JP2009091320A - 1,3-dioxolane derivative, 1,3-dithiolane derivative and 1,3-oxathiolan derivative, and agricultural and horticultural bactericide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new 1,3-dioxolane derivative (I) showing controlling effects against various plant damages from diseases, especially having high soil treatment effect and water surface application effect against rice blast, and an agricultural and horticultural bactericide containing the same. <P>SOLUTION: The compound is expressed by general formula (I) [wherein, X, Y are each independently O or S; R<SB>1</SB>is H, an alkyl or the like; R<SB>2</SB>and R<SB>3</SB>are each hydrogen or an alkyl group; and A is a cyclohexane ring or a cyclopentane ring], and an agricultural and a horticultural bactericide comprising the compound are provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel 1,3-dioxolane derivative, 1,3-dithiolane derivative and 1,3-oxathiolane derivative, and an agricultural and horticultural fungicide containing the derivative.

So far, as the similar compounds of the 1,3-dioxolane derivative, 1,3-dithiolane derivative and 1,3-oxathiolane derivative of the present invention, compounds represented by the following general formulas (III) to (VII) have been known. (See Patent Documents 1 to 5).
These compounds are known to have bactericidal activity against various plant diseases, and are particularly useful against rice blast and tomato, cucumber, and green beans, but have sufficient control effects That's not true. Moreover, although these compounds have a control effect by spraying foliage against rice blast disease, the control effect by soil treatment and water surface application is extremely weak, so it cannot be said that rice blast disease can be controlled satisfactorily.

［式中、一般式（III）におけるＲ、Ｚ_ｎ、Ｘ_ｍは特許文献１によって定義され、一般式（IV）におけるＡ、Ｗ、Ｘ_ｍ、Ｙ_ｎ、Ｚ_ｐは特許文献２によって定義され、一般式（Ｖ）におけるＡ、Ｂ、Ｘ_ｍ、Ｙ_ｐ、Ｚは特許文献３によって定義され、一般式（VI）におけるＡ，Ｘ_ｍ、Ｙ_ｎ、Ｗ_ｐ、Ｚは特許文献４によって定義され、一般式（VII）におけるＡ，Ｒ、Ｘ、Ｙ_ｎは特許文献５によって定義される。］
国際公開特許ＷＯ０２／０８８０８６号パンフレット 国際公開特許ＷＯ０４／００５２６１号パンフレット 特開２００４‐１１５４３５号公報 特開２００５‐２０６５１７号公報 国際公開特許ＷＯ０４／０３９７８３号パンフレット General formula (III)-(VII)

[In the formula, R, Z _n and X _m in the general formula (III) are defined by Patent Document 1, and A, W, X _m , Y _{n and} Z _p in the general formula (IV) are defined by Patent Document 2. , A, B, X _m , Y _{p and} Z in general formula (V) are defined by Patent Document 3, and A, X _m , Y _n , W _p and Z in General Formula (VI) are defined by Patent Document 4. In the general formula (VII), A, R, X, and Y _n are defined by Patent Document 5. ]
International Publication WO02 / 088086 Pamphlet International Patent Publication WO04 / 005261 Pamphlet JP 2004-115435 A JP 2005-206517 A International Publication WO04 / 039783 Pamphlet

  Among various plant diseases, rice blast is one of the important diseases, and many fungicides have been developed so far. However, although there is a control effect by foliage spraying, there are few drugs that show a sufficient control effect even in soil treatment and water surface application situations. Some drugs have a reduced control effect due to the emergence of resistant bacteria, and a drug having a novel chemical structure is strongly desired. Furthermore, in today's situation where the number of farmers is declining and aging, there are hopes for drugs that promote the reduction and labor saving of control work with characteristics such as preventive / therapeutic activity, permeability penetration, and long-term residual effect. It is rare. In addition, the control of rice blast disease by foliar spraying of pesticides in Honda is not a safe control method because there are concerns about the impact on the surrounding environment and the safety of users due to the scattering of chemicals. Therefore, in order to ensure the safety of the user and the surrounding environment as well as the consumer as well as the consumer, there is a strong demand for a chemical having a sufficient control effect in soil treatment and water surface application scenes.

  The present invention is intended to solve the above-mentioned problems, and is a novel 1,3-dioxolane derivative having high soil treatment effect and water surface application effect required in actual situations for rice blast disease, It is an object to provide a 1,3-dithiolane derivative or a 1,3-oxathiolane derivative.

  As a result of intensive studies to solve the above problems, the present inventors have found that the following novel 1,3-dioxolane derivatives, 1,3-dithiolane derivatives, and 1,3-oxathiolane derivatives have been used in various plant diseases. It has been found that it has bactericidal activity and has an excellent soil treatment effect and water surface application effect especially against rice blast.

  Accordingly, the first invention of the present application relates to a novel 1,3-dioxolane derivative, 1,3-dithiolane derivative and 1,3-oxathiolane derivative represented by the following general formula (I).

一般式（Ｉ）中、ＸおよびＹは、それぞれ独立に酸素原子または硫黄原子を示し、Ｒ₁は、アルキル基、アルコキシアルキル基またはハロアルキル基を示し、Ｒ_２およびＲ_３は、それぞれ独立に水素原子またはアルキル基を示し、Ａは、シクロヘキサン環またはシクロペンタン環を示す。
本願の第２の発明は、上記一般式（Ｉ）で表される１，３‐ジオキソラン誘導体、１，３‐ジチオラン誘導体若しくは１,３‐オキサチオラン誘導体を含有することを特徴とする農園芸用殺菌剤に関する Here, the 1,3-dioxolane derivative, 1,3-dithiolane derivative and 1,3-oxathiolane derivative represented by the general formula (I) include stereoisomers as described later.
Formula (I)

