JP2007284386A - 3-pyrazolylphenyl sulfide derivative and insecticide, acaricide and nematicide containing the same as active ingredient - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new 3-pyrazolylphenyl sulfide derivative having excellent soil treatment activity as an agricultural and horticultural insecticide, acaricide and nematicide or its salt and an agricultural and horticultural insecticide, acaricide and nematicide comprising the derivative or its salt as an active ingredient. <P>SOLUTION: The 3-pyrazolylphenyl sulfide derivative is represented by general formula [I] (R<SB>1</SB>is a 1-6C alkyl group or a 3-6C cycloalkyl group; R<SB>2</SB>is a 1-6C alkyl group; n is an integer of 0-2; m is 0 or 1; A<SB>1</SB>and A<SB>2</SB>are each a hydrogen atom or a halogen atom; B<SB>1</SB>is a hydrogen atom, a halogen atom or a methyl group; B<SB>2</SB>is a cyano group, a nitro group or a 1-6C alkyl group) or its salt. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel 3-pyrazolyl phenyl sulfide derivative and an agricultural / horticultural insecticidal / acaricidal / nematicidal agent comprising the same as an active ingredient.

  As known agricultural insecticides and sanitary pest control agents, Patent Documents 1 to 3 disclose 1-phenylpyrazole derivatives. However, these documents do not show any activity against spider mites. Moreover, there is no description regarding soil treatment in this document.

  Moreover, when spraying a chemical | medical agent directly to a plant body, sufficient effect may not be acquired by the chemical | medical agent outflow by nonuniform chemical spraying, transpiration, photolysis, rainfall, etc. On the other hand, the chemical | medical agent which can process soil can acquire the stable effect since a chemical | medical agent spreads to the whole plant body. Furthermore, for farmers, there is a merit that the chemical exposure by spraying is less and safer and the spraying method is simple, so that labor can be saved.

However, at present, there are very few known acaricides having practical soil treatment activity. Therefore, development of an acaricide having soil treatment activity is required.
JP-A-62-228065 (Claims and others) JP 62-164669 A (Claims and others) JP 61-268671 A (claims and others)

  The problem of the present invention is to solve the above-mentioned problems of conventional insecticides, acaricides and nematicides in such circumstances, and further, safety, control effect, residual effect, etc. It is to provide an excellent insecticidal, acaricidal and nematicidal agent.

  The present inventors have synthesized various 3-pyrazolyl phenyl sulfide derivatives and studied their physiological activities in order to develop insecticides, acaricides, and nematicides having the preferable characteristics described above. As a result, 3-pyrazolyl phenyl sulfide derivatives represented by the following general formula [I] (hereinafter also referred to as the compound of the present invention) are various agricultural and horticultural pests, particularly spider mites represented by spider mites, kanzawa spider mites, citrus spider mites, etc. Tables for lepidopterous pests such as white-tailed moth, green moth, white-winged beetle, Hemiptera pestidae, Hemiptera pneumoniae, etc., Coleoptera pesticides such as Azuki beetle It has been found that the present invention has an effect, and further has a soil treatment activity that enables a safe and labor-saving application method, and the present invention has been completed.

That is, this invention has the summary characterized by the following.
(1) General formula [I]

[Where:
R ₁ is a C _{1 to} C ₆ alkyl group (the group is a halogen atom, a C _{3 to} C ₆ cycloalkyl group, a hydroxyl group, a cyano group, a C _{2 to} C ₇ alkoxycarbonyl group, a C _{1 to} C ₆ alkoxy group, or may be mono-substituted or poly-substituted by carboxyl _group), C 3 -C ₆ cycloalkyl _group, C 2 -C ₆ alkenyl _group, C 2 -C ₆ alkynyl _group, C 1 -C ₆ alkoxy group, an amino group, a cyano _group, C 1 -C ₆ monoalkylamino group or a di _(C 1 -C ₆ alkyl) amino group,
R ₂ is a C ₁ -C ₆ alkyl group (the group may be mono-substituted or poly-substituted by a halogen atom or a C ₃ -C ₆ cycloalkyl group), a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ shows an alkynyl group or a _C 3 -C ₈ cycloalkyl group,
n represents an integer of 0 to 2,
m represents 0 or 1,
A ₁ is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group (the group is mono-substituted or poly-substituted by a halogen atom, a hydroxyl group, a cyano group, a C ₁ -C ₆ alkoxy group or a C ₂ -C ₇ alkoxycarbonyl group). may be _{substituted),} C 3 -C ₆ cycloalkyl _group, C 2 -C ₆ alkenyl _group, C 2 -C ₆ alkynyl _group, mono- or polysubstituted by C 1 -C ₆ alkoxy group (said group halogen atom may be _{substituted),} C 2 -C ₇ alkoxycarbonyl group, a cyano group, an amino _group, C 1 -C ₆ monoalkylamino group, a di _(C 1 -C ₆ alkyl) amino _group, C 1 -C ₇ acyl a group or a _C 2 -C ₅ haloalkylcarbonyl group,
A ₂ is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group (this group is mono-substituted or poly-substituted by a halogen atom, a cyano group, a C ₂ -C ₇ alkoxycarbonyl group or a C ₁ -C ₆ alkoxy group) C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₆ alkoxy group (the group is mono- or poly-substituted by a halogen atom) may also be), amino _group, C 1 -C ₆ monoalkylamino group, a di _(C 1 -C ₆ alkyl) amino group, a cyano group, a nitro _group, C 1 -C ₇ acyl _group, NR 3 (COR ₄₎ or NR ₃ (COOR ₄ ) group,
R ₃ and R ₄ each independently represent a hydrogen atom or a C _{1 to} C ₆ alkyl group (the group may be mono-substituted or poly-substituted by a halogen atom);
B ₁ represents a hydrogen atom, a halogen atom or a methyl group,
B ₂ represents a halogen atom, a cyano group, a nitro group or a C ₁ -C ₆ alkyl group (this group may be mono-substituted or poly-substituted by a halogen atom). ] The 3-pyrazolyl phenyl sulfide derivative or its salt characterized by the above-mentioned.

(2) The 3-pyrazolyl phenyl sulfide derivative or the salt thereof according to (1), wherein A ₁ and A ₂ are hydrogen atoms.

(3) The 3-pyrazolylphenyl sulfide derivative or the salt thereof according to (1), wherein R ₂ is a cyclopropylmethyl group, a trifluoroethyl group, or a trifluoropropyl group, and A ₁ and A ₂ are hydrogen atoms.

  (4) An agricultural / horticultural insecticidal / acaricidal / nematicidal agent comprising the 3-pyrazolylphenyl sulfide derivative according to (1) to (3) as an active ingredient.

  The compounds of the present invention are semilepidopterous insects, lepidopterous pests, coleopterous pests, diptera pests, hymenoptera pests, straight moth pests, termite pests, thrips pests, spider mites, plant parasitic nematodes It exhibits an excellent control effect against a wide range of pests such as, and can also control pests with resistance.

  In particular, the compound of the present invention is an agro-horticultural pest, spider mites represented by spider mites, kanzawa spider mites, citrus spider mites, etc., lepidopteran pests represented by spider mites, spider mites, white spider mites, etc. Since it exhibits excellent effects on nematodes such as Coleoptera, such as Coleoptera and Azuki beetle, and nematodes such as sweet potato root nematodes, and has excellent osmotic migration, a safe and labor-saving application method by soil treatment is possible.

  The symbols and terms described in this specification will be described.

  A halogen atom shows a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The notation such as C _{1 to} C ₆ indicates that the number of carbon atoms of the subsequent substituent is 1 to 6 in this case.

The C ₁ -C ₆ alkyl group means a linear or branched alkyl group having 1 to 6 carbon atoms unless otherwise specified, and includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, s -Butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, n-hexyl 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 2,2-trimethyl-propyl, 1-ethyl-1-methylpropyl, it may be mentioned groups such as 1-ethyl-2-methylpropyl.

C ₃ -C ₆ unless specifically limited to the cycloalkyl group, a cycloalkyl group having 3 to 6 carbon atoms, may be mentioned for example, cyclopropyl, cyclobutyl, groups such as cyclopentyl or cyclohexyl.

The C ₂ -C ₆ alkenyl group means a straight or branched alkenyl group having 2 to 6 carbon atoms unless otherwise specified. For example, vinyl, 1-propenyl, isopropenyl, 2-propenyl, 1- Butenyl, 1-methyl-1-propenyl, 2-butenyl, 1-methyl-2-propenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1,3-butadienyl, 1- Pentenyl, 1-ethyl-2-propenyl, 2-pentenyl, 1-methyl-1-butenyl, 3-pentenyl, 1-methyl-2-butenyl, 4-pentenyl, 1-methyl-3-butenyl, 3-methyl- 1-butenyl, 1,2-dimethyl-2-propenyl, 1,1-dimethyl-2-propenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1,2- Methyl-1-propenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,3-pentadienyl, 1-vinyl-2-propenyl, 1-hexenyl, 1-propyl-2-propenyl, 2- Hexenyl, 1-methyl-1-pentenyl, 1-ethyl-2-butenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-4-pentenyl, 1-ethyl-3-butenyl, 1- ( Isobutyl) vinyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-2-propenyl, 1- (isopropyl) -2-propenyl, 2-methyl-2-pentenyl, 3-methyl- 3-pentenyl, 4-methyl-3-pentenyl, 1,3-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 3-methyl-4-pentenyl, 4- Tyl-4-pentenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1,5-hexadienyl, 1-vinyl-3- Groups such as butenyl or 2,4-hexadienyl can be mentioned.

The C ₂ -C ₆ alkynyl group means a straight-chain or branched alkynyl group having 2 to 6 carbon atoms unless specifically limited, and includes, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1 -Methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl, 1-methyl-2-butynyl, 4-pentynyl, 1-methyl -3-butynyl, 2-methyl-3-butynyl, 1-hexynyl, 1- (n-propyl) -2-propynyl, 2-hexynyl, 1-ethyl-2-butynyl, 3-hexynyl, 1-methyl-2 -Pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, 1-ethyl-3-butynyl, 1-ethyl 1-methyl-2-propynyl, 1- (isopropyl) -2-propynyl, it may be mentioned 1,1-dimethyl-2-butynyl or 2,2-dimethyl-3 group butynyl.

