JP2000178247A - Vinyl sulfone derivative or salt, their production, their intermediate and pest controlling agent containing the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of extending a pest controlling spectrum and manifesting excellent preventing and therapeutic effects on various kinds of disease injuries, especially powdery mildew and rust of wheats and barleys. SOLUTION: This vinyl sulfone derivative is represented by formula I [Ar is an aryl or a heteroaryl; A is a haloalkyl; B is naphthyl or the like; (m) is 1 or 2] (except 1-bromo-2-methylsulfonyl-3-phenyl-2-propene), e.g. 1-(3-(3-(trifluoromethyl)-2-pyridyloxy)phenyl)-2-(methylsulfonyl)-3,3,3- trifluoropropene. The compound represented by formula I can be obtained by oxidizing a compound represented by formula II in a suitable solvent. The compound represented by formula II can be prepared by reacting a compound represented by formula III (Hal is a halogen) with a compound represented by the formula (A-CO)2O in the presence of a base, then thermally decomposing the resultant compound and subsequently reacting the prepared compound with thiols in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel vinyl sulfone derivative or a salt thereof, a production method thereof, an intermediate thereof, and a pesticidal composition containing the same as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION Vinyl sulfone derivatives similar to the compounds of the present invention
Examples of the conductor include: Org. Chem.52
(8), 1544-1548 (1987).
Bromo-2-methylsulfonyl-3-phenyl-2-p
Lopen; Tetrahedron Letters,38
(42), 7415-7416 (1997).
-Chloro-3- (4-nitrophenyl) -2-phenyl
And sulfonyl-2- (Z) -propene.
However, the chemical structure of these compounds is
And different. In addition, these compounds are not harmful
There is no description that it has a substance controlling activity.

US Pat. No. 3,039,919 describes that a specific phenylacyl sulfone has a bactericidal activity, and JP-A-6-41054 discloses that a specific trifluoromethyl group is contained. It is described that styryl sulfone derivatives have a preventive effect against various diseases. JP-A-7-10840 discloses that a specific sulfide derivative has a bactericidal action, and JP-A-7-17944 discloses a bactericidal composition containing a specific trifluorobutenone derivative and its structural isomer as an active ingredient. Agents are described. However, the chemical structures of the compounds described in these publications are different from the compounds of the present invention. Furthermore, Japanese Patent Application Laid-Open No. 6-41054 describes one line that the compound described in the publication has a therapeutic effect on various diseases, but does not specifically disclose the therapeutic effect.

[0004]

Many pest control agents provided so far each have a characteristic in their pest control effect, and therefore, some of them have specific pest control properties. The effect is not enough,
Some are less effective than preventive effects,
Alternatively, the residual effect may be relatively short, and depending on the application, may show only a practically insufficient control effect on pests. Therefore, creation of a novel compound having a strong pest control effect is desired.

[0005]

Means for Solving the Problems The present inventors have studied to solve the above problems, and as a result, using a compound represented by the following general formula (I) as an active ingredient, pest control. The present invention has been found not only to be able to expand the spectrum, but also to have excellent preventive and therapeutic effects on various diseases, especially on powdery mildew and rust of wheat.

That is, the present invention provides a compound represented by the general formula (I):

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Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group or a heteroaryl group which may be substituted, and n is 0, 1 or 2),-(CH ₂ ) _p -R ²
A group wherein R ² is an optionally substituted aryl group;
p is 1 or 2) or an optionally substituted naphthyl group; m is an integer of 1 or 2. And a salt thereof, a production method thereof, an intermediate thereof, and a pesticidal agent containing them as an active ingredient.

The wavy line between C and Ar in the general formula (I) represents the presence of a structural isomer (the structural isomers are similarly expressed in the following general formulas). ).

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In the above general formula (I), the optionally substituted aryl group of Ar includes an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted tetrahydronaphthyl group, an optionally substituted tetrahydronaphthyl group, And an indanyl group. Examples of the optionally substituted heteroaryl group for Ar include an optionally substituted isoxazolyl group, an optionally substituted thienyl group, an optionally substituted furyl group, an optionally substituted pyridyl group, and an optionally substituted pyridyl group. A pyrimidinyl group, an optionally substituted pyridazinyl group, and the like. Among these substituents, an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted isoxazole group, and an optionally substituted thienyl group are desirable.

The haloalkyl group represented by A has 1 to 1 carbon atoms.
3, haloalkyl having 1 to 5 halogen atoms is desirable,
_{CF 3, -CHF 2, -CH 2} F, -CF 2 Cl, -C
_{FCl 2, -CCl 3, -CH 2} CF 3, -CF 2 CF
_3, -CHBr _2, further preferably -CH ₂ Br, -
CF ₃ , —CF ₂ Cl, and —CF ₂ CF ₃ are particularly desirable.

[0011] alkyl moieties contained in the substituted alkoxycarbonyl group which may be substituted alkyl groups and substituted also for R ¹ may be one having 1 to 12 carbon atoms, such as methyl, ethyl, n- propyl, Isopropyl, n
-Butyl, sec-butyl, isobutyl, tert-butyl,
n-pentyl, n-hexyl, heptyl, octyl, nonyl, decyl and the like. The cycloalkyl group of R ¹ may have 3 to 7 carbon atoms, but is preferably cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. The heteroaryl part of the optionally substituted heteroaryl group represented by R ¹ may be any as long as the ring contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom; For example, thienyl,
Ruffle, thiazolyl, isoxazolyl, pyridyl, pyrimidinyl, pyridazinyl and the like can be mentioned.

The aryl moiety of the optionally substituted aryl group for R ² is the same as the aforementioned optionally substituted aryl group for Ar, but phenyl and naphthyl are preferred.

Examples of the substituent of the optionally substituted alkyl group and the optionally substituted alkoxycarbonyl group represented by R ¹ include a halogen atom; alkoxy; haloalkoxy; alkylthio; haloalkylthio;

An optionally substituted aryl group and an optionally substituted heteroaryl group for Ar; an optionally substituted heteroaryl group for R ¹ ; an optionally substituted aryl group for R ² ; Examples of the substituent of the naphthyl group include a halogen atom; nitro; cyano; alkyl; haloalkyl; alkoxyalkyl; alkoxycarbonyl; alkoxy; haloalkoxy; methylenedioxy optionally substituted by a halogen atom; ; optionally substituted alkynyloxy be oxy; optionally substituted aryloxy; optionally substituted heteroaryloxy; -NR ₃ R ₄ group (R ₃ and R
₄ are each a hydrogen atom, alkyl, haloalkyl or alkanoyl); - SO _q R ₅ group (R ₅ is alkyl or haloalkyl, q is an integer of 0 to 2)
And the like. The number of the above substituents is preferably from 0 to 5.

The halogen atom as a substituent for Ar, R ¹ , R ² and B may be fluorine, chlorine, bromine or iodine. The alkyl moiety as a substituent of Ar, R ¹ , R ² and B may be the same as the alkyl moiety contained in R ¹ described above. Ar, R ¹ , R ²
And the alkenyl and alkynyl moieties as substituents on B and B may have 2 to 12 carbon atoms. Said A
The optionally substituted aryloxy and the optionally substituted heteroaryloxy as substituents of r, R ¹ , R ² and B are a halogen atom; nitro; cyano; alkyl; haloalkyl; alkoxyalkyl;
Alkoxycarbonyl; alkoxy; haloalkoxy;
Alkenyloxy; haloalkenyloxy; alkynyloxy; haloalkynyloxy; -NR ₃ R ₄ group (R ₃ and R _4, respectively, a hydrogen atom, alkyl, haloalkyl or alkanoyl); - SO _q R ₅ group (R ₅ is alkyl or haloalkyl, and q is an integer of 0 to 2). The number of the above substituents is 0 to 5. And R ₃ and R ₄ together with an adjacent nitrogen atom
5 to 7 which may contain an oxygen atom, a sulfur atom or a nitrogen atom
May form a membered saturated heterocycle, for example, a piperidine ring, a pyrrolidine ring, a morpholine ring, a thiomorpholine ring and the like.