In general formula (I), X and Y each independently represent an oxygen atom or a sulfur atom, R ₁ represents an alkyl group, an alkoxyalkyl group or a haloalkyl group, and R ₂ and R ₃ each independently represent hydrogen. Represents an atom or an alkyl group, and A represents a cyclohexane ring or a cyclopentane ring.
A second invention of the present application contains a 1,3-dioxolane derivative, a 1,3-dithiolane derivative or a 1,3-oxathiolane derivative represented by the above general formula (I), and is characterized by sterilization for agriculture and horticulture About drugs

When the 1,3-dioxolane derivative, 1,3-dithiolane derivative or 1,3-oxathiolane derivative of the present invention is used as an agricultural and horticultural fungicide, the following effects are exhibited.
First, the compound of the present invention exhibits control activity against plant diseases such as cucumber gray mold, barley powdery mildew, wheat red rust, rice blast and the like, and is useful as an agricultural and horticultural fungicide.
Secondly, the compound of the present invention shows osmotic transfer into rice even when soil treatment and water surface application are performed, and rice blast can be controlled by soil treatment and water surface application.
Thirdly, the compound of the present invention has both a prophylactic effect and a therapeutic effect, especially for blast, and the effect exhibits long-term residual effect.
Fourthly, the agricultural and horticultural fungicide of the present invention can be used safely without causing any phytotoxicity to useful crops.
Therefore, the agricultural and horticultural fungicide containing the compound according to the present invention as an active ingredient can be used for various diseases of agricultural and horticultural crops by foliage spraying, soil treatment and water surface application.

  Hereinafter, the novel 1,3-dioxolane derivative, 1,3-dithiolane derivative and 1,3-oxathiolane derivative according to the present invention, the production method thereof, and the agricultural and horticultural fungicide containing this as an active ingredient will be specifically described. .

[1,3-dioxolane derivative, 1,3-dithiolane derivative and 1,3-oxathiolane derivative]
Hereinafter, each of the substituents represented by _R 1, _{R 2} and _{R 3} in the general formula (I), and for A will be described.
However, each substituent in the said general formula (I) is not limited to the example shown here.

Examples of the alkyl group represented by R ₁ include linear or branched alkyl groups having 1 to 6 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl Group, i-pentyl group, neopentyl group, n-hexyl group, 1-methylpentyl group, i-hexyl group, 2-ethylbutyl group and the like. A methyl group and an ethyl group are preferred.

In the alkoxyalkyl group represented by R ₁ , examples of the alkoxy moiety of the alkoxyalkyl group include linear or branched alkoxy having 1 to 6 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2-methyl-1- Examples include butoxy, i-pentyloxy, neopentyloxy, n-hexyloxy, 2-methyl-1-pentyloxy, 2-ethyl-1-butoxy and the like. Preferably it is methoxy. And the alkyl part of the said alkoxyalkyl group can mention a C1-C6 linear or branched alkyl. Specifically, methylene, ethylene, n-propylene, 1-methylethylene, 2-methylethylene, n-butylene, 1-methylpropylene, 2-methylpropylene, n-pentylene, 1-methylbutylene, 2-ethylpropylene, Examples thereof include n-hexylene and 1-methylpentylene. Preferably it is methylene.
Examples of the haloalkyl group represented by R ₁ include linear or branched haloalkyl groups having 1 to 6 carbon atoms. Specifically, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-fluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group Examples thereof include a 1-fluoro-i-butyl group and a 1-fluoro-i-hexyl group. A trifluoromethyl group is preferred.

Examples of the alkyl group represented by R ₂ and R ₃ include linear alkyl groups having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. A methyl group and an ethyl group are preferred.
A represents a cyclohexane ring or a cyclopentane ring.

  The compound represented by the general formula (I) according to the present invention may have one or more asymmetric carbon atoms. Therefore, the compound of the present invention may exist as two or more stereoisomers. The compound of the present invention includes all stereoisomers such as enantiomers and diastereomers, and when it is a mixture of isomers, the ratio is not particularly limited and may be arbitrary.

Although the specific example of a compound represented by general formula (I) is shown in Table 1, the compound of this invention is not limited only to the compound illustrated here.
In Table 1, “cHex” represents a cyclohexane ring, and “cPen” represents a cyclopentane ring.
Et and H in the columns of R ₂ and R _{3 in} Table 1 indicate a mixture of R ₂ = Et, R ₃ = H, R ₂ = H, and R ₃ = Et.
O and S in the columns of X and Y in Table 1 indicate a mixture of X = O, Y = S and X = S, Y = O.
For cis and trans in Table 1, the relative arrangement of cis and trans was determined from the coupling constant between protons belonging to the roots of R ₂ and R _{3 and} the vicinal correlation by Karplus.
The compound numbers in Table 1 are also referred to in the following Table 2, Table 3, Examples and Test Examples.

＊１：表中、ｃＨｅｘはシクロヘキサン環、ｃＰｅｎはシクロペンタン環を表す。
＊２：Ｒ_２＝Ｅｔ、Ｒ_３＝ＨとＲ_２＝Ｈ、Ｒ_３＝Ｅｔの混合物
＊３：Ｘ＝Ｏ，Ｙ＝ＳとＸ＝Ｓ，Ｙ＝Ｏの混合物
＊４:Ｒ_２とＲ_３のそれぞれの付け根に帰属されるプロトン間のカップリング定数とＫａｒｐｌｕｓによるビシナル相関関係からｃｉｓ、ｔｒａｎｓを決定した。

* 1: In the table, cHex represents a cyclohexane ring, and cPen represents a cyclopentane ring.
* 2: R ₂ = Et, R ₃ = H and R ₂ = H, R ₃ = Et mixture * 3: X = O, Y = S and X = S, Y = O mixture * 4: R ₂ Cis and trans were determined from the coupling constant between protons belonging to each base of R _{3 and} the vicinal correlation by Karplus.