C ₁ -C ₆ alkoxy group refers to an (alkyl) -O— group in which the alkyl moiety has the above meaning, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, Groups such as pentyloxy, isopentyloxy or hexyloxy can be mentioned.

The C ₁ -C ₇ acyl group means a (alkyl) -C (═O) — group having 1 to 6 carbon atoms in which the formyl group or the alkyl part has the above-mentioned meaning, for example, a group such as acetyl or propionyl. I can give you.

The C ₂ -C ₇ alkoxycarbonyl group refers to a (alkyl) -O—C (═O) — group having 1 to 6 carbon atoms in which the alkyl portion has the above meaning, for example, methoxycarbonyl, ethoxycarbonyl, n -Groups such as propoxycarbonyl or isopropoxycarbonyl may be mentioned.

The C ₂ -C ₅ haloalkylcarbonyl group is a (haloalkyl) -C (═O which is a linear or branched alkyl group having 1 to 4 carbon atoms substituted with the same or different halogen atoms 1 to 9. )-Group, and examples thereof include chloroacetyl, trifluoroacetyl, pentafluoropropionyl, difluoroacetyl and the like.

The C ₁ -C ₆ monoalkylamino group refers to an amino group in which the alkyl part is mono-substituted by the alkyl group having the above meaning, and examples thereof include methylamino, ethylamino, n-propylamino and the like.

The di (C ₁ -C ₆ alkyl) amino group means an amino group in which the alkyl part has the above meaning and is disubstituted, and includes groups such as dimethylamino, diethylamino, N-ethyl-N-methylamino and the like. be able to.

  Next, although the specific example of this invention compound represented by general formula [I] is described in Table 1-Table 9, this invention compound is not limited to these compounds. These compounds include compounds containing optical isomers. The compound number is referred to in the following description.

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

Me: methyl Et: ethyl Pr: n-propyl Pr-i: isopropyl Pr-c: cyclopropyl Bu: n-butyl Bu-t: tert-butyl Pen: n-pentyl Pen-i: isopentyl Hex: n-hexyl

  Although this invention compound of general formula [I] can be manufactured in accordance with the manufacturing method shown below, it is not limited to these methods.

<Manufacturing method 1>
This invention compound of general formula [I-1] can be manufactured by the method which consists of the reaction formula illustrated below.

(In the formula, L ₁ represents a halogen atom, a C _{1 to} C ₆ alkylsulfonyloxy group, a phenylsulfonyloxy group or SO ₂ M, M represents an alkali metal or an alkaline earth metal, and sodium is a preferred alkali metal. Or potassium, and A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ and n have the same meaning as described above.)
That is, the compound of the present invention represented by the general formula [I-1] is obtained by reacting the compound [II] and the compound [III] in a solvent in the presence or absence of a base, in the presence or absence of a radical initiator. It can manufacture by making it react in presence.

Hereinafter, for example, “a compound represented by the general formula [I-1]” and “compound [I-1]” are agreed.
What is necessary is just to select the usage-amount of compound [III] used here from the range of 1-5 mol suitably with respect to 1 mol of compound [II], Preferably it is 1.2-2.0 mol.

  Solvents that can be used in this reaction 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 N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, acetonitrile, propionitrile, etc. Nitriles, esters such as ethyl acetate and ethyl propionate, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, water or a mixed solvent thereof. It is.

  The usage-amount of a solvent is 0.1-100 liter with respect to 1 mol of compound [II], Preferably it is 0.3-10 liter.

  Examples of the base that can be used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate, potassium carbonate and the like. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, sodium ethoxide, potassium tert Metal salts of alcohols such as butoxide or organic bases such as triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene And the like.

  What is necessary is just to select the usage-amount of a base suitably from the range of 0-5 mol with respect to 1 mol of compound [II], Preferably it is 0-1.2 mol.

  Examples of the radical initiator that can be used in this reaction include sulfite addition products such as sulfite, sulfite, and longalite (trade name, sodium, formaldehyde, sulfoxylate). A base and a radical initiator may be used in combination.

  When using a radical initiator, the usage-amount may be suitably selected from the range of 0-5 mol with respect to 1 mol of compound [II], Preferably it is 0.05-1.2 mol.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, It is good to carry out in the range of 0 to 150 degreeC preferably. The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Manufacturing method 2>
As a raw material for the compound [I-1] of the present invention, compound [IV], which is an oxidative dimer of compound [II] used in Production Method 1, can also be used.

(In the formula, L ₂ represents a halogen atom or SO ₂ M, and A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ , M, and n have the same meaning as described above.)
That is, this invention compound [I-1] can be manufactured by making compound [IV] and compound [V] react in presence of a radical initiator in a solvent.

  What is necessary is just to select the usage-amount of compound [V] used here from the range of 1-5 mol suitably with respect to 1 mol of compound [IV], Preferably it is 1.2-2.0 mol.

  Solvents that can be used in this reaction are, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N -Aprotic polar solvents such as methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, nitriles such as acetonitrile and propionitrile, esters such as ethyl acetate and ethyl propionate, pentane, hexane, cyclohexane and heptane Examples thereof include aliphatic hydrocarbons, pyridines such as pyridine and picoline, water, or a mixed solvent thereof.

  The usage-amount of a solvent is 0.1-100 liter with respect to 1 mol of compound [IV], Preferably it is 0.3-10 liter.

  Examples of the radical initiator that can be used in this reaction include sulfite addition products such as sulfite, sulfite, and longalite (trade name, sodium, formaldehyde, sulfoxylate).

  When using a radical initiator, the usage-amount may be suitably selected from the range of 0.01-5 mol with respect to 1 mol of compound [IV], Preferably it is 0.05-1.2 mol.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, It is good to carry out in the range of 0 to 150 degreeC preferably.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Manufacturing method 3>
The compound [I-1] of the present invention can also be produced by a method comprising the reaction formulas exemplified below.

(Wherein A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ and n have the same meaning as described above, L ₃ represents a halogen atom, a C ₁ -C ₆ alkylsulfonyloxy group, phenylsulfonyloxy _group, C 1 -C ₆ alkylsulfonyl group or represents a phenylsulfonyl group.)
That is, the compound [I-1] of the present invention is obtained by oxidizing the compound [VI] and the compound [VII] in a solvent in the presence of any of base, copper or copper (I) oxide, or base and copper or base and oxidation. It can manufacture by making it react in presence of copper (I).

  What is necessary is just to select the usage-amount of compound [VII] used here from the range of 1-5 mol suitably with respect to 1 mol of compound [VI], Preferably it is 1.0-1.2 mol.

  Solvents that can be used in this reaction are, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N -Aprotic polar solvents such as methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol and methyl cellosolve, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridine and picoline And pyridines such as water, and mixed solvents thereof.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [VI].

  Examples of the base that can be used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate, potassium carbonate and the like. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, sodium ethoxide, potassium Metal salts of alcohols such as tert-butoxide or organic compounds such as triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene Bases and the like.

  What is necessary is just to select suitably the usage-amount of a base, copper, and copper oxide (I) from the range of 1-5 mol with respect to 1 mol of compound [VI], Preferably it is 1.0-1.2 mol. .

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -70 degreeC to the recirculation | reflux temperature in a reaction system, Preferably it is good to carry out in 0-150 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Manufacturing method 4>
The compound [I-1] of the present invention can also be produced by a method comprising the reaction formulas exemplified below.

(In the formula, A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ , M and n have the same meaning as described above.)
That is, the compound [I-1] of the present invention is obtained by subjecting the compound [VIII] to a conventional method [method using a mineral acid (such as hydrochloric acid and sulfuric acid) and nitrite or alkyl nitrite] in a solvent. After the diazonium salt, it can be produced by reacting with a mercaptan salt represented by the general formula [IX] or a disulfide represented by the general formula [X].

  The amount of compound [IX] or compound [X] used here may be appropriately selected from the range of 1 to 5 mol, preferably 1.0 to 2.0 mol, per 1 mol of compound [VIII]. It is.

  Solvents that can be used in this reaction 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, and acetonitrile. Aprotic polar solvents such as tolyl, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, acetonitrile, Nitriles such as propionitrile, esters such as ethyl acetate and ethyl propionate, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, water, or this Mixed solvent, and the like.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [VIII].

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the range of -10 degreeC-100 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Manufacturing method 5>
The compound [I-1] of the present invention can also be produced by a method comprising the reaction formulas exemplified below.

(In the formula, Y ₁ represents a hydrogen atom or a halogen atom, and L ₃ , A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ , and n have the same meaning as described above.)
That is, the compound [I-1] of the present invention is produced by reacting the compound [XI] with a metal or organometallic compound in a solvent and then reacting the compound [XII] or the compound [X]. be able to.

  The amount of compound [XII] or compound [X] used here may be appropriately selected from the range of 1 to 5 mol, preferably 1.0 to 2.0 mol, per 1 mol of compound [XI]. It is.

  Solvents that can be used in this reaction include ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, Examples thereof include pyridines such as pyridine and picoline, or a mixed solvent thereof.

  The amount of the solvent to be used is 0.1-100 liter, preferably 0.3-10 liter, per 1 mol of compound [XI].

  Examples of the metal that can be used in this reaction include alkali metals such as lithium and alkaline earth metals such as magnesium.

  What is necessary is just to select the usage-amount of a metal suitably from the range of 1-3 mol with respect to 1 mol of compound [XI], Preferably it is 1.0-1.1 mol.

  Examples of the organometallic compound that can be used in this reaction include alkyl lithium such as n-butyl lithium.

  What is necessary is just to select the usage-amount of an organometallic compound from the range of 1-3 mol suitably with respect to 1 mol of compound [XI], Preferably it is 1.0-1.1 mol.

  The reaction temperature may be selected from an arbitrary temperature range from −90 ° C. to the reflux temperature in the reaction system, preferably in the range of −78 ° C. to 70 ° C., and the reaction time is the reaction temperature, reaction substrate, Although it varies depending on the reaction amount and the like, it is usually 10 minutes to 20 hours.

<Manufacturing method 6>
This invention compound [I-2] can be manufactured also by the method which consists of reaction formula illustrated below.

(In the formula, A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ and n have the same meaning as described above.)
The compound [I-2] of the present invention can be produced by reacting the compound [I-1] with an oxidizing agent in a solvent in the presence or absence of a catalyst.