Preferred embodiments of the vinyl sulfone derivative represented by the general formula (I) are described below. (1) Ar is

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(Wherein X, Y and Z are hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, cyano, nitro, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, substituted Aryloxy, optionally substituted heteroaryloxy, methylenedioxy, wherein at least 2 of X, Y, Z
May be fused to form a ring), an optionally substituted naphthyl group, an optionally substituted isoxazolyl group or an optionally substituted thienyl group.

(2) Ar is 3-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4- (5-trifluoromethyl-2-pyridyloxy) phenyl,
(5-trifluoromethyl-2-pyridyloxy) phenyl, 4- (3-trifluoromethyl-2-pyridyloxy) phenyl, 3- (3-trifluorotyl-2-pyridyloxy) phenyl, 2-chloro- 4,5-methylenedioxyphenyl, 3,4-methylenedioxyphenyl, β-naphthyl, 2,4-difluorophenyl,
2,4-dichlorophenyl, 3,5-dimethyl-4-isoxazolyl, 3-trifluoromethylphenyl,
-Trifluoromethylphenyl or 3-methylphenyl.

(3) Ar is trifluoromethylpyridyloxyphenyl.

(4) B is 5-trifluoromethyl-2-
Pyridyl, 3-trifluoromethyl-2-pyridyl, 4
-Methyl-benzyl, 4-chloro-benzyl, cyclopropyl, cyclopentyl, cyclohexyl, phenylethyl, methyl, ethyl, propyl, isopropyl, 1-
Methylpropyl, tert-butyl, 4,6-dimethyl-2-pyrimidinyl, ethoxycarbonylethyl or β-naphthyl.

The vinyl sulfone derivative represented by the general formula (I) or a salt thereof is an intermediate represented by the general formula (II):

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[Wherein Ar, A and B are as defined above] or a salt thereof in a suitable solvent. As the oxidizing agent, aqueous hydrogen peroxide, metachloroperbenzoic acid, potassium permanganate or sodium metaperiodate can be used. The reaction temperature can be arbitrarily set in the range of 0 ° C to 160 ° C or the boiling point.
Is desirable. Although the solvent varies depending on the oxidizing agent, a solvent such as acetic acid, dichloromethane, chloroform or methanol is desirable. The reaction time varies depending on the set conditions, but can usually be completed in 5 minutes to 12 hours.

The compound of the general formula (I) includes a compound of the general formula (I-1):

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Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group or a heteroaryl group which may be substituted, and n is 0, 1 or 2),-(CH ₂ ) _p -R ²
A group wherein R ² is an optionally substituted aryl group;
p is 1 or 2) or an optionally substituted naphthyl group; m is 1 or 2. 〕When,

General formula (I-2):

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Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group or a heteroaryl group which may be substituted, and n is 0, 1 or 2),-(CH ₂ ) _p -R ²
A group wherein R ² is an optionally substituted aryl group;
p is 1 or 2) or an optionally substituted naphthyl group; m is 1 or 2. And a compound represented by the formula:

The compound of the general formula (I-1) includes a compound of the general formula (I-1a):

Embedded image

Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group or a heteroaryl group which may be substituted, and n is 0, 1 or 2),-(CH ₂ ) _p -R ²
A group wherein R ² is an optionally substituted aryl group;
p is 1 or 2) or an optionally substituted naphthyl group; m is 1 or 2. And a compound represented by the general formula (I-1b):

[0029]

Embedded image

Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group or a heteroaryl group which may be substituted, and n is 0, 1 or 2),-(CH ₂ ) _p -R ²
A group wherein R ² is an optionally substituted aryl group;
p is 1 or 2) or an optionally substituted naphthyl group; m is 1 or 2. There are two types of structural isomers of the compound represented by the formula:

The compound of the general formula (I-1b) can be obtained by isomerizing the compound of the general formula (I-1a). The compound of the general formula (I-1b) is obtained, for example, by reacting a compound of the general formula (I-1a) with a thiol: D-SH (where D is an organic group) in the presence of a solvent and a base, Can be manufactured directly.

Various thiols can be used in the reaction for producing the above-mentioned intermediate, but thiophenol is most preferably used. Examples of the base include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; hydrides of alkali metals such as sodium hydride; Alternatively, alkoxides such as sodium methoxide and the like can be used. The reaction temperature can be easily set between 0 ° C. and 150 ° C. or the boiling point of the solvent. Examples of the solvent include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, and tetrahydrofuran; benzene,
Aromatic hydrocarbons such as toluene; alcohols such as methanol and ethanol; N, N-dimethylformamide;
Solvents such as dimethyl sulfoxide and water are desirable. The reaction time varies depending on the set conditions, but can usually be completed in 5 minutes to 12 hours.

Similarly, the compound of the general formula (I-2) includes a compound of the general formula (I-2a):

Embedded image

Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group or a heteroaryl group which may be substituted, and n is 0, 1 or 2),-(CH ₂ ) _p -R ²
A group wherein R ² is an optionally substituted aryl group;
p is 1 or 2) or an optionally substituted naphthyl group; m is 1 or 2. And a compound represented by the general formula (I-2b):

[0035]

Embedded image

Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group, a heteroaryl group which may be substituted,
n is 0, 1 or 2, a — (CH ₂ ) _p —R ² group, wherein R ² is an optionally substituted aryl group,
Is an integer of 1 or 2) or an optionally substituted naphthyl group; m is an integer of 1 or 2. There are two types of structural isomers of the compound represented by the formula: Therefore, the compound of the general formula (I) eventually has four types of structural isomers.

The compound of the general formula (II) is, for example, a compound of the general formula (IX):

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Wherein Ar and A are as described above, and Hal is a halogen atom. And a vinyl halide derivative represented by the general formula (VII): HS-B
Is as described above] in the presence of a base and a solvent. The vinyl halide derivative represented by the general formula (IX) is
Due to the difference in reaction conditions, it cannot be specified unconditionally, but usually,
It is used in an equimolar ratio with the thiols of the general formula (VII).

The vinyl halide derivative represented by the general formula (IX) can be produced by a method known per se or a method analogous thereto [for example, Bull. Che
m. Soc. Jpn. , 60 , 4377-4384 (1
987) and JP-A-61-161225]. The base used in the reaction between the vinyl halide derivative of the general formula (X) and the thiols of the general formula (VII) includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium, potassium carbonate and the like; alkali metal hydrides such as sodium hydride; and alkoxides such as sodium methoxide can be used. The reaction temperature ranges from 0 ° C to 160
It can be easily set between ° C and the boiling point of the solvent. Examples of the solvent include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, and tetrahydrofuran; aromatic hydrocarbons such as benzene and toluene; methanol;
Alcohols such as ethanol; and solvents such as N, N-dimethylformamide and dimethylsulfoxide are preferred. The reaction time varies depending on the set conditions, but is usually from 10 minutes to
It can be finished in 12 hours.

The compound of the general formula (II) is
(I) General formula (III):

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(Where Ar is as described above, and Hal
Is a halogen atom] and a compound represented by the general formula (IV): (A-CO) ₂ O (where A is as described above) and / or a compound represented by the general formula (IV '):
A-CO-Hal wherein A is as described above, and Ha is
and l is a halogen atom] in the presence of a base to obtain a compound represented by the general formula (V):

[0042]

Embedded image (Wherein, Ar and A are as defined above),

(Ii) The compound of the general formula (V) obtained in the first step is thermally decomposed to give a compound of the general formula (VI):

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(Wherein Ar and A are as defined above), (iii) the second step
A compound of the general formula (VI) obtained in the step, and a compound of the general formula (VII):
A thiol represented by B-SH (wherein B is as defined above) is reacted in the presence of a base to obtain a compound represented by the general formula (II):

[0045]

Embedded image (Wherein, Ar, A and B are as described above), and can also be produced by a method comprising a third step of producing a compound represented by the formula:

The compound of the formula (V) is obtained by reacting the compound of the formula (III) with the compound of the formula (IV) and / or the compound of the formula (IV ′) in the presence of a base. In the reaction of the first step, the compound of the general formula (IV) and / or the compound of the general formula (IV ′) cannot be unconditionally specified due to a difference in reaction conditions. Is used at a ratio of 1 to 10 mol, preferably 2 to 5 mol. Examples of the halogen atom represented by Hal in the compound of the general formula (IV ′) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred. Specific examples of the base used include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; sodium hydride, potassium hydride, Hydrides of alkali metals such as lithium hydride; alkoxides such as sodium methoxide and sodium ethoxide; In order to efficiently perform the reaction in the first step, it is desirable to carry out the reaction in the presence of a solvent. Specific solvents used are dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, 1,
Ethers such as 4-dioxane; aromatic hydrocarbons such as benzene and toluene; aprotic polar solvents such as N, N-dimethylformamide and dimethylsulfoxide. The reaction product, a compound of the general formula (V), is isolated by a general method, and can be subjected to the reaction in the second step.