［式中、Ｘは、酸素原子または硫黄原子を示し、Ｒ₁は、水素、アルキル基、アルコキシアルキル基またはハロアルキル基を示し、Ｒ_２およびＲ_３は、水素原子またはアルキル基を示し、Ａはシクロヘキサン環またはシクロペンタン環を示し、Ｈａｌはハロゲン原子を示す。］ [Method for producing compound of the present invention]
The compound represented by the general formula (I) according to the present invention can be produced, for example, according to Production Method A and Production Method B described below.
[Production method A]

[Wherein, X represents an oxygen atom or a sulfur atom, R ₁ represents hydrogen, an alkyl group, an alkoxyalkyl group or a haloalkyl group, R ₂ and R ₃ represent a hydrogen atom or an alkyl group, and A represents A cyclohexane ring or a cyclopentane ring is shown, Hal shows a halogen atom. ]

Step A-1 can be carried out under any reaction conditions, but is preferably carried out in an inert organic solvent. An inert solvent means an organic solvent that does not react with a solute, that is, a raw material, a product, or the like (hereinafter also referred to as an inert organic solvent).
Examples of the inert solvent that can be used in this production method include halogen solvents such as dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride, diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, and the like. Examples include ether solvents, aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene. Of these, dichloromethane and chloroform are preferred.
Examples of the halogenating agent used in the reaction include oxalyl chloride, thionyl chloride, phosphorus trichloride, and phosphorus pentachloride.
The amount of the halogenating agent used in the reaction is usually 1 to 2 mol, preferably 1 to 1.5 mol, per 1 mol of the compound represented by the general formula (II). . This reaction is usually performed at a temperature of 0 to 100 ° C, preferably 20 to 80 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours.
After completion of the reaction, the compound represented by the general formula (VIII) can be isolated by performing post-treatment such as concentrating the reaction mixture as it is. “End of reaction” means, for example, that one or both of raw materials in a solvent are consumed, and can be confirmed by, for example, thin layer chromatography (hereinafter, the same meaning is expressed unless otherwise noted). The isolated compound represented by the formula (VIII) can be used in the next step without purification.

Step A-2 can be carried out under any reaction conditions, but is preferably carried out in an inert organic solvent. Examples of the inert solvent that can be used in this production method include halogen solvents such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, and the like. And ether hydrocarbon solvents, aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene. Of these, dichloromethane, chloroform, and tetrahydrofuran (THF) are preferred.
Examples of the base used in the reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine, tri-n-propylamine, N, N-diisopropylethylamine and the like.
The amount of the reagent used in the reaction is usually 1 to 5 mol, preferably 1 to 2 mol of the base, based on 1 mol of the compound represented by the general formula (IX), and represented by the general formula (VIII). The compound to be used is usually used in an amount of 1 to 2 mol, preferably 1.05 mol.
This reaction is usually performed at a temperature of 0 to 100 ° C, preferably 20 to 80 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 24 hours.
After completion of the reaction, the 1,3-dioxolane derivative or 1,3-dithiolane derivative represented by the general formula (I) -a of the present invention is extracted, for example, by adding water and an organic solvent to the reaction solution containing the derivative. Thereafter, it is further washed with water and saturated saline, and the solvent is distilled off. The obtained object product (I) -a can be further purified by operations such as column chromatography or recrystallization, if necessary.

［式中、Ｘは、それぞれ独立に酸素原子または硫黄原子を示し、Ｒ₁は、水素、アルキル基、アルコキシアルキル基またはハロアルキル基を示し、Ｒ_２およびＲ_３は水素原子またはアルキル基を示し、Ａは、シクロヘキサン環またはシクロペンタン環を示す。］ [Production method B]

[Wherein X independently represents an oxygen atom or a sulfur atom, R ₁ represents hydrogen, an alkyl group, an alkoxyalkyl group or a haloalkyl group, R ₂ and R ₃ represent a hydrogen atom or an alkyl group, A represents a cyclohexane ring or a cyclopentane ring. ]

By reacting the carboxylic acid derivative represented by the general formula (II) with a condensing agent in the presence of a base (dehydration condensation), 1,3-dioxolane represented by the general formula (I) -a of the present invention Derivatives or 1,3-dithiolane derivatives can be prepared.
This reaction can be carried out under any reaction conditions, but is preferably carried out in an inert organic solvent. Examples of the inert solvent that can be used in this production method include halogen solvents such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, and the like. And ether solvents, aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene, and solvents containing heteroatoms such as acetonitrile and N, N-dimethylformamide. Of these, acetonitrile and N, N-dimethylformamide are preferred.
Examples of condensing agents include 1,3-dicyclohexylcarbodiimide, 1-ethyl-3- (3'-dimethylaminopropyl) carbodiimide, 2-methyl-6-nitrobenzoic anhydride, methanesulfonyl chloride, p-toluenesulfonyl chloride, etc. Can be mentioned.
Examples of the base that can be used include pyridine, triethylamine, tri-n-propylamine, N, N-diisopropylethylamine, and 4-dimethylaminopyridine.
The amount of the condensing agent to be used is generally 1 to 2 mol, preferably 1 to 1.1 mol, and the base is usually 1 to 4 mol, preferably 1 mol, relative to 1 mol of the compound represented by the general formula (IX). The compound represented by 1 to 2 mol and general formula (II) can be used in an amount of usually 1 to 2 mol, preferably 1.05 mol. This reaction is usually performed at a temperature of 0 to 80 ° C, preferably 0 to 40 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 24 hours.
After completion of the reaction, the 1,3-dioxolane derivative or 1,3-dithiolane derivative represented by the general formula (I) -a of the present invention can be obtained, for example, by adding water and an organic solvent to the reaction solution containing the derivative. After extraction, it is further washed with water and saturated saline, and the solvent is distilled off. The obtained object (I) -a can be further purified by operations such as column chromatography or recrystallization, if necessary.