  Examples of the oxidizing agent that can be used in this reaction include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, oxone (OXONE, trade name of EI DuPont; potassium peroxohydrogensulfate-containing product), N-chloro. Examples thereof include succinimide, N-bromosuccinimide, tert-butyl hypochlorite, and sodium hypochlorite.

  What is necessary is just to select the usage-amount of an oxidizing agent from the range of 1-6 mol suitably with respect to 1 mol of compound [I-1], Preferably it is 1.0-1.2 mol.

  Examples of the catalyst that can be used in this reaction include sodium tungstate.

  What is necessary is just to select the usage-amount of a catalyst suitably from the range of 0-1 mol with respect to 1 mol of compound [I-1], Preferably it is 0.01-0.1 mol.

  Solvents that can be used in this reaction are, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N -Aprotic polar solvents such as methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, pentane, hexane, cyclohexane and Examples thereof include aliphatic hydrocarbons such as heptane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetic acid, water, and a mixed solvent thereof.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [I-1].

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the range of -10 degreeC-100 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Manufacturing method 7>
The compound [I] of the present invention can also be produced by a method comprising the reaction formulas exemplified below.

(In the formula, A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ , n and m have the same meaning as described above.)
That is, the compound [I] of the present invention can be produced by reacting compound [XIII] with compound [XIV] and an anhydrous copper salt in a solvent in the presence of an organic base.

  What is necessary is just to select the usage-amount of compound [XIV] used here from the range of 1-5 mol suitably with respect to 1 mol of compound [XIII], Preferably it is 1.0-2.0 mol.

  The solvent that can be used in this reaction may be any solvent that 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, and 1,2 -Ethers such as dimethoxyethane and dioxane; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aprotic polar solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; Examples thereof include aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, and mixed solvents thereof.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [XIII].

  Examples of anhydrous copper salts that can be used in this reaction include anhydrous copper acetate.

  What is necessary is just to select the usage-amount of an anhydrous copper salt from the range of 1-5 mol suitably with respect to 1 mol of compound [XIII], Preferably it is 1.2-2.2 mol.

  Examples of the organic base that can be used in this reaction include triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, and the like. can give.

  What is necessary is just to select the usage-amount of an organic base from the range of 1-5 mol suitably with respect to 1 mol of compound [XIII], Preferably it is 1.2-4.4 mol.

  The reaction temperature may be selected from an arbitrary temperature range from 0 ° C. to the reflux temperature in the reaction system, and preferably in the range of 10 ° C. to 30 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 8 to 48 hours.

<Manufacturing method 8>
In the present compound [I], B ₂ is a cyano group, if having an electron withdrawing group such as nitro group, can be prepared by a process comprising exemplified by the following scheme.

(In the formula, L ₄ represents a leaving group such as a halogen atom, a C ₁ -C ₆ alkylsulfonyloxy group or a phenylsulfonyloxy group, and A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ , n and m have the same meaning as described above.)
That is, the compound [I] of the present invention can be produced by reacting the compound [XIII] and the compound [XV] in a solvent in the presence of a base.

  Here, the amount of compound [XV] to be used may be appropriately selected from the range of 1 to 5 mol, preferably 1.0 to 1.2 mol, per 1 mol of compound [XIII].

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

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [XIII].

  Examples of the base that can be used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate, potassium carbonate and the like. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, sodium ethoxide, potassium tert Metal salts of alcohols such as butoxide or organic bases such as triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene And the like.

  What is necessary is just to select the usage-amount of a base from the range of 1-5 mol suitably with respect to 1 mol of compound [XIII], Preferably it is 1.1-1.2 mol.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -70 degreeC to the recirculation | reflux temperature in a reaction system, Preferably it is good to carry out in -20 degreeC-150 degreeC.

The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.
<Manufacturing method 9>
This invention compound [I-3] can be manufactured by the method of consisting of the reaction formula illustrated below.

(In the formula, A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ , L ₁ , and m have the same meaning as described above.)
That is, compound [I-3] which is the compound of the present invention comprises compound [XVI] and compound [III-b] in a solvent in the presence or absence of a base, in the presence or absence of a radical initiator. It can manufacture by making it react under.

  What is necessary is just to select the usage-amount of compound [III-b] used here from the range of 1-5 mol suitably with respect to 1 mol of compound [XVI], Preferably it is 1.2-2.0 mol.

  Solvents that can be used in this reaction 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 N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, acetonitrile, propionitrile, etc. Nitriles, esters such as ethyl acetate and ethyl propionate, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, water or a mixed solvent thereof. It is.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [XVI].

  Examples of the base that can be used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate, potassium carbonate and the like. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, sodium ethoxide, potassium tert Metal salts of alcohols such as butoxide or organic bases such as triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene And the like.

  What is necessary is just to select the usage-amount of a base from the range of 0-5 mol suitably with respect to 1 mol of compound [XVI], Preferably it is 0-1.2 mol.

  Examples of the radical initiator that can be used in this reaction include sulfurous acid adducts such as sulfurous acid, sulfite, and longalite (sodium, formaldehyde, sulfoxylate). A base and a radical initiator may be used in combination.

  When using a radical initiator, the usage-amount may be suitably selected from the range of 0-5 mol with respect to 1 mol of compound [XVI], Preferably it is 0.05-1.2 mol.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, It is good to carry out in the range of 0 to 150 degreeC preferably.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Manufacturing method 10>
The compound [I] of the present invention can also be produced by a method comprising the reaction formulas exemplified below.

(In the formula, A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ , n and m have the same meaning as described above.)
The compound [I] of the present invention can be produced by reacting the compound [I-3] with an oxidizing agent in a solvent in the presence or absence of a catalyst.

  Examples of the oxidizing agent that can be used in this reaction include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, oxone (OXONE, trade name of EI DuPont; potassium peroxohydrogensulfate-containing product), N-chloro. Examples thereof include succinimide, N-bromosuccinimide, tert-butyl hypochlorite, and sodium hypochlorite.

  What is necessary is just to select the usage-amount of an oxidizing agent from the range of 1-6 mol suitably with respect to 1 mol of compound [I-3], Preferably it is 1.0-1.2 mol.

  Examples of the catalyst that can be used in this reaction include sodium tungstate.

  What is necessary is just to select the usage-amount of a catalyst suitably from the range of 0-1 mol with respect to 1 mol of compound [I-3], Preferably it is 0.01-0.1 mol.

  Solvents that can be used in this reaction are, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N -Aprotic polar solvents such as methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, pentane, hexane, cyclohexane and Examples thereof include aliphatic hydrocarbons such as heptane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetic acid, water, and a mixed solvent thereof.

  The usage-amount of a solvent is 0.1-100 liter with respect to 1 mol of compound [I-3], Preferably it is 0.3-10 liter.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the range of -10 degreeC-100 degreeC.

The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.
<Manufacturing method 11>
The compound [I-5] of the present invention can be produced by a method consisting of the reaction formulas exemplified below.

(In the formula, X represents a halogen atom, and A ₁ , B ₁ , B ₂ , R ₁ , R ₂ , n and m have the same meaning as described above.)
That is, the compound [I-5] of the present invention is obtained by subjecting the compound [I-4] to a conventional method [a method using a mineral acid (such as hydrochloric acid and sulfuric acid) and a nitrite or an alkyl nitrite]. The diazonium salt can be prepared by reacting with copper halide.

  Examples of the copper halide that can be used in this reaction include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (II) chloride, and copper (II) bromide.

  What is necessary is just to select the usage-amount of the copper halide used here from the range of 0.5-5 mol suitably with respect to 1 mol of compound [I-4], Preferably it is 0.5-2.0 mol. .

  Solvents that can be used in this reaction 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, and acetonitrile. Aprotic polar solvents such as tolyl, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, acetonitrile, Nitriles such as propionitrile, esters such as ethyl acetate and ethyl propionate, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, water, or this Mixed solvent, and the like.

  The usage-amount of a solvent is 0.1-100 liter with respect to 1 mol of compound [I-4], Preferably it is 0.3-10 liter.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the range of -10 degreeC-100 degreeC.

The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.
<Manufacturing method 12>
This invention compound [I-6] can be manufactured by the method of consisting of Reaction formula illustrated below.

(In the formula, A ₁ , B ₁ , B ₂ , R ₁ , R ₂ , n and m have the same meaning as described above.)
That is, the compound [I-6] of the present invention is obtained by subjecting compound [I-4] to a conventional method [method using mineral acid (such as hydrochloric acid and sulfuric acid) and nitrite or nitrite] in a solvent. After diazotization, it can be produced by denitrification.

  The amount of the mineral acid to be used is 0 mol to large excess, preferably 0 to 5 mol, per 1 mol of compound [I-4].

  The usage-amount of nitrite or nitrites is 1-5 mol with respect to 1 mol of compound [I-4], Preferably it is 1-2 mol.

  Solvents that can be used in this reaction 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, and acetonitrile. Aprotic polar solvents such as tolyl, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, acetonitrile, Nitriles such as propionitrile, esters such as ethyl acetate and ethyl propionate, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, water, or this Mixed solvent, and the like.

  The usage-amount of a solvent is 0.1-100 liter with respect to 1 mol of compound [I-4], Preferably it is 0.3-10 liter.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the range of -10 degreeC-100 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Manufacturing method 13>
The compound [I] of the present invention can also be produced by a method comprising the reaction formulas exemplified below.

(In the formula, A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , R ₂ , X, n, and m have the same meaning as described above.)
(Process A)
The compound [I] of the present invention is obtained by subjecting compound [I-4] and an electrophilic reagent to dehydration condensation in the presence or absence of a solvent, in the presence or absence of a base, in the presence or absence of an acid. It can be produced by reacting in the presence or absence of an agent.

  Electrophilic reagents that can be used in this step include halogenated alkanes such as methyl iodide, ethyl iodide, and propyl iodide, acid anhydrides such as acetic anhydride, trifluoroacetic anhydride, and chlorodifluoroacetic anhydride, acetyl chloride, Examples include acyl halides such as propionyl chloride, difluoroacetyl chloride, trifluoroacetyl chloride, methylchloroformate, and ethylchloroformate, and alcohols such as methanol, ethanol, and benzyl alcohol.

  The amount of the electrophilic reagent used may be appropriately selected from the range of 1 to 100 mol, preferably 1 to 10 mol, more preferably 1 to 3 mol, relative to 1 mol of compound [I-4]. is there.