The reaction of the second step for obtaining the compound of the general formula (VI) by thermally decomposing the compound of the general formula (V)
It is desirable to carry out the reaction at a reaction temperature of 230 ° C. Further, in order to carry out the reaction efficiently, it is desirable to carry out the reaction under reduced pressure. After completion of the reaction, the compound of the general formula (VI) can be isolated by purification or distillation.

The compound of the general formula (VI) is reacted with a thiol of the general formula (VII) in the presence of a base to obtain a compound of the general formula (II). VI)
The compound of formula (I) cannot be specified unconditionally due to the difference in reaction conditions, but is usually used in an equimolar ratio with the thiols of the general formula (VII). In the reaction of the third step, the reaction solution is
It is desirable to carry out the reaction by stirring at 30 ° C. to 100 ° C. for 0.1 to 24 hours.
More desirably, stirring is carried out for 5 to 12 hours. Examples of the base used in the reaction of the third step include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; sodium hydride; Hydrides of alkali metals such as potassium hydride and lithium hydride; alkoxides such as sodium methoxide and sodium ethoxide; tertiary amines such as triethylamine and pyridine; It is desirable to use a class. In order to carry out the reaction in the second step efficiently, it is desirable to carry out the reaction in the presence of a solvent. Specific solvents used include dimethyl ether, diethyl ether, methyl ethyl ether,
Ethers such as tetrahydrofuran and 1,4-dioxane; aromatic hydrocarbons such as benzene and toluene; N, N
Polar aprotic solvents such as dimethylformamide, acetonitrile or dimethylsulfoxide, etc., but it is preferred to use polar aprotic solvents or ethers. The compound of the general formula (II), which is a reaction product, is isolated by a general method, and subjected to the above-mentioned oxidation reaction to produce the compound of the general formula (I).

The compound of the general formula (II) has the general formula (II-1):

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Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group or a heteroaryl group which may be substituted, and n is 0, 1 or 2),-(CH ₂ ) _p -R ²
A group wherein R ² is an optionally substituted aryl group;
p is 1 or 2) or a naphthyl group which may be substituted. A compound represented by the formula:

Formula (II-2):

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Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group;
Is a haloalkyl group; B is a — (CH ₂ ) _n —R ¹ group, wherein R ¹ is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group,
A cyano group or a heteroaryl group which may be substituted, and n is 0, 1 or 2),-(CH ₂ ) _p -R ²
A group wherein R ² is an optionally substituted aryl group;
p is 1 or 2) or a naphthyl group which may be substituted. And a compound represented by the formula:

The compound of the general formula (II-1) and the compound of the general formula (II-2) each have two types of structural isomers. That is, the compound of the general formula (II) has four types of structural isomers. These four types of structural isomers are shown below.

[0054]

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The compound of the general formula (II) contains at least one of the four types of structural isomers, and often exists as a mixture of two or more types of structural isomers.
Each structural isomer can be separated and purified by recrystallization, silica gel chromatography, medium pressure liquid chromatography, etc., and each separated isomer is subjected to an oxidation reaction to obtain a compound of the general formula (I). You can also. However, usually, the compound of the general formula (II) can be directly subjected to the oxidation reaction without performing such separation and purification operations.

The compound of the general formula (II-1) is represented by the general formula (III):

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(Where Ar is as described above and Hal
Is a halogen atom) and a compound represented by the general formula (V
III);

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Wherein A and B are as described above.
By reacting with a compound represented by the formula in the presence of a base. In this case, the general formula (III)
The compound of the formula (1) cannot be specified unconditionally due to the difference in reaction conditions, but is usually used in an equimolar ratio to the compound of the formula (VIII). The halogen atom represented by Hal in the compound of the general formula (III) includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.

In the reaction of the compound of the general formula (III) with the compound of the general formula (VIII), specific bases to be used include alkali metals such as sodium and potassium; and sodium hydroxide and potassium hydroxide. Alkali metal hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium hydride, potassium hydride,
Hydrides of alkali metals such as lithium hydride;
Alkyl lithiums such as n-butyllithium, t-butyllithium and the like; alkoxides such as sodium methoxide, sodium ethoxide and the like. , Sodium hydride, n-butyllithium and the like are more desirable. Also,
In order to carry out the above reaction efficiently, it is desirable to carry out the reaction in the presence of a solvent. Specific examples of the solvent include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene and toluene; N, N-dimethylformamide and acetonitrile. Alternatively, a polar aprotic solvent such as dimethyl sulfoxide may be mentioned, but ethers are desirable, and tetrahydrofuran and 1,4-dioxane are more desirable.

The reaction of the compound of the general formula (III) with the compound of the general formula (VIII) is carried out at 0 ° C. to 100 ° C. for 0.1 to 0.1 ° C.
The reaction is preferably performed by stirring for 24 hours, and more preferably by stirring the reaction solution at 5 ° C. to 50 ° C. for 0.5 to 12 hours. The reaction product, a compound of the general formula (II-1), is isolated by a general method,
By subjecting this to the above-mentioned oxidation reaction, the compound of the aforementioned general formula (I-1) can be produced.

As listed above, the compounds of the general formula (I) in the present invention are shown in the following flow charts [A] to
It can be manufactured by the method [C].

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[0062]

Embedded image

[0063]

Embedded image [Wherein, Ar, A, B and m are as described above. Hal is a halogen atom.]

[0064]

EXAMPLES Next, specific examples of the method for producing the vinyl sulfone derivative represented by the general formula (I) and specific examples of the vinyl sulfone derivative represented by the general formula (I) and intermediates for producing the same will be described. A synthesis example will be described.

<Synthesis Example 1> 1- (3- (3- (Trifur
(Oromethyl) -2-pyridyloxy) phenyl) -2-
(Methylsulfonyl) -3,3,3-trifluoropro
Method for producing pen (compound No. 9) (1) 3- (3- (trifluoromethyl) -2-pyridi
Synthesis of 3-hydroxybenzaldehyde 4.71 g (38.6 mmol)
l), 7.0 g (38.6 mmol) of 2-chloro-3,3,3-trifluoromethylpyridine and 10.6 of potassium carbonate
g in a mixed solvent consisting of 20 ml methyl ethyl ketone and 10 ml dimethyl sulfoxide to 110 ° C.,
Stirred. Two hours later, the reaction solution was poured into water, and the reaction product was extracted with ethyl acetate. After washing with water, drying over sodium sulfate and distilling off the solvent under reduced pressure, 9.9 g of colorless crystals, 3- (3-
(Trifluoromethyl) -2-pyridyloxy) benzaldehyde (melting point 71-73 ° C) was obtained.

(2) 1- (3- (3- (trifluoromethyl )
Tyl) -2-pyridyloxy) phenyl) -2,2-di
Chloro-3,3,3-trifluoropropyl alcohol
Synthesis of 3- (3- (trifluoromethyl) -2-pyridyloxy) benzaldehyde 9.46 g (35.4 mmol), 1,
1,1-trichloro-3,3,3-trifluoroethane
9.3 g (49.6 mmol) and stannous chloride 10.75 g
(56.6 mmol) was stirred in 40 ml of dimethyl sulfoxide at room temperature overnight. The reaction solution was poured into water, and the reaction product was extracted with ethyl acetate. After washing with water, the solvent was distilled off under reduced pressure to obtain 14.67 g of the desired product (melting point: 93 to 94 ° C).