  The compound represented by the general formula (II), which is a raw material of the compound represented by the general formula (I) of the present invention, can be synthesized by any method, but a particularly preferable general production method is represented by the following production methods C to C. This is shown in Production Method E.

［式中、Ｘは、酸素原子または硫黄原子を示し、Ｒ_１は水素原子を示し、Ｒ_６は炭素数１〜６の低級アルキル基を示し、Ｒ_２およびＲ_３は、それぞれ独立に水素原子または炭素数１〜６の低級アルキル基を示し、Ａは、シクロヘキサン環またはシクロペンタン環を示し、Ｑは水素原子またはトリメチルシリル基を示す。］ [Production Method C]

[Wherein, X represents an oxygen atom or a sulfur atom, R ₁ represents a hydrogen atom, R ₆ represents a lower alkyl group having 1 to ₆ carbon atoms, and R ₂ and R ₃ each independently represent a hydrogen atom. Alternatively, it represents a lower alkyl group having 1 to 6 carbon atoms, A represents a cyclohexane ring or a cyclopentane ring, and Q represents a hydrogen atom or a trimethylsilyl group. ]

Step C-1 can be carried out under any reaction conditions, but is preferably carried out in an inert organic solvent. Examples of the inert solvent that can be used in the present production method include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, and ethylene glycol dimethyl ether, hydrocarbon solvents such as n-hexane and cyclohexane, benzene, Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene. Of these, tetrahydrofuran (THF) is preferred.
Examples of the base used in the reaction include lithium diisopropylamide, lithium hexamethyldisilazide, sodium hydride, potassium hydride, potassium t-butoxide and the like. Examples of the formylating agent include methyl formate and ethyl formate.
The amount of the formylating agent used in the reaction is usually 1 to 10 mol, preferably 1.5 to 5 mol, per 1 mol of the compound represented by the general formula (XII), and the amount of the base is usually 1 It is used in an amount of -10 mol, preferably 1.1-5 mol. This reaction is usually performed at a temperature of -80 to 20 ° C, preferably -70 to 0 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours.
After completion of the reaction, the compound represented by the general formula (XIII) is extracted, for example, by adding water and an organic solvent to the reaction solution containing the derivative, followed by washing with water and saturated saline, and distilling off the solvent. Can be obtained. The obtained target product (XIII) can be purified by an operation such as column chromatography, if necessary.

Step C-2 can be carried out under any reaction conditions, but is preferably carried out in an inert organic solvent. Examples of the inert solvent that can be used in this production method include halogen solvents such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, and the like. And ether hydrocarbon solvents, aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene. Of these, dichloromethane and toluene are preferred.
Catalysts used in the reaction include hydrogen chloride (or hydrochloric acid), hydrogen bromide, Bronsted acids such as p-toluenesulfonic acid, ammonium salts such as ammonium chloride and pyridinium hexafluoroantimonate, trimethylsilylfluoromethanesulfonate, and trifluoride. Examples include Lewis acids such as boron etherate, titanium tetrachloride, and scandium trifluoromethanesulfonate. Of these, p-toluenesulfonic acid is preferred.
Examples of the compound represented by the general formula (XIV) used in the reaction include ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1 , 2-heptanediol, 1,2-octanediol, ethylenedioxybis (trimethylsilane), 2,3-butanediol, 1,2-ethanedithiol, 1,2-propanedithiol, 2,3-butanedithiol, And ethylenedithiobis (trimethylsilane).
The amount of the reagent used in the reaction is usually 1 to 30 mol, preferably 4 to 20 mol of the compound represented by the general formula (XIV) with respect to 1 mol of the compound represented by the general formula (XIII). Used. The amount of the catalyst is usually 0.01 to 1.0 mol, preferably 0.02 to 0.5 mol. This reaction is usually performed at a temperature of 0 to 120 ° C, preferably 20 to 100 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 24 hours.
After completion of the reaction, the compound represented by the general formula (XV) is extracted, for example, by adding water and an organic solvent to the reaction solution containing the derivative, and further washed with water and saturated brine, and the solvent is distilled off. Can be obtained. The obtained target product (XV) can be further purified by an operation such as column chromatography, if necessary.

Step C-3 can be carried out under any reaction conditions, but is preferably carried out in an inert organic solvent. For example, alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, dimethyl sulfoxide, acetonitrile, N, N-dimethylformamide What mixed the solvent containing hetero atoms, such as these, and water in arbitrary ratios can be mentioned. Of these, dimethyl sulfoxide: water is preferably mixed at a ratio of 1 to 10: 1.
Examples of the base used in the reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and potassium t-butoxide.
The amount of the base used for the reaction can be generally 1 to 10 mol, preferably 3 to 5 mol, per 1 mol of the compound represented by the general formula (XV).
This reaction is usually performed at a temperature of 0 to 130 ° C, preferably 20 to 120 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 24 hours.
After completion of the reaction, the compound represented by the general formula (II) is made acidic by adding hydrochloric acid, sulfuric acid or the like after adding water to the reaction solution containing the derivative, for example, diethyl ether, toluene, ethyl acetate, After extraction with a solvent for extraction such as dichloromethane and chloroform, it can be obtained by washing with water and saturated saline and distilling off the solvent. The obtained object (II) can be further purified by an operation such as column chromatography, if necessary.

In production method C, the compound represented by the general formula (XIII) is a known compound, and Journal of Organic
(XIII) can also be synthesized and used according to the method described in Chemistry 38, No. 1, Item 36 (1973).