  Examples of the solvent that can be used in this step include ethers such as diethyl ether, tetrahydrofuran, and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, Aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol and isopropyl alcohol, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, pentane, hexane and cyclohexane And aliphatic hydrocarbons such as heptane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, or a mixed solvent thereof.

  The usage-amount of a solvent is 0-100 liter with respect to 1 mol of compound [I-4], Preferably it is 0-10 liter.

  When a base is used in this step, the usable base is, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide, or carbonate. Inorganic bases such as alkali metal carbonates such as sodium and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide , Metal salts of alcohols such as sodium ethoxide and potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0]- And organic bases such as 7-undecene.

  What is necessary is just to select the usage-amount of a base suitably from the range of 0-3 mol with respect to 1 mol of compound [I-4], Preferably it is 0.1-2 mol, More preferably, it is 0.1-1. 2 moles.

  When an acid is used in this step, usable acids are, for example, sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid, inorganic acids such as hydrochloric acid, hydrobromic acid or sulfuric acid, carboxylic acids such as acetic acid or trifluoroacetic acid Examples include acids.

  What is necessary is just to select the usage-amount of an acid suitably from the range of 0-5 mol with respect to 1 mol of compound [I-4], Preferably it is 0.01-2 mol, More preferably, it is 0.03-1. 0 mole.

  Examples of the dehydrating condensing agent that can be used include carbodiimides such as dicyclohexylcarbodiimide.

  When the dehydrating condensing agent is used, the amount of the dehydrating condensing agent may be appropriately selected from the range of 0 to 3 mol, preferably 1.0 to 1.2 mol, relative to 1 mol of the compound [I-4]. is there.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -20 degreeC to the recirculation | reflux temperature in a reaction system, It is good to carry out in the range of 0 to 80 degreeC preferably.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 15 minutes to 24 hours.

(Process B)
The compound [I] of the present invention can be produced by reacting the compound [I-5] with the compound [XVII] in a solvent in the presence or absence of a base.

  When a base is used in this step, the usable base is, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide, or carbonate. Inorganic bases such as alkali metal carbonates such as sodium and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide , Metal salts of alcohols such as sodium ethoxide and potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0]- And organic bases such as 7-undecene.

  What is necessary is just to select the usage-amount of a base from the range of 0-10 mol suitably with respect to 1 mol of compound [I-5], Preferably it is 1-3 mol, More preferably, it is 1.0-1.2 mol It is.

  Examples of the solvent that can be used in this step include ethers such as diethyl ether, tetrahydrofuran, and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, Aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol and isopropyl alcohol, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, pentane, hexane and cyclohexane And aliphatic hydrocarbons such as heptane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, or water, and a mixed solvent thereof can also be used.

  The usage-amount of a solvent is 0.1-100 liter with respect to 1 mol of compound [I-5], Preferably it is 0.1-10 liter.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -20 degreeC to the reflux temperature in a reaction system, It is good to carry out in the range of -10 degreeC-150 degreeC preferably.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 15 minutes to 12 hours.

<Intermediate Production Method 1>
Production of production intermediate [XVI]

(In the formula, A ₁ , A ₂ , B ₁ , B ₂ , R ₂ , M and m have the same meaning as described above.)
(Process C)
Compound [XX] can be produced by reacting compound [XVIII], compound [XIX] and bromine in a solvent.

  Solvents that can be used in this step are ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N- Aprotic polar solvents such as methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol and isopropyl alcohol, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, pentane, hexane, cyclohexane and heptane And aliphatic hydrocarbons such as acetone, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and water.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.1 to 10 liters, per 1 mol of compound [XVIII].

  What is necessary is just to select suitably the compound [XIX] usage-amount used at this process from the range of 1-5 mol with respect to 1 mol of compound [XVIII], Preferably it is 1.0-2.0 mol.

  What is necessary is just to select the usage-amount of the bromine used at this process suitably from the range of 1-5 mol with respect to 1 mol of compound [XVIII], Preferably it is 1.0-2.0 mol.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the temperature range of -20 degreeC-100 degreeC.

The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.
(Process D)
Compound [XVI] can be produced by reacting compound [XX] with a reducing agent in a solvent.

  Examples of the reducing agent that can be used in this step include lithium aluminum hydride and sodium tetrahydroborate.

  What is necessary is just to select the usage-amount of the reducing agent used at this process suitably from the range of 1-5 mol with respect to 1 mol of compound [XX], Preferably it is 1.0-2.0 mol.

  Solvents that can be used in this step are ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N- Aprotic polar solvents such as methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol and isopropyl alcohol, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, pentane, hexane, cyclohexane and heptane And aliphatic hydrocarbons such as acetone, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and water.

  The usage-amount of a solvent is 0.1-100 liter with respect to 1 mol of compound [XX], Preferably it is 0.1-10 liter.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the temperature range of -20 degreeC-100 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Intermediate production method 2>
Production of Production Intermediates [II] and [IV] Compound [II] can be produced by the following steps E, F, G and H, and compound [IV] can be produced by the following step I.
Compound [II] and compound [IV] can be converted into each other by an oxidation-reduction reaction, and compound [II] may be easily oxidized by oxygen in the air to become compound [IV]. .

(In the formula, R ₂ ′ represents a methyl group or a trifluoromethyl group, and A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , L ₃ and n have the same meaning as described above.)
(Process E)
That is, the target compound [II] is obtained by oxidizing compound [XXI] with an oxidizing agent to form methyl sulfoxide, and then reacting with acetic anhydride or trifluoroacetic anhydride to produce compound [XXII]. It can be produced by conventional hydrolysis.

  Examples of the oxidizing agent that can be used in this step include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, oxone (OXONE, trade name of EI Dupont, containing potassium peroxohydrogensulfate), N-chloro. Examples thereof include succinimide, N-bromosuccinimide, tert-butyl hypochlorite, and sodium hypochlorite.

  What is necessary is just to select the usage-amount of an oxidizing agent from the range of 1-3 mol suitably with respect to 1 mol of compounds of general formula [XXI], Preferably it is 1.0-1.2 mol.

  The amount of acetic anhydride or trifluoroacetic anhydride to be used can also be used as a reaction solvent from 1 mol to 1 mol of compound [XXI], and preferably 1.0 to 3.0 mol.

  In any reaction, the reaction temperature may be selected from an arbitrary temperature range from −10 ° C. to the reflux temperature in the reaction system, and preferably in the temperature range of 0 ° C. to 50 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 5 minutes to 12 hours.

(Process F)
Compound [II] can be produced by reacting compound [VI] with a metal or organometallic compound in a solvent and then reacting with sulfur.

  Examples of the solvent that can be used in this step 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, and mixed solvents thereof.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [VI].

  Examples of the metal that can be used in this step include lithium and magnesium.

  What is necessary is just to select the usage-amount of a metal suitably from the range of 1-3 mol with respect to 1 mol of compound [VI], Preferably it is 1.0-1.2 mol.

  Examples of the organometallic compound that can be used in this step include alkyllithiums such as n-butyllithium.

  What is necessary is just to select the usage-amount of an organometallic compound from the range of 1-3 mol suitably with respect to 1 mol of compound [VI], Preferably it is 1.0-1.2 mol.

  What is necessary is just to select the usage-amount of sulfur suitably from the range of 1-5 mol with respect to 1 mol of compound [VI], Preferably it is 1.0-2.0 mol.

  In any reaction, the reaction temperature may be selected from an arbitrary temperature range from −60 ° C. to the reflux temperature in the reaction system, and preferably in the temperature range of −60 ° C. to room temperature.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 30 minutes to 12 hours.

(Process G)
Compound [II] is obtained by converting compound [VIII] into a diazonium salt by a conventional method [method using mineral acid (such as hydrochloric acid and sulfuric acid) and nitrite or alkyl nitrite], and then xanthate or thiocyanate. It can be produced by reacting with a salt and subjecting it to alkaline hydrolysis.

  What is necessary is just to select the usage-amount of a xanthate or thiocyanate from the range of 1-3 mol suitably with respect to 1 mol of compound [VIII], Preferably it is 1.0-1.5 mol.

What is necessary is just to select reaction temperature from the range of arbitrary temperature from -70 degreeC to the reflux temperature in a reaction system, It is good to carry out in the temperature range of -20 degreeC-100 degreeC preferably.
The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

(Process H)
Compound [II] reacts compound [XXIII] with chlorosulfonic acid to give a sulfonyl chloride represented by the general formula [XXIV], which is lithium aluminum hydride, zinc / acid, tin / acid or red phosphorus / iodine. It can manufacture by reducing using.

  What is necessary is just to select the usage-amount of the chlorosulfonic acid used at this process suitably from the range of 2-5 mol with respect to 1 mol of compound [XXIII], Preferably it is 2.2-3.0 mol.

  Examples of the acid include hydrochloric acid and sulfuric acid.

  The amount of lithium aluminum hydride, zinc / acid, tin / acid, red phosphorus / iodine used may be appropriately selected from the range of 1 to 5 mol, preferably 1.5 to 2 with respect to 1 mol of compound [XXIV]. 0.0 mole.

  In any reaction, the reaction temperature may be selected from an arbitrary temperature range from 0 ° C. to the reflux temperature in the reaction system, and is preferably performed in a temperature range of 0 ° C. to 100 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

(Process I)
Compound [IV] can be produced by reacting compound [XXIII] with disulfur dichloride in a solvent in the presence or absence of a catalyst.

  What is necessary is just to select the usage-amount of sulfur dichloride from the range of 1-5 mol suitably with respect to 1 mol of compound [XXIII], Preferably it is 1.1-1.5 mol.

  Examples of the catalyst that can be used in this step include Lewis acid catalysts such as aluminum chloride, tin (II) chloride, and tin (IV) chloride.

  What is necessary is just to select the usage-amount of a catalyst from the range of 1-5 mol suitably with respect to 1 mol of compound [XXIII], Preferably it is 1.1-2.0 mol.

  Examples of the solvent that can be used in this step include halogenated hydrocarbons such as dichloromethane, chloroform, and dichloroethane, and aromatic hydrocarbons such as chlorobenzene and dichlorobenzene.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [XXIII].

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the range of -10 degreeC-100 degreeC.

The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 1 to 20 hours.
Furthermore, compound [II] can be produced by reducing compound [IV] by a conventional method.