(3) Acetic acid 1- (3- (3- (trifur
(Oromethyl) -2-pyridyloxy) phenyl) -2
Combination of 2-dichloro-3,3,3-trifluoropropyl
Adult 1- (3- (3- (trifluoromethyl) -2-pyridyloxy) phenyl) -2,2-dichloro-3,3,3
-Trifluoropropyl alcohol 14.2 g (33.8 mmol
l) is dissolved in 80 ml of dimethyl sulfoxide, and acetic anhydride is dissolved.
11.8 ml (108.2 mmol) was added, followed by pyridine (5.9 g), and the mixture was stirred at 50 to 60 ° C for 2 hours and then at 40 ° C overnight. After treating the reaction mixture, it was subjected to silica gel column chromatography (hexane / ethyl acetate = 9: 1).
14.54 g of the desired product was obtained as a colorless oil.

(4) 2-chloro-1- (3- (3- (to
Trifluoromethyl) -2-pyridyloxy) phenyl)
Synthesis of 3,3,3-trifluoropropene acetic acid 1- (3- (3- (trifluoromethyl) -2-
Pyridyloxy) phenyl) -2,2-dichloro-3,
5 g (10.8 mmol) of 3,3-trifluoropropyl was stirred in 20 ml of dimethylsulfoxide solvent, and 1.2 g (18.4 mmol) of zinc powder was added at room temperature. The reaction solution was treated by stirring at 60 ° C. for 50 minutes. As usual, 3.72 g of the target compound was obtained as a colorless oily substance by introducing into water and extracting with ethyl acetate.

(5) 1- (3- (3- (trifluoromethyl )
Tyl) -2-pyridyloxy) phenyl) -2- (methyl
Ruthio) -3,3,3-trifluoropropene (intermediate
No. 9) Production method 2-chloro-1- (3- (3- (trifluoromethyl)
0.27 g of methanethiol sodium salt was added to a solution of 1.3 g (3.5 mmol) of 2-pyridyloxy) phenyl) -3,3,3-trifluoropropene in 15 ml of tetrahydrofuron.
(3.9 mmol) and the mixture was stirred at room temperature overnight. The reaction solution was poured into water, and the product was extracted with ethyl acetate. After washing with water, the solvent is distilled off under reduced pressure to obtain 1.33 g of the desired product as an oily product.
I got

(6) 1- (3- (3- (trifluoromethyl )
Tyl) -2-pyridyloxy) phenyl) -2- (methyl
Rusulfonyl) -3,3,3-trifluoropropene
Production method of (Compound No. 9) 2-chloro-1- (3- (3- (trifluoromethyl)
1.3 g (3.4 mmol) of (-2-pyridyloxy) phenyl) -3,3,3-trifluoropropene was dissolved in 20 ml of methylene chloride, and 1.2 g of metachloroperbenzoic acid was added. After stirring at room temperature overnight, the reaction mixture was poured into an aqueous solution of sodium bisulfite to decompose excess peroxide. The methylene chloride layer was washed with an aqueous sodium carbonate solution, dried, and the solvent was distilled off under reduced pressure. The obtained crude product is subjected to silica gel column chromatography (hexane / ethyl acetate =
8: 2) to give 0.59 g of the desired product as a colorless oil.

<Synthesis Example 2> 1- (3-chlorophenyl)
-2- (cyclohexylsulfonyl) -3,3,3-to
Production method of trifluoropropene (compound No. 2) (1) 1- (3-chlorophenyl) -2- (cyclohexene)
Silthio) -3,3,3-trifluoropropene (intermediate
Body No. Process 2) 3-chlorobenzyl-triphenylphosphonium chloride 4
g (9.46 mmol) and 2.02 g (9.46 mmol) of S-trifluoroacetylcyclohexanethiol were stirred in 30 ml of anhydrous dioxane to give 1,1,1,3,3,3-hexamethyldisilazane.
0.2 g was added. On a water bath, 0.4 g of 60% sodium hydride was added little by little to this mixed solution and stirred for 4 hours. The reaction solution was poured into water, and the product was extracted with ethyl acetate. After washing with water, the solvent was distilled off under reduced pressure, and the crude product was subjected to silica gel column chromatography (hexane) to obtain 2.5 g of the target compound as a colorless oil.

(2) 1- (3-chlorophenyl) -2-
(Cyclohexylsulfonyl) -3,3,3-trifur
Preparation of olopropene (Compound No. 2) 1.91 g (5.96 m) of 1- (3-chlorophenyl) -2- (cyclohexylthio) -3,3,3-trifluoropropene
mol) was dissolved in 30 ml of dichloromethane, and 3.85 g (17.9 mmol) of 80% metachloroperbenzoic acid was added. After stirring at room temperature for 2.5 hours, methylene chloride was distilled off under reduced pressure. The residue was poured into an aqueous sodium hydrogen sulfite solution to decompose excess 80% metachloroperbenzoic acid, and then extracted with ethyl acetate. The solvent layer was separated, washed with an aqueous solution of sodium carbonate, and dried over sodium sulfate. The crude product obtained by evaporating the solvent under reduced pressure was subjected to silica gel column chromatography (hexane:
Ethyl acetate = 9: 1) to give the target compound as a colorless oil 2.04
g was obtained.

<Synthesis Example 3> 1- (3-chlorophenyl)
-1- (4-methylbenzylsulfonyl) -3,3,3
Method for producing trifluoropropene (Compound No. 44) (1) Triphenyl 3- (3-chlorophenyl) -2
-Oxy-1,1,1-trifluoro-2-propylide
Preparation of diphosphorane 300 ml of anhydrous dioxane were added to 21.4 g (50.6 mmol) of 3-chlorobenzyl-triphenylphosphonium chloride, and 55 ml of a 1.55 mol / l n-butyllithium hexane solution (85.
0 mmol) was added dropwise in small portions. One hour later, 13 g (61.7 mmol) of trifluoroacetic anhydride was added dropwise to the reaction mixture in small portions. After an additional hour, the reaction mixture was poured into a large amount of water and extracted with an appropriate amount of methylene chloride. After separating the solvent layer, it was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was subjected to column chromatography (methylene chloride) to obtain 9.41 g (38.5%) of the target compound as colorless crystals (melting point: 217 to 218.5 ° C).

(2) 1- (3-chlorophenyl) -3
Preparation of 3,3-trifluoropropyne Triphenyl 3- (3-chlorophenyl) -2-oxy-1,1,1-trifluoro-3 was prepared under reduced pressure distillation apparatus.
9.4 g of propylidenephosphorane (19.5 mmol
1) was heated to about 250 to 300 ° C. on a silicone oil bath to obtain 2.68 g (67%) of a target colorless liquid.

(3) 1- (3-chlorophenyl) -1-
(4-methylbenzylthio) -3,3,3-trifluoro
Preparation of Lopropene (Intermediate No. 44) 495 mg (2.42 mmol) of 1- (3-chlorophenyl) -3,3,3-trifluoropropyne and 334 mg (2.42 mmol) of 4-methylbenzylmercaptan were dissolved in 20 ml of tetrahydrofuran. 244 mg of triethylamine were added. At room temperature
After 5 hours, the reaction solution was poured into water, made weakly acidic with hydrochloric acid, and the product was extracted with ethyl acetate. After washing with water, the solvent was distilled off under reduced pressure, and the crude product was subjected to silica gel column chromatography (hexane) to obtain 332 mg of the target compound as a colorless oil.

(4) 1- (3-chlorophenyl) -1-
(4-methylbenzylsulfonyl) -3,3,3-tri
Preparation of Fluoropropene (Compound No. 44 ) 251 mg of 1- (3-chlorophenyl) -1- (4-methylbenzylthio) -3,3,3-trifluoropropene (0.
73 mmol) was dissolved in 10 ml of methylene chloride, and 474 mg (2.20 mmol) of 80% metachloroperbenzoic acid was added. After stirring at room temperature overnight, methylene chloride was distilled off under reduced pressure. The residue was poured into an aqueous sodium hydrogen sulfite solution to decompose excess 80% metachloroperbenzoic acid, and then extracted with ethyl acetate. The solvent layer was separated, washed with an aqueous solution of sodium carbonate, and dried over sodium sulfate. The crude product obtained by evaporating the solvent under reduced pressure was subjected to silica gel column chromatography (hexane: ethyl acetate = 9: 1) to obtain 231 mg of the target compound as a colorless oil.