［式中、Ｘは、酸素原子または硫黄原子を示し、Ｒ₁は、炭素数１〜６の低級アルキル基、アルコキシアルキル基またはハロアルキル基を示し、Ｒ_２およびＲ_３は、それぞれ独立に水素原子または炭素数１〜６の低級アルキル基を示し、Ｒ_６は炭素数１〜６の低級アルキル基を示し、Ｒ_７は炭素数１〜５の低級アルキル基、アルコキシアルキル基またはハロアルキル基を示し、Ａは、シクロヘキサン環またはシクロペンタン環を示し、Ｑは、水素原子またはトリメチルシリル基を示す。］ [Production Method D]

[Wherein, X represents an oxygen atom or a sulfur atom, R ₁ represents a lower alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group or a haloalkyl group, and R ₂ and R ₃ each independently represents a hydrogen atom. Or a lower alkyl group having 1 to 6 carbon atoms, R ₆ represents a lower alkyl group having 1 to ₆ carbon atoms, R ₇ represents a lower alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or a haloalkyl group, A represents a cyclohexane ring or a cyclopentane ring, and Q represents a hydrogen atom or a trimethylsilyl group. ]

Step D-1 can be carried out under any reaction conditions, but is preferably carried out in an inert organic solvent. Examples of the inert solvent that can be used in the present production method include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, and ethylene glycol dimethyl ether, hydrocarbon solvents such as n-hexane and cyclohexane, benzene, Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene. Of these, tetrahydrofuran (THF) is preferred.
Examples of the base a used in the reaction include lithium diisopropylamide, lithium hexamethyldisilazide, sodium hydride, potassium hydride, potassium t-butoxide and the like.
As the acylating agent used in the reaction, acetic anhydride, anhydrous n-propionic acid, anhydrous n-butyric acid, anhydrous i-butyric acid, anhydrous n-valeric acid, anhydrous i-valeric acid, anhydrous n -Hexanoic acid, anhydrous -n-heptanoic acid, methyl acetate, ethyl acetate, methyl propionate, methyl n-butyrate, methyl i-butyrate, methyl n-valerate, methyl 2-methylbutanoate, methyl i-valerate, n-hexanoic acid methyl, 2-methylpentanoic acid methyl, t-butyl ethyl acetate, n-heptanoic acid methyl, 2-methyl hexanoic acid methyl, acetyl chloride, propionic acid chloride, n-butyric acid chloride, i-butyric acid chloride, n -Valeric acid chloride, 2-methylbutanoic acid chloride, i-valeric acid chloride, n-hexanoic acid chloride, 2-methylpentanoic acid chloride, 3-methyl Rupentanoic acid chloride, i-hexanoic acid chloride, t-butyl acetic acid chloride, n-heptanoic acid chloride, 2-methylhexanoic acid chloride, i-heptanoic acid chloride, 3-ethylpentanoic acid chloride, methoxyacetic acid chloride, ethoxyacetic acid chloride, n-propoxyacetic acid chloride, i-propoxyacetic acid chloride, n-butoxyacetic acid chloride, s-butoxyacetic acid chloride, i-butoxyacetic acid chloride, n-pentoxyacetic acid chloride, 1-methyl-butoxyacetic acid chloride, 2-methyl-butoxyacetic acid Chloride, i-pentoxyacetic acid chloride, 2,2-dimethylpropoxyacetic acid chloride, n-hexoxyacetic acid chloride, 1-methyl-n-pentoxyacetic acid chloride, 2-methyl-pentoxyacetic acid chloride, 2-methoxy-propionic acid chloride, 2-ethoxy-propionic acid chloride, 3-methoxy-propionic acid chloride, 3-methoxy-2-methyl-propionic acid chloride, 3-methoxy-3-methyl-propionic acid chloride, 4- Methoxy-butanoic acid chloride, 3-methoxy-2-methyl-propionic acid chloride, 3-methoxy-3-methyl-propionic acid chloride, 5-methoxy-n-pentanoic acid chloride, 4-methoxy-2-methyl-n- Butanoic acid chloride, 6-methoxy-hexanoic acid chloride, 7-methoxy-heptanoic acid chloride, 6-methoxy-1-methyl-hexanoic acid chloride, trifluoroacetic anhydride, pentafluoropropionic anhydride, anhydrous n-heptafluorobutane Acid, monofluoroacetic acid ethyl , Ethyl difluoroacetate, ethyl trifluoroacetate, ethyl pentafluoro-n-propionate, ethyl heptafluoro-n-butanoate, ethyl nonafluoro-n-pentanoate, 2-trifluoromethyl-3,3,3-trifluoro Mention may be made of methyl propionate, methyl 2-fluoro-hexanoate, methyl 2-fluoro-i-hexanoate, methyl 2-fluoro-heptanoate, methyl 2-fluoro-i-heptanoate and the like.
The amount of the acylating agent used in the reaction is usually 1 to 10 mol, preferably 1.5 to 5 mol, relative to 1 mol of the compound represented by formula (XII), and the amount of base a is usually 1 It can be used in an amount of -10 mol, preferably 1.1-5 mol. This reaction is usually performed at a temperature of -80 to 20 ° C, preferably -70 to 0 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours.
After completion of the reaction, the reaction solution containing the derivative is extracted by adding water and an organic solvent, and further washed with water and saturated brine, the solvent is distilled off, and the resulting crude product is subjected to column chromatography, etc. To obtain a compound represented by the general formula (XIII). In Step D-1, in addition to the target compound represented by the general formula (XIII), the compound represented by the general formula (XVI) may be generated as a by-product. The compound represented by the general formula (XVI) is converted from the state of the crude product obtained in the step D-1 into the compound represented by the general formula (XIII) by performing the operation of the step D-2. can do.

Step D-2 can be carried out under any reaction conditions, but is preferably carried out in an inert organic solvent. Examples of the inert solvent that can be used in this production method include alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, and ethylene glycol dimethyl ether. Etc. and water mixed at an arbitrary ratio. Of these, a mixture of methanol and water at a ratio of 1: 1 is preferable.
Examples of the base b that can be used for the reaction include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like.
The amount of the base b used in the reaction can be generally 1 to 5 mol, preferably 1.1 to 2 mol, per 1 mol of the compound represented by the general formula (XII).
This reaction is usually performed at a temperature of 0 to 100 ° C, preferably 20 to 80 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 24 hours.
After completion of the reaction, the compound represented by the general formula (XIII) is extracted, for example, by adding water and an organic solvent to the reaction solution containing the derivative, followed by washing with water and saturated saline, and distilling off the solvent. Can be obtained. The obtained target product (XIII) can be further purified by an operation such as column chromatography, if necessary.