<Intermediate production method 3>
In compound [II], when B ₂ is an electron-withdrawing group such as a cyano group or a nitro group, a synthetic intermediate of general formula [II] can be produced by a method consisting of the reaction formulas exemplified below. .

(In the formula, A ₁ , A ₂ , B ₁ , B ₂ , R ₁ , L ₃ and n have the same meaning as described above.)
That is, the target compound [II] can be produced by reacting compound [VI] with sodium sulfide in a solvent in the presence of a base and then neutralizing with a mineral acid or the like.

  What is necessary is just to select the usage-amount of the sodium sulfide used here from the range of 1-3 mol suitably with respect to 1 mol of compound [VI], Preferably it is 1.0-1.5 mol.

  Solvents that can be used in this step are ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N- Aprotic polar solvents such as methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol and isopropyl alcohol, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, pentane, hexane, cyclohexane and heptane And aliphatic hydrocarbons such as acetone, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and water.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [VI].

  Examples of the base that can be used in this step include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate and potassium carbonate. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, sodium ethoxide, potassium Metal salts of alcohols such as tert-butoxide or organic compounds such as triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene Bases and the like.

  What is necessary is just to select the usage-amount of a base from the range of 1-5 mol suitably with respect to 1 mol of compound [VI], Preferably it is 1.0-1.2 mol.

  Examples of the mineral acid include hydrochloric acid and sulfuric acid.

  What is necessary is just to select the usage-amount of a mineral acid from the range of 1-5 mol suitably with respect to 1 mol of compound [VI], Preferably it is 1.0-2.0 mol.

  What is necessary is just to select reaction temperature from the range of arbitrary temperature from -30 degreeC to the reflux temperature in a reaction system, Preferably it is good to carry out in the temperature range of -20 degreeC-100 degreeC. The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

<Intermediate production method 4>
Synthesis of production intermediate [XVIII-1]

(In the formula, A ₁ , B ₁ , B ₂ , R ₂ and m have the same meaning as described above.)
(Process J)
Compound [XVIII-1] is obtained by reacting compound [XXVI] with compound [XXVII] in a solvent in the presence or absence of an acid to form compound [XXVIII], followed by cyclization reaction in the solvent. Can be manufactured.

  What is necessary is just to select the usage-amount of compound [XXVII] used here from the range of 1-5 mol suitably with respect to 1 mol of compound [XXVI], Preferably it is 1.0-1.1 mol.

  Solvents that can be used in this step include, for example, 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 N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, acetonitrile, propionitrile, etc. Nitriles, esters such as ethyl acetate and ethyl propionate, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, water, or a mixed solvent thereof And the like.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [XXVI].

  Examples of the acid that can be used in this step include sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, inorganic acids such as hydrochloric acid, hydrobromic acid and sulfuric acid, and carboxylic acids such as acetic acid and trifluoroacetic acid.

What is necessary is just to select the usage-amount of an acid suitably from the range of 0-5 mol with respect to 1 mol of compound [XXVI], Preferably it is 0-2 mol.
In any reaction, the reaction temperature may be selected from an arbitrary temperature range from 0 ° C. to the reflux temperature in the reaction system, and preferably in the temperature range of 0 ° C. to 100 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

(Process K)
Compound [XVIII-1] can be produced by reacting compound [XXVI] with compound [XXIX] or [XXX] in a solvent in the presence or absence of a base.

  The amount of compound [XXIX] or [XXX] used here may be appropriately selected from the range of 1 to 5 mol, preferably 1.0 to 1.1 mol, relative to 1 mol of compound [XXVI]. is there.

  Solvents that can be used in this step include, for example, 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 N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropyl alcohol, acetonitrile, propionitrile, etc. Nitriles, esters such as ethyl acetate and ethyl propionate, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, water, or a mixed solvent thereof And the like.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [XXVI].

  Examples of the base that can be used in this step include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate and potassium carbonate. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, sodium ethoxide, potassium Metal salts of alcohols such as tert-butoxide or organic compounds such as triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene Bases and the like.

  The amount of the base to be used is 0 to large excess mol, preferably 0 to 1.2 mol, per 1 mol of compound [XXVI].

<Intermediate production method 5>
The phenylhydrazine represented by the general formula [XXVI-b] is prepared from the corresponding aniline in a conventional manner, for example, Comprehensive Organic Functional Group Transformations Vol. 2, Vol. It can be synthesized according to the method described on page 769.

(In the formula, B ₁ , B ₂ and R ₂ have the same meaning as described above, and Ac represents an acetyl group.)
Compound [XXXV] is a disulfide represented by the general formula [XXXIII] or a thiol represented by the general formula [XXXIV] in the same manner as described in the intermediate production method 2 for the acetanilide represented by the general formula [XXXI]. Furthermore, it can be produced by using the method described in the production method 1 or the production method 2.

  As the solvent, base, and radical initiator that can be used in this step, the same solvents as those used in Production Method 1 or Production Method 2 can be used.

  The phenylhydrazine represented by the general formula [XXVI-b] is a diazonium salt obtained by converting the compound [XXXV] into a conventional method [method using a mineral acid (such as hydrochloric acid and sulfuric acid) and nitrite or nitrite]. And reduced with zinc powder, sulfites, tin chloride, and the like.

  Examples of the mineral acid include hydrochloric acid and sulfuric acid.

  What is necessary is just to select the usage-amount of a mineral acid from the range of 2-10 mol suitably with respect to 1 mol of compound [XXXV], Preferably it is 3-5 mol.

  What is necessary is just to select the usage-amount of nitrite or nitrite ester suitably from the range of 1.0-5.0 mol with respect to 1 mol of compound [XXXV], Preferably it is 1.0-1.2 mol.

  In any reaction, the reaction temperature may be selected from a temperature range of −20 ° C. to 50 ° C., and preferably in the temperature range of −5 ° C. to 20 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 30 minutes to 5 hours.

  When the compound of the present invention is used as an active ingredient of a pest control agent, the compound of the present invention may be used as it is, but carriers, surfactants, and other auxiliary agents generally used for formulation as agricultural chemical adjuvants. Formulated with emulsion, suspension, powder, granule, tablet, wettable powder, water solvent, liquid, flowable, granule wettable powder, aerosol, paste, oil, emulsion, smoke It can be formulated into various forms such as an agent. These blending ratios are usually 0.1 to 90% by weight of the active ingredient and 10 to 99.9% by weight of the agrochemical adjuvant.

  Carriers used in the formulation herein are classified into solid carriers and liquid carriers. Examples of solid carriers include animal and vegetable powders such as starch, activated carbon, soybean flour, wheat flour, wood flour, fish flour, and milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, ammonium sulfate, and urea. Inorganic powders such as Examples of the liquid carrier include water; alcohols such as isopropyl alcohol and ethylene glycol; ketones such as cyclohexanone, methyl ethyl ketone and isophorone; ethers such as dioxane and tetrahydrofuran; aliphatic hydrocarbons such as kerosene and light oil; xylene and trimethyl. Aromatic hydrocarbons such as benzene, 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 dimethyl sulfoxide.

  Examples of the surfactant include alkylbenzene sulfonic acid metal salt, dinaphthylmethane disulfonic acid metal salt, alcohol sulfate ester salt, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether, Examples thereof include polyoxyethylene sorbitan monoalkylate, salt of naphthalenesulfonic acid formalin condensate, and the like.

  Other adjuvants include, for example, carboxymethyl cellulose, gum arabic, sodium alginate, guar gum, tragacanth gum, polyvinyl alcohol and other sticking agents or thickeners, metal soap and other antifoaming agents, fatty acids, alkyl phosphates, silicones, paraffins And the like, and physical property improvers, colorants and the like can be used.

  In actual use of these preparations, they can be used as they are or diluted to a predetermined concentration with a diluent such as water. Application of various preparations containing the compound of the present invention, or dilutions thereof, is usually carried out by a commonly used application method, ie, spraying (eg spraying, misting, atomizing, dusting, dusting, water surface application, box application). Etc.), soil application (for example, mixing, irrigation, etc.), surface application (for example, application, powder coating, coating, etc.), immersion, poison bait, smoke application, etc. It is also possible to feed the livestock with the active ingredient in a feed to control the occurrence and growth of harmful insects, particularly harmful insects, in the excreta. It can also be applied by the so-called ultra-high concentration and small quantity spraying method. In this method, it is possible to contain 100% of the active ingredient. The blending ratio of the active ingredient is appropriately selected as necessary, but 0.1 to 20% (weight) when used as a powder and granule, and 1 to 80% (weight) when used as an emulsion and wettable powder. Is appropriate.

  Application of the pest control agent of the present invention is generally carried out at an active ingredient concentration of 0.1 to 5000 ppm when it is diluted with a diluent. When the preparation is used as it is, the application amount per unit area is 0.1 to 5000 g per ha as an active ingredient compound, but is not limited thereto.

  In addition, it goes without saying that the compound of the present invention alone is sufficiently effective, but if necessary, other fertilizers, agricultural chemicals such as insecticides, acaricides, nematicides, bactericides, antiviral agents, It can be mixed and used in combination with attractants, herbicides, plant growth regulators, and the like, and in this case, a more excellent effect may be exhibited.

  Representative examples of insecticides, fungicides, acaricides and the like that 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, bamidothion, phenthoate, dimethoate , Formothion, malathion, trichlorfon, thiometon, phosmet, dichlorvos, acephate, EPBP (EPBP), parathion-methyl, oxydimethone Methyl (oxydemeton-methyl), ethion, dioxabenzofos, cyanophos, isoxathion, pyridaphenthion, phosalone, methidathio (Methidathion), sulprofos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, disulfoton, profenofos ), Pyraclofos, monocrotophos, azinphos-methyl, aldicarb, metomyl, thiodicarb, carbofuran, carbosulfan, benfuracarb ), Furathiocarb, propoxur, fenobucarb, metolcarb, isoprocarb, carbaryl, pirimicarb, ethiophene Ethiofencarb, dichlofenthion, pirimiphos-methyl, quinalphos, chlorpyrifos-methyl, prothiofos, nared, EPN (EPN), XMC (XMC), Bendiocarb, bendiocarb, oxamyl, alanycarb, chlorethoxyfos, etc. Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate , Fenpropathrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, proparthrin, phenothrin, protothrin (Prothrin), fluvalinate, cyfluthrin, cyhalothrin, flucythrinate, etofenprox, cycloprothrin, tralomethrin, silafluofen Tefluthrin, bifenthrin, acrinathrin and the like.