<Synthesis Example 4> 1- (4-chlorophenyl)
-2- (cyclohexylsulfonyl) -3,3,3-to
Trifluoropropene (Compound No. 30) and 1-
(4-Chlorophenyl) -2- (cyclohexyl sulf)
Inyl) -3,3,3-trifluoropropene (compound
No. 61) Production method (1) 1- (4-chlorophenyl) -2- (cyclohexyl)
Silthio) -3,3,3-trifluoropropene (intermediate
Body No. 30) Production method 3-chlorobenzyl-triphenylphosphonium chloride 3
g (7.1 mmol) and 1.52 g (7.1 mmol) of S-trifluoroacetylcyclohexanethiol were stirred in 30 ml of anhydrous dioxane, and 0.2 g of 1,1,1,3,3,3-hexamethyldisilazane was added. On a water bath, 0.4 g of 60% sodium hydride was added little by little to this mixed solution and stirred for 4 hours. The reaction solution was poured into water, and the product was extracted with ethyl acetate. After washing with water, the solvent was distilled off under reduced pressure, and the crude product was subjected to silica gel column chromatography (hexane) to obtain 1.96 g of the target compound as a colorless oil.

(2) 1- (4-chlorophenyl) -2-
(Cyclohexylsulfonyl) -3,3,3-trifur
Olopropene (Compound No. 34) and 1- (4-
(Rolophenyl) -2- (cyclohexylsulfinyl)
-3,3,3-trifluoropropene (Compound No. 6
Production method of 1) 1- (4-chlorophenyl) -2- (cyclohexylthio) -3,3,3-trifluoropropene 1.9 g (5.9 mm
ol) was dissolved in 30 ml of dichloromethane, and 2.0 g (9.3 mmol) of 80% metachloroperbenzoic acid was added. After stirring at room temperature for 2.5 hours, methylene chloride was distilled off under reduced pressure. The residue was poured into an aqueous sodium hydrogen sulfite solution to decompose excess metachloroperbenzoic acid, and then extracted with ethyl acetate. The solvent layer was separated, washed with an aqueous solution of sodium carbonate, and dried over sodium sulfate. The crude product obtained by evaporating the solvent under reduced pressure was subjected to silica gel column chromatography (hexane: ethyl acetate = 9: 1), and 0.75 g of the desired product (compound No. 34) having a melting point of 101 to 104 ° C. and a melting point of 84 were obtained. 0.74 g of the target product (compound No. 61) at 85 ° C. was obtained.

<Synthesis Example 5> 1- (4-trifluoromethyl)
Ruphenyl) -2- (cyclohexylsulfonyl)-
3,3,3-trifluoropropene (Compound No. 2
9) and 1- (4-trifluoromethylphenyl)-
2- (cyclohexylsulfinyl) -3,3,3-to
Production method of trifluoropropene (compound No. 60) 1- (4- (trifluoromethyl) phenyl-2- (4-tolylthio) obtained by the same method as in Synthesis Example 4 (1).
―3,3,3-trifluoropropene 2.0 g (5.3 mmol)
Was dissolved in 30 ml of dichloromethane, and 1.6 g (7.4 mmol) of 80% metachloroperbenzoic acid was added. After stirring at room temperature for 3.5 hours, methylene chloride was distilled off under reduced pressure. The residue was poured into an aqueous sodium hydrogen sulfite solution to decompose excess 80% metachloroperbenzoic acid, and then extracted with ethyl acetate. The solvent layer was separated, washed with an aqueous solution of sodium carbonate, and dried over sodium sulfate. The crude product obtained by evaporating the solvent under reduced pressure was subjected to silica gel column chromatography (hexane: ethyl acetate = 8: 2), and 0.30 g of the desired product (Compound No. 29) having a melting point of 87 to 90 ° C. was obtained. 1.44 g of the target product (compound No. 60) at 75 to 77 ° C. was obtained.

<Synthesis Example 6> 2- (ethylsulfonyl)-
1- (2-naphthyl) -3,3,3-trifluoropro
Pen (Z-form) (Compound No. 121) and 2- (ethyl
Rusulfyl) -1- (2-naphthyl) -3,3,3-
Production method of trifluoropropene (compound No. 122) (1) 2- (ethylthio) -1- (2-naphthyl)-
3,3,3-trifluoropropene (intermediate No. 1
5) Preparation of 2-naphthyltrifluorophosphonium bromide 5 g (10.35
mmol) and S-ethyltrifluorothioacetate 1.69
g (10.35 mmol) in 40 ml of anhydrous dioxane,
1,1,1,3,3,3 hexamethyldisilazane 0.4
g was added. 0.43 g of 60% sodium hydride was added little by little to this mixed solution, and the mixture was stirred for 16 hours. The reaction solution was poured into water, and the product was extracted with ethyl acetate.
After washing with water, the solvent was distilled off under reduced pressure, and the crude product was subjected to silica gel column chromatography (hexane) to obtain 2.6 g of the target compound as a colorless oil.

(2) 2- (ethylsulfonyl) -1-
(2-naphthyl) -3,3,3-trifluoropropene
(Z form) (Compound No. 121) and 2- (ethyls)
Rufinyl) -1- (2-naphthyl) -3,3,3-to
Production method of trifluoropropene (Compound No. 122) 2- (ethylthio) -1- (2-naphthyl) -3,3,3
2.57 g of 3-trifluoropropene (9.1 mmo
l) was dissolved in 50 ml of dichloromethane, and 2.83 g (13.1 mmol) of 80% metachloroperbenzoic acid was added. After stirring at room temperature for 4 hours, methylene chloride was distilled off under reduced pressure. The residue was poured into an aqueous sodium sulfite solution to decompose excess metachlorobenzoic acid, and then extracted with ethyl acetate. The crude product obtained by evaporating the solvent under reduced pressure was subjected to silica gel column chromatography (hexane: ethyl acetate =
8: 2) to give a colorless oily target compound (Compound No.
121) and 0.425 g of the target compound (compound No. 122) as a colorless oil were obtained.

<Synthesis Example 7> 2- (ethylsulfonyl)-
1- (2-naphthyl) -3,3,3-trifluoropro
Method for producing pen (E-form) (compound No. 126) 2- (ethylsulfonyl) -1 obtained in Synthesis Example 6 above
-(2-Naphthyl)-3,3,3-trifluoropropene (Z form) (Compound No. 121) 0.99 g (3.
15 mmol) and 0.347 g (3.1) of thiophenol.
0.318 g (3.15 mmol) of triethylamine was added to a 30 ml THF solution of 5 mmol). After stirring at room temperature for 1 hour, the reaction solution was poured into water and extracted with ethyl acetate. The crude product was treated with a mixed solvent of n-hexane / methylene chloride to obtain 0.556 g of the target compound as a colorless oil.

The following Tables 1 to 17 show production examples of the compounds of the general formula (I) produced by the methods according to Synthesis Examples 1 to 7. Tables 1 to 5 and 8 to 16 show the compounds of the general formula (I-1a) among the compounds of the general formula (I),
Tables 6 and 7 show the compounds of the general formula (I), and Table 17 shows the compounds of the general formula (I-1b).

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

[0091]

[Table 8]

[0092]

[Table 9]

[0093]

[Table 10]

[0094]

[Table 11]

[0095]

[Table 12]

[0096]

[Table 13]

[0097]

[Table 14]

[0098]

[Table 15]

[0099]

[Table 16]

[0100]

[Table 17]

Synthesis Example 1 (1) to (5), Synthesis Example 2
Tables 18 to 26 below show production examples of the compound of the general formula (II) produced by the method according to (1), Synthesis Example 3 (1) and Synthesis Example 4 (1).