  In step D-3, a compound represented by the general formula (XV) can be obtained by the same synthesis method as in step C-2.

In step D-4, the compound represented by the general formula (II) can be obtained by the same synthesis method as in step C-3.
In production method D, the compound represented by the general formula (XIII) is a known compound, and (XIII) can be synthesized and used according to the method described in EP 1246825. .

［式中、Ｒ₁は、炭素数１〜６の低級アルキル基、アルコキシアルキル基またはハロアルキル基を示し、Ｒ_２およびＲ_３は、それぞれ独立に水素原子または炭素数１〜６の低級アルキル基を示し、Ｒ_６は、炭素数１〜６の低級アルキル基を示し、Ａは、シクロヘキサン環またはシクロペンタン環を示し、Ｈａｌはハロゲン原子を示す。］ [Production Method E]

[Wherein, R ₁ represents a lower alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group or a haloalkyl group, and R ₂ and R ₃ each independently represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. R ₆ represents a lower alkyl group having 1 to 6 carbon atoms, A represents a cyclohexane ring or a cyclopentane ring, and Hal represents a halogen atom. ]

Step E-1 can be carried out under any reaction conditions, but is preferably carried out in the absence of a solvent or in an inert organic solvent. Examples of the inert solvent that can be used in this production method include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, and ethylene glycol dimethyl ether, and aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene. Examples thereof include a solvent, a solvent containing a heteroatom such as dimethyl sulfoxide, acetonitrile, N, N-dimethylformamide, and the like. Of these, tetrahydrofuran (THF) and N, N-dimethylformamide are preferred. In addition, compound (XVII) can be used in a large excess and used as a solvent.
Examples of the base used in the reaction include sodium hydride, potassium hydride, N, N-diisopropylethylamine and the like.
The compound represented by the general formula (XVII) used in the reaction includes 2-chloroethanol, 2-bromoethanol, 2-iodoethanol, 2-chloro-1-propanol, 2-bromo-1-propanol, 1 -Bromo-2-butanol, 1-chloro-2-propanol, 1-bromo-2-propanol and the like.
The amount of compound (XVII) used in the reaction is usually 1 to 100 mol, preferably 3 to 10 mol, and the amount of base is usually 1 to 5 mol, preferably 1 mol of the compound represented by formula (XIII). Can be used in an amount of 1.1 to 2 moles. This reaction is usually performed at a temperature of 0 to 100 ° C, preferably 20 to 80 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 24 hours.
After completion of the reaction, the compound represented by the general formula (XV) is extracted, for example, by adding water and an organic solvent to the reaction solution containing the derivative, followed by washing with water and saturated saline, and distilling off the solvent. Can be obtained. If necessary, the obtained target product (XV) can be further purified by an operation such as column chromatography.

  In step E-2, the compound represented by the general formula (II) can be obtained by the same synthesis method as in step C-3.

  The compound represented by the general formula (I) can be analyzed, confirmed and identified by melting point, infrared absorption spectrum, 1H-NMR, 13C-NMR, mass spectrometry, X-ray structural analysis, etc., if necessary.

  The more specific manufacture example of the compound represented with general formula (I) based on this invention is described in Examples 1-6 in the Example of this specification.

[Agricultural / horticultural fungicide of the present invention]
The compounds represented by the general formula (I) according to the present invention include a wide variety of filamentous fungi such as, for example, Plasmodiophoromycetes, algae fungi (Oomycetes), Ascomycetes fungi (Ascomycetes), incomplete It can be controlled at low doses against bacteria belonging to fungi (Deuteromycetes) and basidiomycetes, and is useful, for example, as a bactericidal composition for agriculture and horticulture.