  Acylurea, other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, teflubenzuron, flufenoxuron, flucyclooxuron flucycloxuron, buprofezin, pyriproxyfen, lufenuron, cyromazine, metoprene, endosulfan, diafenthiuron, imidacloprid (imidacloprid), acetamiprid, nitenpyram, clothianidin, dinotefuran, thiamethoxam, thiacloprid, pymetrozine, fipronil (Fipronil), pyridalyl, nicotine-sulfate, rotenone, metaldehyde, machine oils, microbial pesticides such as BT and entomopathogenic viruses, phenoxycarb , Cartap, thiocyclam, bensultap, tebufenozide, chlorfenapyr, emamectin-benzoate, acetamiprid, aceticiprid, nitenpyram, oleic acid sodium salt), rape seed oil and the like.

  Nematicides: fenamiphos, fosthiazate, ethoprophos, methyl isothiocyanate, methyl isocyanate, 1,3-dichloropropene, DCIP (DCIP) and the like.

  Acaricides: chlorobenzilate, phenisobromolate, dicohol, amitraz, propargite, benzomate, hexythiazox, fenbutatin oxide oxide, polynactins, quinomethionate, chlorfenson, tetradifon, abamectin, milbemycin, clofentezine, pyridaben, fenpyroximate (fenpyroximate) ), Tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor, etoxazole, bifenazate, acequinosyl ( acequinocyl), halfenprox, spirodiclofen, etc.

  Bactericides: thiophanate-methyl, benomyl, carbendazol, thiabendazole, folpet, thiuram, ziram, zineb, maneb ), Polycarbamate, iprobenfos, edifenphos, fthalide, probenazole, isoprothiolane, chlorothalonil, captan, polyoxin, blastsai Gin S (blasticidin-S), kasugamycin, streptomycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil mepronil, flutolanil, pencicuron, iprodione, hymexazol, metalaxyl, triflumizole, triforine, triadimefon, ertanol, bitteranol Fenarimol, propiconazole, cymoxanil, prochloraz, pefurazoate, hexaconazole, microbutanyl, diclomezine, tecloftal, tecloftal (Propineb), dithianon, fosetyl, vinchlozoline, procymidone, oxadixyl, guazatine, propamocarb hydrochloride (propineb) propamocarb), fluazinam, oxolinic acid, hydroxyisoxazole, mepanipyrim, etc.

  The compounds of the present invention are semilepidopterous insects, lepidopterous pests, coleopterous pests, diptera pests, hymenoptera pests, straight moth pests, termite pests, thrips pests, spider mites, plant parasitic nematodes It shows excellent control effect against such pests. Examples of such pests include the following pests.

  Hemiptera pests such as Riptortus clavatus, Nezara viridula, Lyme sp., Blissus leucopterus, Stephanitis nashi, etc. Heteroptera), leafhoppers (Nephotettix cincticeps), leafhoppers such as Empoasca sp., Erythroneura sp., Circulifer sp. Planthoppers, Psylla sp. And other killer whales, Silver leaf whitefly (Bemisia tabaci), Whitefly whitefly (Trialeurodes vaporariorum) whitefly, Grape aphid (Viteus vitifolii), Peach aphid (Myzus persicae), Aphis aphid pomi), cotton aphid (A aphids such as phis gossypii), Aphis fabae, Rhopalosiphum psedobrassicas, Aulacorthum solani, Schizaphis graminum, Pseudococ Scale insects such as the scale insect (Comstockaspis perniciosa) and the scale insect (Unaspis yanonensis), and the scale turtle (Rhodnius sp.).

  Lepidopterous pests, such as Homona magnanima, Adoxophyes orana, Sparganothis pilleriana, Grapholitha molesta, Leguminivora glycinivorella, Spaspanobea , Mosquitoes such as Eupoecillia ambiguella, minoga such as Bambalina sp., Nesting moths (Nemapogon granellus), squirrels (Tinea translucens), and hummingbirds such as lingon moth (Lyonetia prunifoliella) Hosogaga such as Phyllonorycter rigoniella, Pseudomonas such as Phyllocnistis citrella, Suga such as Plutella xylostella, Prays citri, Paranthrene regalis, Paranthreneon moth, Synanthedon sp. (Pectinophora gossypiella), Potato moth (Phthorimaea operculella), Stomopteryx sp. ), Ostrinia nubilalis, Ostrinia furnacalis, Hellula undalis, Honey moth (Galleria mellonella), Elasmopalpus lignosellus, Loxostege sticticalis, etc., Pieris rapae ) And other species, such as male moth (Malacosoma neustria), male moths such as Manduca sexta, giant moths (Euproctis pseudoconspersa), Japanese moths (Lymantria dispar) and other species, Hyphantria cunea, etc. Taba Bad worms (Heliothis virescens), ball worms (Helicoverpa zea), scallop moth (Spodoptera exigua), giant cigarette moth (Helicoverpa armigera), Spodoptera litura, mamestra brassicae, paramedo, iron Yagas such as Trichoplusia ni.

  Coleopterous insects, for example, Anomala cuprea, Popillia japonica, Scarabae (Anomala rufocuprea), Eutheola rugiceps, etc., wire worms (Agriotes sp.), Connodeus sp. (Epilachna vigintioctopunctata), ladybirds such as common beetle (Epilachna varivestis), bark beetles such as Tribolium castaneum, Anoplophora malasiaca, tusnoaccelus tuss, Monochamus alternatus ), Beetle weevil (Callosobruchus chinensis), Colorado potato beetle (Leptinotarsa decemlineata), corn root worm (Diabrotica sp.), Rice plant beetle (Oulema oryzae), chaetococci beetle (Chaetoc) nema concinna), Phaedon cochlearias, Oulema melanopus, Dicladispa armigera and other potato beetles, Apion godmani and other weevil weevil (Lissorhoptrus oryzophilus) Large weeviles, bark beetles, cutworms, beetles, etc.

  Diptera pests such as Tipra ano, Tanytarsus oryzae, Oreseolia oryzae, Ceratitis capitata, Hydrellia griseola, Sutro ros D (Oscinella frit), rice flies (Chlops oryzae), common beetle (Ophiomyia phaseoli), bean fly (Liriomyza trifolii), red beetle (Pegomya hyoscyami), fly fly (Hylemia platura), sorghum fly (Atherigona soccae) Musca domestica, Gastrophilus sp., Stomoxys sp., Aedes aegypti, Culex pipiens, Anopheles slnensis, Culex tritaeniorhynchus, etc.

  Hymenopteran pests, for example, Cephus sp., Harmolita sp., Athalia sp., Vespa sp., Fire ant, etc.

  Diptera, such as German cockroach (Blatella germanica), American cockroach (Periplaneta americana), Kera (Gryllotalpa africana), Grasshopper (Locusta migratoria migratoriodes), Melanoplus sanguinipes, etc.

  Termite pests, for example, Yamato termites (Reticulitermes speratus), termites (Coptotermes formosanus) and the like.

  Thrips of the order Thrips thrips (Scirtothrips dorsalis), Southern thrips (Thrips palmi), Croton thrips (Heliothrips haemorrhoidalis), Citrus thrips (Frankliniella occidentalis), rip

  Spider mites, such as the spider mite (Tetranychus urticae), the Kanzawa spider mite (Tetranychus kanzawai), the mandarin spider mite (Panonychus citri), the apple spider mite (Panonychus ulmi), the yellow mito (Eotetranychus carpini), the Texas citrus mito (Eotetranychus carite), Chinese mite (Polyphagotarsonemus latus), Japanese red spider mite (Brevipalpus sp.), Robin mite (Rhizoglyphus robini), Japanese black tick (Tyrophagus putrescentiae), etc.

  Plant parasitic nematodes, for example Meloidogyne sp., Pratylenchus sp., Soybean cyst nematode (Heterodera glycines), Potato cyst nematode (Globodera rostochiensis), Banana moth nematode (Radopholus similis) , Strawberry nematode (Aphelenchoides fragariae), rice scented nematode (Aphelenchoides besseyi), pine wood nematode (Bursaphelenchus xylophilus) and the like.

  Other harmful animals, unpleasant animals, sanitary pests, parasites such as Pomacea canaliculata, slugs (Incilaria sp.), Gastropods such as Achatina fulica (Gastropoda), armadillidium sp. Isopods such as barley beetle and centipede (Isopoda), Chatterus such as Liposcelis sp., Spots such as Ctenolepisma sp., Fleas such as Pulex sp. And Ctenocephalides sp., Hazel worms such as Trichodectes sp., Cimex Examples include bed bugs such as sp., animal parasitic mites such as Boophilus microplus, Haemaphysalis longicornis, and leopard mites.

Furthermore, it is also effective against pests that are resistant to organophosphorus compounds, carbamate compounds, synthetic pyrethroid compounds, acylurea compounds, or existing insecticides.
Next, the production method, formulation method and use of the compound of the present invention will be described specifically by way of examples.

[Example 1]
Preparation of 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] -3-methyl-4-trifluoromethylthio-1H-pyrazole (present compound number 253) Dissolve 0.34 g of 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-trifluoromethylthio-1H-pyrazole in 10 ml of chloroform. Under ice cooling, 0.24 g (purity 65%) of m-chloroperbenzoic acid was added. After stirring for 1 hour under ice cooling, the organic layer was washed with an aqueous sodium thiosulfate solution, then washed with an aqueous sodium hydrogen carbonate solution, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] -3-methyl-4-trifluoromethylthio-1H- 0.35 g of pyrazole was obtained.

[Example 2]
Preparation of 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-trifluoromethylthio-1H-pyrazole (present compound number 252) 0.74 g of 5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-trifluoromethylthio-1H-pyrazole was added to tetrahydrofuran. It melt | dissolved in 10 ml, 0.56 g of t-butyl nitrites were added, and it stirred at 50 degreeC for 1 hour. The reaction mixture was cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-trifluoromethylthio- 0.44 g of 1H-pyrazole was obtained.

[Example 3]
5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-trifluoromethylthio-1H-pyrazole (the present compound number) 260) 5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-mercapto-1H-pyrazole 1.62 g Was dissolved in 20 ml of N, N-dimethylformamide, 1.1 g of Rongalite and 1.4 g of trifluoroiodomethane were added, and the mixture was stirred for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic 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 give 5-amino-1- [2-fluoro-4-methyl- There was obtained 0.84 g of 5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-trifluoromethylthio-1H-pyrazole.