[0102]

[Table 18]

[0103]

[Table 19]

[0104]

[Table 20]

[0105]

[Table 21]

[0106]

[Table 22]

[0107]

[Table 23]

[0108]

[Table 24]

[0109]

[Table 25]

[0110]

[Table 26]

The vinyl sulfone derivative represented by the general formula (I) or a salt thereof is useful as an active ingredient of a pesticidal agent, particularly as an active ingredient of an agricultural and horticultural fungicide. Examples of fungicides for agricultural and horticultural use include rice blast, sesame leaf blight, and sheath blight; wheat powdery mildew, red mold, rust,
Snow rot, naked smut, eye spot, leaf blight, wilt; citrus black spot, scab; apple monilia, powdery mildew, spot leaf spot, scab; pear scab; Black spot disease; peach scab, scab, phomopsis rot; grape black rot, late rot, powdery mildew, downy mildew; oyster anthracnose, deciduous disease; cucumber anthracnose , Powdery mildew, vine blight, downy mildew; tomato leaf spot, leaf mold, plague; black spot of cruciferous vegetables, summer blight of potato, plague; strawberry powdery mildew; various crops It is effective for controlling diseases such as gray mold and sclerotium, and shows an excellent control effect on powdery mildew and rust of wheat in particular. It is also effective in controlling soil diseases caused by plant pathogens such as Fusarium, Picium, Rhizoctonia, Verticillium, and Plasmodiophora. The compound of the present invention not only has a long residual effect and shows an excellent preventive effect, but also has an excellent therapeutic effect, so that it is possible to control diseases by treatment after infection. The compound of the present invention further includes agricultural and horticulturally harmful insects, mites, nematodes, for example, insects such as planthoppers, diamondback moths, leafhoppers, adzuki beetles, tobacco cutworm, peach aphids, mites such as spider mites, spider mites, and red mites. It also has an excellent control effect against nematodes, such as nematodes and sweet potato nematodes.

When the pesticidal composition of the present invention is used, various forms such as emulsions, wettable powders, powders, liquids, granules, suspensions and the like are used together with auxiliaries as in the case of conventional agricultural chemical preparations. Can be formulated. In the actual use of these preparations, they can be used as they are or diluted to a predetermined concentration with a diluent such as water. As the auxiliary agent mentioned here, a carrier, an emulsifier, a suspending agent, a dispersing agent,
Examples include a spreading agent, a penetrant, a wetting agent, a thickener, a stabilizer and the like, and may be added as needed. Carriers are divided into solid carriers and liquid carriers.Solid carriers include animal and plant powders such as starch, sugar, cellulose powder, cyclodextrin, activated carbon, soy flour, wheat flour, rice flour, wood flour, fish flour, milk powder, etc. , Talc, kaolin, bentonite,
Organic bentonite, calcium carbonate, calcium sulfate,
Sodium bicarbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, silica, mineral powders such as sulfur powder and the like, as a liquid carrier, water, soybean oil, animal and vegetable oils such as cottonseed oil, ethyl alcohol, Alcohols such as ethylene glycol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, aliphatic hydrocarbons such as kerosene, kerosene and liquid paraffin, xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, and solvent naphtha Aromatic hydrocarbons such as chloroform,
Halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, ethyl acetate, esters such as glycerin ester of fatty acid, nitriles such as acetonitrile, sulfur-containing compounds such as dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylformamide and the like.

A suitable compounding weight ratio of the compound of the present invention to the auxiliary agent is generally 0.005: 99.95 to 90:10, preferably,
0.2: 99.8 to 80:20. The use concentration of the compound of the present invention varies depending on the target crop, the method of use, the form of preparation, the amount of application, etc., and cannot be unconditionally specified.However, in the case of foliage treatment, usually 0.1 to 10,000 ppm per active ingredient, preferably, 1 to 2,000 ppm. In the case of soil treatment,
Usually 10-100,000 g / ha, preferably 200-20,000 g / ha
ha.

The pesticidal composition of the present invention may contain, if necessary, other pesticides such as insecticides, acaricides, nematicides, fungicides, antivirals, attractants, herbicides, plant growth regulators. It can be mixed and used together with an agent or the like, and in this case, an even more excellent effect may be exhibited.

Examples of the pesticides, acaricides, or nematicides in the other pesticides, that is, the active ingredient compounds (generic names; partially included) of the pesticides include, for example, Profenofos (Profenofos). , Dichlorvos (Dic
hlorvos), Fenamiphos (Fenamiphos)
s), fenitrothion (Fenitrothio)
n), EPN, diazinon, Chlorpyrifos-me (Chlorpyrifos-me)
thyl), acephate, prothiofos, fosthiazate, phosphocarb (Phos)
organic phosphate compounds such as phocarb);

Carbaryl, Propoxur, Aldicarb (Aldi)
carb), Carbofuran,
Thiodicarb, Methomil (M
ethomyl), oxamyl (Oxamyl), ethiophencarb (Ethiofencarb), pirimicarb (Pirimicarb), fenobucarb (F
carbamate compounds such as enobucarb);

Nereistoxin derivatives such as Cartap, Thiocyclam;

Organochlorine-based compounds such as Dicofol and Tetradifon;

Fenbutati oxide (Fenbutati)
organometallic compounds such as n Oxide);

Fenvalerate (Fenvalerate)
e), permethrin (Cypermethrin), cypermethrin (Cypermethrin), deltamethrin (Deltamethrin), cyhalothrin (Cy)
halotrin), tefluthrin (Tefluth)
rin), Etofenprx (Ethofenpr)
ox) pyrethroid compounds;

Diflubenzuron (Diflubenzuron)
ron), chlorfluazuron (Chlorfluaz)
uron), teflubenzuron
ron) Benzoylurea-based compounds such as Novaluron;

Juvenile hormone-like compounds such as Methoprene;

Pyridazinone compounds such as pyridaben;

Fenpyroximate (Fenpyrox)
pyrazole-based compounds such as imate), fipronil, and tebufenpyrad;

Imidacloprid (Imidcloprr)
id), Nitenpyram, Acetamiprid, Diacloden, Thiacloprid (Thiac)
neonicotinoids such as loprid);

Tebufenozid (Tebufenozid)
e), methoxyfenozide
ide), chromafenozide (Chromafenoz)
hydrazine compounds such as ide);

A dinitro compound, an organic sulfur compound, a urea compound, a triazine compound, a hydrazone compound, and other compounds such as buprofezin (Bupr
ofezin), Hexythiazox (Hexithia)
zox), Amitraz, Chlordimform, Silafluofen, Triazamate (T
riazamate), pymetrozine (Pymetro)
zine), pyrimidifen
n), Chlorfenapyr (Chlorfenapy)
r), Indoxacarb, Acequinocyl, Etoxazole, Cyromazine (Cyroma)
compound), and the like. Furthermore,
Microbial pesticides such as BT agents, entomopathogenic virus agents, etc.
Avermectin, Milbemycin, Spinosad (Spi)
Nosad) and other antibiotics.

Examples of the active ingredient compounds of the fungicides (generic names; partially included) in the other pesticides include, for example, mepanipyrim, pyrimethanil, cyprodinil, and cyprodinil.
pyrimidinamine-based compounds such as Rodilin);

Triadimefo (Triadimefo)
n), Bitertanol, Triflumizole, Etaconazole, Propiconazole, Penconazole (P)
Enconazole, Flusilazole (Flusi)
lazole), microbutanil (Myclobut)
anil), cyproconazole (Cyproconaz)
ole), terbuconazole (Terbuconazo)
le), Hexaconazole
e), Furconazole
-Cis), Prochloraz,
Azo-based compounds such as metconazole, epoxyconazole, and tetraconazole;

Quinomethionate (Quinomethi)
quinoxaline-based compounds such as onate);

Maneb, Zineb (Zin)
eb), Manzezeb, Polycarbamate, Propineb (P
dithiocarbamate-based compounds such as ropineb);

Organic chlorine compounds such as fthalide, chlorothalonil and quintozene;

Benomyl, Thiophanate-Methyl
l), Carbendazim, 4
-Chloro-2-cyano-1-dimethylsulfamoyl-
Imidazole-based compounds such as 5- (4-methylphenyl) imidazole;

A pyridinamine compound such as Fluazinam;

A cyanoacetamide compound such as Cymoxanil;

