaricide containing the 3-arylphenyl sulfide derivative according to claim 1 as an active ingredient. 7. An insecticide and acaricide comprising the 3-arylphenyl sulfide derivative according to claim 2 as an active ingredient. 8. An insecticide and acaricide containing the 3-arylphenyl sulfide derivative according to claim 3 as an active ingredient. 9. An insecticide and acaricide comprising the 3-arylphenyl sulfide derivative according to claim 4 as an active ingredient. 10. An insecticide and acaricide comprising the 3-arylphenyl sulfide derivative according to claim 5 as an active ingredient.