Specific examples of plant diseases that can be controlled by the present invention include:
Rice Blast (Pyricularia
grisea), sesame leaf blight (Cochliobolus miyabeanus), coat blight (Thanatephorus cucumeris, stupid seedling (Gibberella)
fujikuroi), seedling blight (Fusarium fungus, Rhizopus fungus, Pythium fungus, Trichoderma viride), rice bran disease (Claviceps virens),
Gibberella of wheat
zeae, Fusarium avenaceum, Fusarium
culmorum, Monographella nivale), snow rot (Pythium, Typhula, Monographella)
nivalis, Myriosclerotinia borealis), Bare scab (Ustilago nuda), Nagusa scab (Tilletia controversa), Eye spot (Pseudocercosporella herpotrichoides), Leaf blight (Septoria)
tritici), blight (Phaeosphaeria nodorum),
Citrus spot disease (Diaporthe
citri), small sunspot disease (Diaporthe medusa, Alternaria citri), common scab (Elsinoe fawcettii), brown rot (Phytophthora)
citrophthra), green mold (Penicillium digitatum), blue mold (Penicillium italicum),
Monilinia in apple
mali), black spot disease (Venturia inaequalis), spotted leaf disease (Alternaria mali), black spot disease (Mycosphaerella pomi), soot spot disease (Gloeodes pomigena), soot spot disease (Zygophiala)
jamaicensis), ring rot (Botryosphaeria berengeriana), brown spot (Diplocarpon mali), red scab (Gymnosporangium)
yamadae), rot (Valsa ceratosperma)
Pear black spot disease (Venturia
nashicola), red scab (Gymnosporangium asiaticum), ring rot (Botryosphaeria berengeriana), blight (Phomopsis)
fukushii),
Peach blight (Taphrina)
deformans), gray scab (Monilinia fructicola, Monilinia fructigena), black scab (Cladosporium)
carpophilum), homophosis rot (Phomopsis),
Monsinia in sweet cherry
fructicola, Monilinia fructigena), larvae nuclear disease (Monilinia kusanoi),
Black scab of ume (Cladosporium
carpophilum),
Grapes Black Tooth (Elsinoe
ampelina), late rot (Colletotrichum acutatum, Glomerella cingulata), brown spot (Pseudocercospora)
vitis), vine split disease (Phomopsis viticola)
Peripheral leaf spot (Cercospora)
kaki), lobster leaf disease (Mycosphaerella nawae),
Tea ring spot disease (Pestalotiopsis)
longiseta, Pestalotiopsis theae), brown streak disease (Pseudocercospora ocellata, Cercospora chaae), blast (Exobasidium vexans), net blast (Exobasidium)
reticulatum),
Mycosphaerella
melonis), vine split disease (Fusarium oxysporum), black spot disease (Cladosporium cucumerinum), brown spot disease (Corynespora)
cassiicola),
Tomato leaf mold (Fulvia
fulva), ring rot (Alternaria solani),
Eggplant brown spot (Phomopsis)
vexans), moldy mildew (Mycovellosiella nattrassii),
Cruciferous vegetables white rust (Albugo macrospora), white spot (Cercosporella)
brassicae, Pseudocercosporella capsellae),
Onion gray rot (Botrytis allii),
Strawberry Janome Disease (Mycosphaerella
fragariae),
Potato summer plague (Alternaria
solani),
Phytophthora of soybean
sojae), purpura (Cercospora kikuchii),
Phytophthora
vignae)
Peanut disease of peanuts (Mycosphaerella
arachidis),
Brown spot of sugar beet (Cercospora
beticola), leaf rot (Thanatephorus cucumeris),
Shiva Carbularia leaf blight (Curvularia fungus), Dollar spot disease (Sclerotinia homoeocarpa), Helmintosporium leaf blight (Cochliobolus fungus),
Rose scab (Diplocarpon)
rosae),
Chrysanthemum rust (Puccinia)
horiana),
And mildew of various crops (Peronospora, Pseudoperonospora, Plasmopara, Bremia), plague (Phytophthora), powdery mildew (Erysiphe, Blumeria, Sphaerotheca, Podosphaerea, Phyllactinia, Uncinula, Oidiopsis ), Rust (Puccinia, Uromyces, Physopella), anthrax (Glomerella, Colletotrichum, Gloeosporium), black spot (Alternaria), gray mold (Botrytis cinerea), sclerotia (Sclerotinia) sclerotiorum), white crest (Rosellinia)
necatrix), purple herb disease (Helicobasidium mompa), white silkworm disease (Sclerotium rolfsii), various other soil diseases (Fusarium, Rhizoctonia, Pythium, Aphanomyces, Phoma, Verticillium, Plasmodiophora brassicae, etc.)
And other diseases.

  The 1,3-dioxolane derivative, 1,3-dithiolane derivative or 1,3-oxathiolane derivative represented by the general formula (I) according to the present invention exhibits bactericidal activity. In particular, a composition containing the compound represented by formula (I) as an active ingredient can be used as an agricultural and horticultural fungicide.

  The composition of the agricultural and horticultural fungicide containing the compound represented by the general formula (I) according to the present invention as an active ingredient is ordinary agricultural and horticultural except that it contains the compound represented by the general formula (I) as an active ingredient. It is good also as a composition of the disinfectant. The normal composition is described in, for example, an agrochemical formulation guide (edited by: Japan Agricultural Chemical Society Application Method Research Group, published by Japan Society for Plant Protection). That is, a compound represented by the general formula (I), an appropriate carrier, an auxiliary agent, a surfactant, a binder, a stabilizer, and the like may be blended.

  The composition of the agricultural and horticultural fungicide containing the compound represented by the general formula (I) according to the present invention can be formulated into any dosage form generally used as an agrochemical dosage form. For example, powder, coarse powder, DL (driftless type) powder, flow dust, fine granules, fine granules, granules, wettable powder, wettable powder, liquid, sol (flowable), emulsion, and Although it can be formulated into an oil or the like, it is not limited to these.

  The content of the compound represented by the general formula (I) according to the present invention can be appropriately selected depending on the dosage form of the preparation and the method of use. In general, the preferable content is in the range of 0.1 to 90% by weight based on the total amount of the preparation.

  The active compound of the formula (I) according to the present invention is a fungicide (fungicides, bactericides, antiviral agents, plant resistance inducers) at the time of formulation or spraying as necessary when used as an agrochemical. , Insecticide, acaricide, nematocide, herbicide, avian repellent, growth regulator, fertilizer and / or soil conditioner, etc.

Representative examples that can be used by mixing and mixing with the compound of the formula (I) of the present invention are shown below, but are not necessarily limited thereto.
Fungicide:
Probenazole, acibenzolar, tiadinil, carpropamid, diclocymet, fenoxanil, phthalide, pyroquilon, tricyclazole, azoxyst Robin (azoxystrobin), mettominostrobin, oryzastrobin, blasticidin-S (blasticidin-S), kasugamycin, ferimzone, isoprothiolane, iprobenfos, Benomyl, thiophanate-methyl, pefurzoate, ipconazole, prochloraz, triflumizole, fludioxonil Thiram (thiram),
Flutolanil, mepronil, thifluzamide, furametpyr, penencycuron, diclomedine, validamycin, metalaxyl, hymexazol, hymexazol
Insecticide:
Fipronil, dinotefuran, imidacloprid, clothianidin, thiaclopid, thiamethoxam, nitenpyram, carb, carb, bet, carb ), Silafluofen, spinosad, cartap fenthion, fenitrothion, buprofezin, etofenprox, fenobucarb, fenobucarb, tebfenide, tebfenide bensultap), acephate, ethiprole, pymetrozine and the like.