Metalaxyl, oxadixyl, off-race (Of
urace), Benalaxyl,
Phenylamide compounds such as Furalaxyl and Cyprofuram;

Diclofluanid (Dichloflua)
sulfenic acid-based compounds such as nid);

Cupric hydroxide (cuprichydrox)
ide), copper-based compounds such as organic copper (Oxine Copper);

Hydroxisoxazole (Hydrox)
isoxazole-based compounds such as yisoxazole);

Fosetyl aluminum (Fosetyl-
Al), Turkish phos-methyl (Tolcofos-Met)
hyl), organic phosphorus compounds such as S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate;

Captan, Captafol, Folpet (Folpe)
N-halogenothioalkyl-based compounds such as t); Procymidone, Iprodione, Vinclozolin (Vincl)
dicarboximide compounds such as ozolin);

Flutolanil,
Benzanilide-based compounds such as Mepronil;

Piperazine compounds such as Triforine;

Pyrifenox (Pyrifenox)
A pyridine compound such as

Carbinol-based compounds such as fenarimol and flutriafol;

Fenpropidin (Fenpropid)
piperidine compounds such as ine);

Fenpropimorph (Fenpropim)
morpholine-based compounds such as

Fentin hydroxide (Fentin hydroxide)
Hydroxide), Fentin Acetate (Fen)
organotin-based compounds such as tin acetate);

[0149] Pencycuron
Urea compounds such as;

Dimethomorph (Dimethomorph)
h) a cinamic acid-based compound;

Dietofencarb (Diethofen)
phenylcarbamate-based compounds such as carb);

Fludioxonil
l) cyanopyrrole-based compounds such as fenpiclonil;

Azoxystrobin (Azoxystrobin)
bin), kresoxim-M
etyl), Metominophen
β-methoxy acrylate compounds such as n);

3-anilino-5-methyl-5- (4-phenoxyphenyl) -1,3-oxazolidine-2,4
Oxazolidinedione compounds such as diones;

Atraquinone compounds; crotonic acid compounds; antibiotics and other compounds such as isoprothiolane, tricyclazole, and pyroquilone;
roquilon), diclomedine (Dicromez)
ine), probenazole (Pro.benazol)
e), quinoxyfen, propamocarb hydrochloride (Propamocarb Hydr)
ochloride), spiroxamine (Spirox)
amine); and the like.

The test examples of the agricultural and horticultural pest control agents according to the present invention are described below. In each test, the control index followed the following criteria. [Control index] [Degree of pathogenesis: macroscopic observation] 5: No lesion or sporulation is observed at all. 4: Lesion area, number of lesions or spore formation area is less than 10% of the untreated area 3: Lesion area, number of lesions or spore formation area is less than 40% of the untreated area 2: Lesion area, The number of lesions or the area of sporulation is less than 70% of the untreated area 1: The area of the lesion, the number of lesions or the area of sporulation is 70% or more of the untreated area

Test Example 1 Test for Preventive Effect on Wheat Powdery Mildew Wheat (cultivar: Norin 61) was grown in a plastic pot having a diameter of 7.5 cm, and the compound of the present invention was adjusted to be 500 ppm when the 1.5 leaf stage was reached. 10 ml of the drug solution was sprayed using a spray gun. After the drug solution was dried, conidiospores of powdery mildew were sprinkled and inoculated, and kept in a constant temperature room at 20 ° C. Four to nine days after inoculation, the area of spore formation was examined, and the control index was determined according to the following evaluation criteria.

Test Example 2 Test for Preventive Effect on Tomato Blight Tomato (cultivar: Ponterosa) was grown in a plastic pot having a diameter of 7.5 cm, and sprayed with 10 ml of a chemical solution adjusted to 500 ppm of the compound of the present invention when the four-leaf stage was reached. Sprayed using a gun. After the drug solution was dried, the suspension of the zoospores of the disease-causing fungus was spray-inoculated, kept in a humid chamber at 20 ° C for 18 hours, and then kept in a constant temperature room at 20 ° C. 3 to 5 days after the inoculation, the lesion area was examined, and the control index was determined according to the evaluation criteria described above.

Test Example 3 Rice Blast Prevention Effect Test Rice (cultivar: Nipponbare) was cultivated in a plastic pot having a diameter of 7.5 cm.
When the 5 leaf stage was reached, 10 ml of a drug solution adjusted so that the compound of the present invention became 500 ppm was sprayed using a spray gun. After the drug solution was dried, a conidia suspension of blast fungus was sprayed and inoculated, kept in an inoculation box at 20 ° C for 24 hours, and then kept in a constant temperature room at 20 ° C. Six to eleven days after the inoculation, the number of lesions was examined, and a control index was determined according to the evaluation criteria described above.

Test Example 4 Tomato Epidemic Treatment Effect Test Tomato (variety: Ponterosa) was cultivated in a plastic pot having a diameter of 7.5 cm, and when it reached the 4-leaf stage, a suspension of the zoosporangium of the epidemic was sprayed and inoculated. It was kept in a humidity chamber at ℃. Five hours after the inoculation, 10 ml of a chemical solution adjusted so that the compound of the present invention became 500 ppm was sprayed using a spray gun. After the chemical was dried, it was kept in a constant temperature room at 20 ° C. After 3 to 5 days from the treatment, the lesion area was examined, and the control index was determined according to the evaluation criteria.

Test Example 5 Wheat Powdery Mildew Treatment Effect Test Wheat (cultivar: Norin 61) was cultivated in a plastic pot having a diameter of 7.5 cm, and when it reached the 1.5-leaf stage, the conidiospores of powdery mildew were sprinkled and inoculated. , Kept in a constant temperature room at 20 ° C. One day after the inoculation, 10 ml of a chemical solution adjusted to 500 ppm of the compound of the present invention was sprayed using a spray gun. After the chemical has dried,
It was kept in a constant temperature room at 20 ° C. Seven days after the treatment, the area of spore formation was investigated, and the control index was determined according to the evaluation criteria.

Tables 27 to 32 show the results of Test Examples 1 to 5 above.
It was shown to.

[0163]

[Table 27]

[0164]

[Table 28]

[0165]

[Table 29]

[0166]

[Table 30]

[0167]

[Table 31]

[0168]

[Table 32]

Next, Formulation Examples of the present invention will be described. However, the compounds, dosage amounts, dosage forms and the like in the present invention are not limited only to the described Examples. Formulation Example 1 (A) Compound No. 21 50 parts by weight (b) Kaolin 40 parts by weight (c) Sodium ligninsulfonate 7 parts by weight (d) Dialkyl sulfosuccinate 3 parts by weight The above components are uniformly mixed to obtain a wettable powder.

Formulation Example 2 (A) Compound No. 33 20 parts by weight (b) 72 parts by weight of kaolin (c) 4 parts by weight of sodium ligninsulfonate (4) 4 parts by weight of polyoxyethylene alkylaryl (aryl) ether Can be

Formulation Example 3 (A) Compound No. 35 6 parts by weight (b) Diatomaceous earth 88 parts by weight (c) Dialkyl sulfosuccinate 2 parts by weight (d) Polyoxyethylene alkyl phenyl ether sulfate 4 parts by weight The above components are uniformly mixed to obtain a wettable powder. Can be

Formulation Example 4 (a) 78 parts by weight of kaolin (b) 2 parts by weight of formalin condensate of β-naphthalenesulfonic acid sodium (c) 5 parts by weight of polyoxyethylene alkyl aryl (aryl) sulfate 5 parts by weight of hydrous amorphous carbon dioxide Silicon 15 parts by weight A mixture of the above components and Compound No. 17 and 4: 1
To obtain a wettable powder.

Formulation Example 5 (A) Compound No. 6 20 parts by weight (b) N, N-dimethylacetamide 60 parts by weight (c) polyoxyethylene alkylaryl (aryl) ether 20 parts by weight The above components are mixed and dissolved to obtain an emulsion.