(1) Synthesis of 5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-mercapto-1H-pyrazole 5- 1.66 g of amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-thiocyanato-1H-pyrazole was dissolved in 20 ml of methanol. Then, 0.3 g of sodium tetrahydroborate was added to the solution cooled to 0 ° C. in a nitrogen atmosphere, and stirred at 0 ° C. for 1 hour. The reaction mixture was poured into water, adjusted to pH <4 with hydrochloric acid and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl]- 1.62 g of 3-methyl-4-mercapto-1H-pyrazole was obtained.

(2) Synthesis of 5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-4-thiocyanato-1H-pyrazole 5- Amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-1H-pyrazole was dissolved in 50 ml of methanol to obtain 6.3 g of potassium thiocyanate. Was added and cooled to 0 ° C. To the solution, 3.4 g of bromine was added dropwise and stirred for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl]- 4.38 g of 3-methyl-4-thiocyanate-1H-pyrazole was obtained.

(3) Synthesis of 5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -3-methyl-1H-pyrazole 4.0 g of ethyl acetate, Acetonitrile 2.3 g and sodium hydride 2.4 g (purity 55%) were dissolved in 30 ml of tetrahydrofuran and refluxed for 4 hours. The reaction mixture was poured into water, adjusted to pH <4 with hydrochloric acid and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was dissolved in 40 ml of isopropanol, and 9.4 g of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenylhydrazine and a catalytic amount of methanesulfonic acid were added and refluxed for 24 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer 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 give 5-amino-1- [2-fluoro-4-methyl-5- (2, There were obtained 6.88 g of 2,2-trifluoroethylthio) phenyl] -3-methyl-1H-pyrazole.

[Example 4]
Production of 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] -4-pentafluoroethylthio-1H-pyrazole (present compound number 62) 1- [ 2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -4-pentafluoroethylthio-1H-pyrazole 0.7 g was dissolved in 20 ml of chloroform, m -0.37 g of chloroperbenzoic acid (purity 75%) was added. After stirring for 1 hour under ice cooling, the organic layer was washed with an aqueous sodium thiosulfate solution, then washed with an aqueous sodium hydrogen carbonate solution, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] -4-pentafluoroethylthio-1H-pyrazole. 39 g was obtained.

[Example 5]
Preparation of 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -4-pentafluoroethylthio-1H-pyrazole (Compound No. 61 of the present invention) -4-1- [2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -pentafluoroethylthio-1H-pyrazole (0.72 g) was dissolved in 20 ml of tetrahydrofuran. 0.8 g of tert-butyl nitrate was added at room temperature, and the mixture was stirred at 70 ° C. for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to give 1- [2-fluoro-4-methyl-5- (2 , 2,2-trifluoroethylthio) phenyl] -4-pentafluoroethylthio-1H-pyrazole 0.7 g was obtained.

(1) Synthesis of 5-amino-1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -4-pentafluoroethylthio-1H-pyrazole 5-amino To a solution of 2.7 g of -1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -4-mercapto-1H-pyrazole in 20 ml of N, N-dimethylformamide, 2.4 g of pentafluoroethyl iodide and 2.2 g of Rongalite were added, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into water and extracted with ethyl acetate. 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 1- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethyl). 1.2 g of thio) phenyl] -5-amino-4-pentafluoroethylthio-1H-pyrazole was obtained.

The structural formula and physical property values of the compound [I] of the present invention synthesized according to the examples are shown in Tables 10 to 12, including the examples. However, the symbols in the table have the same meaning as described above.
The compound number is referred to in the following description.

Compound No. 3, 7, 15, 41, 44, 46, 50, 66, 68, 70, 79, 81, 82, 86, 87, 90, 124, 126, 128, 133, 135, 142, 144, 146, 148, 150, 153, 156, 160, 162, 165, 166, 167, 208, 210, 212, 217, 218, 219, 221, 223, 225, 227, 230, 232, 233, 260, 266, 268, As for 274 and 276, ¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value) is shown below.
Compound No. 3: 2.43 (3H, s), 3.65 (1H, m), 3.40 (2H, q), 7.09 (1H, t), 8.50 (5H, m),
Compound No. 7: 1.23 (3H, s), 1.25 (3H, s), 2.50 (3H, s), 3.04 (1H, m), 3.40 (2H, q), 7.14 (1H, d), 7.71 (1H, s), 8.01 (1H, d), 8.08 (1H, d)
Compound No. 15: 0.21 (2H, q), 0.56 (2H, q), 1.23 (1H, m), 2.49 (3H, s), 2.66 (2H, d), 3.46 (2H, q), 7.13 (1H, d), 7.73 (1H, s), 8.03 (1H, d), 8.06 (1H, s)
Compound No. 41: 2.49 (3H, s), 3.58 (2H, m), 8.14 (1H, d), 8.52 (1H, s), 8.70 (1H, d), 8.73 (1H, s)
Compound No. 44: 3.42 (2H, q), 6.93 (1H, t), 7.70 (5H, m)
Compound No. 46: 2.19 (3H, s), 2.50 (3H, s), 3.40 (2H, q), 7.20 (1H, s), 7.46 (1H, s), 7.82 (1H, s), 7.85 (1H, s)
Compound No. 50: 3.57 (2H, q), 7.64 (1H, s), 7.79 (1H, s), 7.89 (1H, s), 8.16 (1H, s)
Compound No. 66: 2.12 (3H, s), 2.50 (3H, s), 3.42 (2H, s), 7.20 (1H, s), 7.45 (1H, s), 7.81 (1H, s), 7.84 (1H, s)
Compound No. 68: 3.57 (2H, q), 7.64 (1H, s), 7.78 (1H, s), 7.88 (1H, s), 8.15 (1H, s)
Compound No. 70: 2.49 (3H, s), 3.48 (2H, q), 7.41 (1H, s), 7.68 (1H, s), 7.85 (1H, s), 8.11 (1H, s)
Compound No. 79: 3.57 (2H, q), 5.85 (1H, tt), 7.64 (1H, s), 7.79 (1H, s), 7.86 (1H, s), 8.14 (1H, s)
Compound No. 81: 3.75 (2H, m), 6.31 (1H, tt), 7.75 (1H, s), 8.18 (1H, s), 8.26 (1H, s), 8.50 (1H, s)
Compound No. 82: 2.51 (3H, s), 3.44 (2H, q), 7.18 (1H, d), 7.85 (1H, s), 8.09 (1H, d), 8.23 (1H, d)
Compound No. 86: 2.18 (3H, s), 2.50 (3H, s), 3.40 (2H, q), 7.21 (1H, s), 7.46 (1H, s), 7.82 (1H, s), 7.85 (1H, s)
Compound No. 87: 2.29 (3H, s), 2.43 (3H, s), 3.46 (2H, m), 7.27 (1H, s), 7.87 (1H, s), 7.88 (1H, s), 7.94 (1H, s)
Compound No. 90: 2.52 (3H, s), 3.42 (2H, q), 7.15 (1H, d), 7.86 (1H, s), 8.08 (1H, d), 8.22 (1H, s)
Compound No. 124: 2.24 (3H, s), 2.56 (3H, s), 3.43 (2H, q), 4.14 (2H, s), 7.17 (1H, d), 7.58 (1H, s), 7.68 (1H, d)
Compound No. 126: 1.25 (3H, t), 2.53 (3H, s), 2.61 (2H, q), 3.41 (2H, q), 4.14 (2H, s), 7.17 (1H, d), 7.56 (1H, s), 7.69 (1H, d)
Compound No. 128: 1.24 (3H, s), 1.25 (3H, s), 2.53 (3H, s), 2.99 (1H, m), 3.40 (2H, q), 4.14 (2H, s), 7.17 (1H, d), 7.54 (1H, s), 7.67 (1H, d)
Compound No. 133: 2.50 (3H, s), 3.49 (2H, q), 4.37 (2H, s), 7.39 (2H, m), 7.64 (1H, s), 7.72 (1H, s)
Compound No. 135: 3.54 (2H, q), 4.23 (2H, s), 7.63 (1H, s), 7.64 (1H, s), 7.68 (1H, s)
Compound No. 142: 2.08 (3H, s), 2.50 (3H, s), 3.42 (2H, q), 4.13 (2H, s), 7.22 (1H, s), 7.43 (1H, s), 7.59 (1H, s)
Compound No. 144: 3.55 (2H, q), 4.23 (2H, s), 7.62 (2H, s), 7.68 (1H, s)
Compound No. 146: 2.51 (3H, s), 3.45 (2H, q), 4.21 (2H, s), 7.44 (1H, s), 7.54 (1H, s), 7.60 (1H, s)
Compound No. 148: 2.54 (3H, s), 3.41 (2H, q), 4.31 (2H, s), 5.83 (1H, tt), 7.19 (1H, d), 7.62 (2H, s), 7.68 (1H, d)
Compound No. 150: 3.53 (2H, q), 4.23 (2H, s), 5.83 (1H, tt), 7.61 (1H, s), 7.62 (1H, s), 7.68 (1H, s)
Compound No. 153: 2.55 (3H, s), 3.41 (2H, q), 3.70 (21H, m), 4.92 (1H, s), 7.21 (1H, d), 7.64 (1H, d)
Compound No. 156: 2.08 (3H, s), 2.49 (3H, s), 3.41 (2H, q), 4.13 (2H, s), 7.24 (1H, s), 7.43 (1H, s), 7.57 (1H, s)
Compound No. 160: 2.06 (3H, s), 2.55 (3H, s), 3.41 (2H, q), 7.14 (1H, d), 7.18 (1H, s), 7.69 (1H, d), 7.97 (1H, s)
Compound No. 162: 2.54 (3H, s), 3.40 (2H.q), 7.16 (1H, d), 7.72 (1H, d), 7.93 (1H, s), 8.50 (1H, s)
Compound No. 165: 2.50 (3H, s), 3.51 (2H.m), 7.26 (1H, d), 7.95 (1H, s), 8.13 (1H, d),
Compound No. 166: 2.57 (3H, s), 3.43 (2H, q), 7.23 (1H, d), 7.63 (1H, d), 7.93 (1H, s)
Compound No. 167: 2.53 (3H, s), 3.55 (2H, m), 7.25 (1H, d), 7.98 (1H, s), 8.21 (1H, s)
Compound No. 208: 1.55 (3H, s), 3.44 (2H, q), 7.19 (1H, d), 8.05 (1H, d), 8.28 (1H, s)
Compound No. 210: 1.55 (3H, s), 3.12 (2H, q), 7.18 (1H, d), 8.05 (1H, d), 8.25 (1H, s)
Compound No. 212: 2.53 (3H, s), 3.26 (2H, q), 3.43 (2H, q), 7.15 (1H, d), 8.10 (1H, d), 8.15 (1H, s)
Compound No. 217: 2.54 (3H, s), 3.40 (2H, q), 7.22 (1H, d), 8.06 (1H, d), 8.26 (1H, s)
Compound No. 218: 2.48 (3H, s), 3.50 (2H, m), 7.24 (1H, d), 8.29 (1H, s), 8.54 (1H, d)
Compound No. 219: 2.54 (3H, s), 3.41 (2H, q), 4.46 (2H, s), 7.21 (1H, d), 7.67 (1H, d)
Compound No. 221: 2.55 (3H, s), 3.42 (2H, q), 4.41 (2H, s), 6.66 (1H, t), 7.21 (1H, d), 7.66 (1H, d)
Compound No. 223: 2.54 (3H, s), 3.20 (2H, q), 3.41 (2H, q), 4.34 (2H, s), 7.20 (1H, d), 7.63 (1H, d)
Compound No. 225: 2.54 (3H, s), 3.41 (2H, q), 4.46 (2H, s), 7.22 (1H, d), 7.68 (1H, d)
Compound No. 227: 2.55 (3H, s), 3.43 (2H, q), 4.47 (2H, s), 7.22 (1H, d), 7.69 (1H, d)
Compound No. 230: 2.51 (3H, s), 3.52 (2H, m), 7.29 (1H, d), 8.17 (1H, d)
Compound No. 232: 2.50 (3H, s), 3.32 (2H, q), 3.55 (2H, m), 7.23 (1H, d), 8.20 (1H, d)
Compound No. 233: 2.54 (3H, s), 3.46 (2H, q), 7.22 (1H, d), 8.06 (1H, d), 8.32 (1H, d)
Compound No. 260: 2.31 (3H, s), 2.53 (3H, s), 3.41 (2H, q), 4.28 (2H, s), 7.17 (1H, d), 7.68 (1H, d)
Compound No. 266: 2.30 (3H, s), 2.53 (3H, s), 3.41 (2H, q), 4.27 (2H, s), 7.17 (1H, d), 7.67 (1H, d)
Compound No. 268: 1.47 (9H, s), 2.50 (3H, s), 3.43 (2H, q), 7.13 (1H, d), 8.12 (1H, d), 8.16 (1H, d)
Compound No. 274: 1.47 (9H, s), 2.50 (3H, s), 3.43 (2H, q), 7.13 (1H, d), 8.12 (1H, d), 8.14 (1H, d)
Compound No. 276: 1.43 (9H, s), 2.52 (3H, s), 3.41 (2H, q), 4.28 (2H, s), 7.16 (1H, d), 7.69 (1H, d)

  Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description, “parts” means parts by weight.

[Formulation Example 1] Emulsion Compound No. 6 Compound 30 parts Cyclohexanone 20 parts Polyoxyethylene alkyl aryl ether 11 parts
Calcium alkylbenzenesulfonate 4 parts
Methyl naphthalene 35 parts or more was uniformly dissolved to prepare an emulsion. Moreover, it can replace with compound number 6 and can obtain an emulsion similarly using each of the compound of Tables 1-9.

[Formulation Example 2] Wetting agent Compound No. 6 10 parts Naphthalenesulfonic acid formalin condensate sodium salt 0.5 part
Polyoxyethylene alkyl aryl ether 0.5 part Diatomaceous earth 24 parts Clay 65 parts
The above was mixed and ground uniformly to obtain a wettable powder. Moreover, it can replace with compound number 6 and a wettable powder can be obtained similarly using each of the compounds of Tables 1-9.

[Formulation Example 3] Powder Compound of Compound No. 6 2 parts Diatomaceous earth 5 parts Clay 93 parts
The above was uniformly mixed and pulverized to obtain a powder. Moreover, it can replace with compound number 6 and can obtain a dust similarly using each of the compounds of Tables 1-9.

[Formulation Example 4] Granule Compound No. 6 Compound 5 parts Sodium salt of lauryl alcohol sulfate 2 parts Lignin sulfonate 5 parts Carboxymethyl cellulose 2 parts Clay 86 parts or more were uniformly mixed and ground. The mixture was kneaded with an equivalent amount of 20 parts of water, processed into granules of 14 to 32 mesh using an extrusion granulator, and dried to give granules. Moreover, it can replace with the compound number 6 and can obtain a granule similarly using each of the compounds of Tables 1-9.

  Next, the effect of the pest control agent comprising the compound of the present invention as an active ingredient will be described with test examples.

[Test Example 1] Spider mite control test (immersion treatment)
A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm as an active ingredient. Soybean seedlings previously inoculated with adult spider mites were immersed in the chemical solution and air-dried. The treated soybean seedlings were placed in a thermostatic chamber at 25 ° C., and the number of living insects was examined after 13 days, and the control value was determined by the formula of Formula 1. The test was conducted in a single run. The results in this test are shown in Table 13.

[Test Example 2] Spider mite control test (soil treatment)
A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 100 ppm as an active ingredient. 5 ml of the drug solution was irrigated into the soil (100 g) of a soybean seedling cup that had previously been inoculated with adult spider mites. The treated soybean seedlings were placed in a thermostatic chamber at 25 ° C., and the number of living insects was examined after 13 days, and the control value was determined by the formula of Formula 1. The test was conducted in a single run. The results of this test are shown in Table 14.

[Test Example 3] Brown planthopper insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm as an active ingredient. Rice buds and rice bran were immersed in the chemical solution and placed in a plastic cup having a capacity of 60 ml. To this, 10 3rd instar larvae were released, covered and placed in a thermostatic chamber at 25 ° C. Six days later, the number of surviving insects was counted, and the mortality rate was determined by the formula of Formula 2. The test was conducted in a single run. The results of this test are shown in Table 15.

[Test Example 4] Nematode nematode control test compound was dissolved in an N, N-dimethylformamide solution containing 1% of tween20, and this solution was diluted with distilled water to a concentration of 20 ppm as an active ingredient. 0.5 ml of the drug solution and 0.5 ml of a suspension containing about 30 larvae of the second stage of the sweet potato root nematode were mixed and placed in a thermostatic chamber at 25 ° C. Five days later, the number of immobile and viable nematodes was counted under a microscope, and the rate of the nematode was determined by the formula (3). The test was conducted in a two-run system. The results of this test are shown in Table 16.

Claims (4)

Formula [I]

[Where:
R ₁ is a C _{1 to} C ₆ alkyl group (the group is a halogen atom, a C _{3 to} C ₆ cycloalkyl group, a hydroxyl group, a cyano group, a C _{2 to} C ₇ alkoxycarbonyl group, a C _{1 to} C ₆ alkoxy group, or may be mono-substituted or poly-substituted by carboxyl _group), C 3 -C ₆ cycloalkyl _group, C 2 -C ₆ alkenyl _group, C 2 -C ₆ alkynyl _group, C 1 -C ₆ alkoxy group, an amino group, a cyano _group, C 1 -C ₆ monoalkylamino group or a di _(C 1 -C ₆ alkyl) amino group,
R ₂ is a C ₁ -C ₆ alkyl group (the group may be mono-substituted or poly-substituted by a halogen atom or a C ₃ -C ₆ cycloalkyl group), a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ shows an alkynyl group or a _C 3 -C ₈ cycloalkyl group,
n represents an integer of 0 to 2,
m represents 0 or 1,
A ₁ is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group (the group is mono-substituted or poly-substituted by a halogen atom, a hydroxyl group, a cyano group, a C ₁ -C ₆ alkoxy group or a C ₂ -C ₇ alkoxycarbonyl group may be _{substituted),} C 3 -C ₆ cycloalkyl _group, C 2 -C ₆ alkenyl _group, C 2 -C ₆ alkynyl _group, mono- or polysubstituted by C 1 -C ₆ alkoxy group (said group halogen atom may be _{substituted),} C 2 -C ₇ alkoxycarbonyl group, a cyano group, an amino _group, C 1 -C ₆ monoalkylamino group, a di _(C 1 -C ₆ alkyl) amino _group, C 1 -C ₇ acyl a group or a _C 2 -C ₅ haloalkylcarbonyl group,
A ₂ is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group (this group is mono-substituted or poly-substituted by a halogen atom, a cyano group, a C ₂ -C ₇ alkoxycarbonyl group or a C ₁ -C ₆ alkoxy group) C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₆ alkoxy group (the group is mono- or poly-substituted by a halogen atom) may also be), amino _group, C 1 -C ₆ monoalkylamino group, a di _(C 1 -C ₆ alkyl) amino group, a cyano group, a nitro _group, C 1 -C ₇ acyl _group, NR 3 (COR ₄₎ or NR ₃ (COOR ₄ ) group,
R ₃ and R ₄ each independently represent a hydrogen atom or a C _{1 to} C ₆ alkyl group (the group may be mono-substituted or poly-substituted by a halogen atom);
B ₁ represents a hydrogen atom, a halogen atom or a methyl group,
B ₂ represents a halogen atom, a cyano group, a nitro group or a C ₁ -C ₆ alkyl group (this group may be mono-substituted or poly-substituted by a halogen atom). ] The 3-pyrazolyl phenyl sulfide derivative or its salt characterized by the above-mentioned. A 3-pyrazolyl phenyl sulfide derivative or a salt thereof according to claim 1, wherein A ₁ and A ₂ are hydrogen atoms. The 3-pyrazolyl phenyl sulfide derivative or a salt thereof according to claim 1, wherein R ₂ is a cyclopropylmethyl group, a trifluoroethyl group, or a trifluoropropyl group, and A ₁ and A ₂ are hydrogen atoms. An agricultural / horticultural insecticidal / acaricidal / nematicidal agent comprising the 3-pyrazolylphenyl sulfide derivative according to claim 1 as an active ingredient.