Formulation Example 6 (A) Compound No. 13 10 parts by weight (b) Diatomaceous earth 69 parts by weight (c) Calcium carbonate powder 15 parts by weight (d) Dialkyl sulfosuccinate 1 part by weight (e) Polyoxyethylene alkyl phenyl ether sulfate 3 parts by weight (f) β- A wettable powder is obtained by uniformly mixing 2 parts by weight or more of sodium naphthalene sulfonate formalin condensate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 317/12 C07C 317/12 317/14 317/14 317/18 317/18 317/44 317/44 323 / 07 323/07 323/16 323/16 323/52 323/52 C07D 213/34 C07D 213/34 213/61 213/61 213/64 213/64 213/89 213/89 239/38 239/38 261 / 08 261/08 317/56 317/56 317/62 317/62 333/28 333/28 (72) Inventor Munekazu Ogawa 2-3-1 Nishi-Shibukawa, Kusatsu City, Shiga Prefecture Ishihara Sangyo Co., Ltd. (72) Inventor Akihiro Nishimura 2-3-1 Nishi-Shibukawa, Kusatsu-shi, Shiga Ishihara Sangyo Co., Ltd. Central Research Laboratory F-term (reference) 4C055 AA01 BA02 BA03 BA39 BA42 BA46 BB04 BB07 BB09 CA01 CA02 CA06 CA13 DA01 DA06 DA20 4C056 AA01 AB01 AC01 AD01 AE03 AF05 FA03 FB07 FC01 4H006 AA01 AA02 AB03 AB84 AC62 AC63 BA69 TA03 TA04 TB54 TB56 TB57 TB77 TC06 TC09 4H011 AA01 AA03 AC01 AC04 BB07 BB08 BB09 BB10 DA01 DA12 DD03 DE15

Claims (11)

[Claims] 1. A compound of the general formula (I): Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group; A is a haloalkyl group; and B is a-(CH ₂ ) _n -R ¹ group, wherein R ¹ Is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group, a cyano group or an optionally substituted heteroaryl group;
Or 2), — (CH ₂ ) _p —R ² group (wherein R ²
Is an optionally substituted aryl group, and p is 1 or 2
Or an optionally substituted naphthyl group; m
Is 1 or 2. However, 1-bromo-2-methylsulfonyl-3-phenyl-2-propene is excluded. ] The vinyl sulfone derivative represented by these, or its salt. 2. A compound of the general formula (I-1): Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group; A is a haloalkyl group; and B is a-(CH ₂ ) _n -R ¹ group, wherein R ¹ Is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group, a cyano group or an optionally substituted heteroaryl group;
Or 2), — (CH ₂ ) _p —R ² group (wherein R ²
Is an optionally substituted aryl group, and p is 1 or 2
Or an optionally substituted naphthyl group; m
Is 1 or 2. However, 1-bromo-2-methylsulfonyl-3-phenyl-2-propene is excluded. The vinylsulfone derivative of claim 1 or a salt thereof represented by the formula: 3. Ar is embedded image (Wherein X, Y, and Z are hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, cyano, nitro, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, Good aryloxy, optionally substituted heteroaryloxy, methylenedioxy, at least two of X, Y and Z may be fused to form a ring), an optionally substituted naphthyl group, The vinylsulfone derivative or a salt thereof according to claim 1 or 2, which is an optionally substituted isoxazolyl group or an optionally substituted thienyl group. 4. A is a compound having 1 to 3 carbon atoms and 1 to 5 halogen atoms.
4. The vinylsulfone derivative or a salt thereof according to claim 1, which is a haloalkyl group of 5. B is-(CH ₂ ) _n -R ¹ [wherein R ¹
Alkyl group which may be substituted, a cycloalkyl group, an optionally substituted alkoxycarbonyl group or a cyano group, n represents either 0, 1 or 2, B is - (CH _{2)
A p-} R ² group, wherein R ² is a phenyl group which may be substituted, and p is 1 or 2, or B is a naphthyl group which may be substituted. 4. A vinyl sulfone derivative or a salt thereof. 6. A compound of the general formula (I): Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group; A is a haloalkyl group; and B is a-(CH ₂ ) _n -R ¹ group, wherein R ¹ Is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group, a cyano group or an optionally substituted heteroaryl group;
Or 2), — (CH ₂ ) _p —R ² group (wherein R ²
Is an optionally substituted aryl group, and p is 1 or 2
Or an optionally substituted naphthyl group; m
Is 1 or 2. A method for producing a vinyl sulfone derivative or a salt thereof represented by the general formula (II): (Wherein Ar, A and B are as defined above) in a suitable solvent, wherein said compound is oxidized in a suitable solvent. 7. A compound of the general formula (I): Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group; A is a haloalkyl group; and B is a-(CH ₂ ) _n -R ¹ group, wherein R ¹ Is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group, a cyano group or an optionally substituted heteroaryl group;
Or 2), — (CH ₂ ) _p —R ² group (wherein R ²
Is an optionally substituted aryl group, and p is 1 or 2
Or an optionally substituted naphthyl group; m
Is 1 or 2. A method for producing a vinyl sulfone derivative or a salt thereof represented by the following general formula (II):
I): (Wherein Ar is as defined above), a compound represented by the general formula (IV): (A-CO) ₂ O, wherein A is as defined above, and And / or reacting a compound represented by the general formula (IV ′): A-CO-Hal wherein A is as described above and Hal is a halogen atom in the presence of a base, Formula (V): (Wherein, Ar and A are as defined above), (ii) the compound of the general formula (V) obtained in the first step is thermally decomposed to give a compound of the general formula (VI): (Wherein, Ar and A are as defined above), (iii) a compound of the general formula (VI) obtained in the second step, and a compound of the general formula (VII) : HS-B (wherein B is as defined above) is reacted with a thiol in the presence of a base to give a compound of the general formula (II): (Wherein Ar, A and B are as defined above), (iv) the compound of general formula (II) obtained in the third step in an appropriate solvent Oxidized by the fourth
A method for producing the vinyl sulfone derivative or a salt thereof, comprising the steps of: 8. A compound of the general formula (I-1): Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group; A is a haloalkyl group; and B is a-(CH ₂ ) _n -R ¹ group, wherein R ¹ Is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group, a cyano group or an optionally substituted heteroaryl group;
Or 2), — (CH ₂ ) _p —R ² group (wherein R ²
Is an optionally substituted aryl group, and p is 1 or 2
Or an optionally substituted naphthyl group; m
Is 1 or 2. A method for producing a vinyl sulfone derivative or a salt thereof represented by the general formula (III): (Wherein Ar is as described above), and a compound represented by the general formula (VIII): (Wherein A and B are as defined above) in the presence of a base to give a compound of the general formula (II-1): (Wherein Ar, A and B are as defined above), and then oxidizing the compound in an appropriate solvent to produce the vinyl sulfone derivative or a salt thereof. Method. 9. A compound of the general formula (II): Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group; A is a haloalkyl group; and B is a-(CH ₂ ) _n -R ¹ group, wherein R ¹ Is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group, a cyano group or an optionally substituted heteroaryl group;
Or 2), — (CH ₂ ) _p —R ² group (wherein R ²
Is an optionally substituted aryl group, and p is 1 or 2
Or a naphthyl group which may be substituted. ]
Or a salt thereof. 10. The general formula (II-1): Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group; A is a haloalkyl group; and B is a-(CH ₂ ) _n -R ¹ group, wherein R ¹ Is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group, a cyano group or an optionally substituted heteroaryl group;
Or 2), — (CH ₂ ) _p —R ² group (wherein R ²
Is an optionally substituted aryl group, and p is 1 or 2
Or a naphthyl group which may be substituted. ]
Or a salt thereof. 11. A compound of the general formula (I): Wherein Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group; A is a haloalkyl group; and B is a-(CH ₂ ) _n -R ¹ group, wherein R ¹ Is an optionally substituted alkyl group, a cycloalkyl group, an optionally substituted alkoxycarbonyl group, a cyano group or an optionally substituted heteroaryl group;
Or 2), — (CH ₂ ) _p —R ² group (wherein R ²
Is an optionally substituted aryl group, and p is 1 or 2
Or an optionally substituted naphthyl group; m
Is 1 or 2. A pesticidal agent comprising a vinyl sulfone derivative represented by the formula (1) or a salt thereof.