  The agricultural and horticultural fungicide containing the compound represented by the general formula (I) according to the present invention as an active ingredient can be used in the same manner as a method in which a general agricultural and horticultural fungicide is used. Specifically, in the case of a wettable powder, liquid, emulsion, sol (flowable), granular wettable powder, or oil, it is diluted 50 to 10,000 times with water, and generally has an active ingredient of 1 to 10,000 ppm. The dilute solution is prepared depending on the form of crops such as paddy rice and fruit trees, but it is 50 to 1000 L per farm area, usually 100 to 600 L. Can be sprayed on.

  Moreover, in the case of a liquid agent, an emulsion, or a sol (flowable agent), it is not diluted with water or diluted within 50 times, and a quantity of 5 to 5000 mL per 10 are as a microdispersant is mainly used. It can be sprayed in the air. Air spraying is performed using a helicopter.

  In addition, in the case of powder, coarse granule, DL powder, flow dust, fine granule, fine granule, or granule, 0.3 to 5 kg of agent per 10 ares (active ingredient content is about 5 to 500 g) May be applied to the foliage, the soil surface, the soil, or the water surface at the plant disease occurrence site.

Also, in seedling box cultivation such as paddy rice, a granule is used in a seedling box (standard size: 30 cm).
10 to 100 g per x 60 cm x 5 cm) can be applied to the soil surface during the seedling raising period before or after sowing, without any dilution of the flowable or the like, or after dilution.

Specific examples of the method for formulating the compound represented by the general formula (I) according to the present invention as an agricultural and horticultural fungicide are shown in Examples 7 to 11.
Hereinafter, the present invention will be specifically described with reference to examples and test examples, but the scope of the present invention is not limited by these examples.
Hereinafter, in Examples 1 to 6, production examples of the compound represented by the general formula (I) according to the present invention are specifically shown. The NMR data described is data measured with an LNM-LA300 spectrometer (manufactured by JEOL Datum Co., Ltd.), and all δ values are shown in ppm.

Preparation of 1- (1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 1)

[Production Method C]
Step C-1 Synthesis of methyl 1-formyl-1-cyclohexanecarboxylate In a 500 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer, diisopropylamine (25.6 g, 253 mmol) and tetrahydrofuran (THF) (100 mL) was added. To this was added n-butyllithium hexane solution (1.58 mol / L) (147 mL, 232 mmol) at −65 ° C., and the mixture was stirred under a nitrogen atmosphere. After 1 hour, methyl cyclohexanecarboxylate (30.0 g, 211 mmol) was added at −65 ° C. and stirred. After 1 hour, methyl formate (38.0 g, 633 mmol) was added at −10 ° C., and the mixture was stirred for 1 hour while gradually returning to room temperature. After completion of the reaction, the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was further chromatographed on silica gel (trade name: silica gel 60H, manufactured by Merck & Co., Inc.) (developing solvent; hexane). : Ethyl acetate = 40: 1 (solvent volume ratio)} to obtain 25.2 g (yield 70%) of the title object product as a colorless transparent liquid.

Step C-2 Synthesis of methyl 1- (1,3-dioxolan-2-yl) -1-cyclohexanecarboxylate Four 100 mL equipped with Dean-Stark tube, reflux condenser, stirrer, calcium chloride tube and thermometer In a neck flask, methyl 1-formyl-1-cyclohexanecarboxylate (6.3 g, 37.0 mmol), ethylene glycol (9.2 g, 148 mmol), toluene (30 mL) and p-toluenesulfonic acid obtained above were obtained. Hydrate (0.21 g, 1.10 mmol) was added and refluxed for 4 hours. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was further chromatographed on silica gel (trade name: silica gel 60H, manufactured by Merck & Co., Inc.) (developing solvent; hexane). : Ethyl acetate = 20: 1 (solvent volume ratio)} to obtain 5.15 g (yield 65%) of the title object product as a colorless transparent liquid.

Step C-3 Synthesis of 1- (1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid In a 30 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer, potassium hydroxide (1 0.0 g, 17.8 mmol), water (3 mL), dimethyl sulfoxide (7 mL) and methyl 1- (1,3-dioxolan-2-yl) -1-cyclohexanecarboxylate obtained above (1.3 g, 6. 10 mmol) was added, and the mixture was stirred at 100 ° C. for 3 hours. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with water and toluene, acidified with 1N hydrochloric acid, extracted with toluene, and washed with water and saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.01 g (yield 83%) of the title object as a white solid.

[Production method A]
Synthesis of 1- (1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 1) in a 30 mL four-necked flask equipped with a reflux condenser, stirrer, and thermometer 1- (1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid (0.27 g, 1.35 mmol), chloroform (5.0 mL) and oxalyl chloride (0.2 g, 1) obtained above. .58 mmol) was added and stirred at room temperature. After 30 minutes, 2 drops of N, N-dimethylformamide was added, and the mixture was further stirred at room temperature. After 1 hour, the reaction solution was concentrated under reduced pressure, and the resulting residue was diluted with chloroform (1 mL). Then, in a 30 mL four-necked flask equipped with a separately prepared reflux condenser, stirrer and thermometer, 3-aminoquinoline (0.095 g, 0.66 mmol), triethylamine (0.2 g, 1.98 mmol) and Chloroform (3 mL) was added. The diluted chloroform solution was added to this and stirred overnight at room temperature. After completion of the reaction, the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was further chromatographed on silica gel (trade name: silica gel 60H, manufactured by Merck & Co., Inc.) (developing solvent; hexane). : Ethyl acetate = 3: 1 (solvent volume ratio)} to give 0.14 g (yield 68%) of the title object as a white solid.

Preparation of 1- (2-methyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 4)

[Production Method D]
Process D-1
Synthesis of methyl 1-acetyl-1-cyclohexanecarboxylate and purification by Step E-2 In a 200 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer, diisopropylamine (8.7 g, 86.0 mmol) And tetrahydrofuran (THF) (50 mL) were added. To this, n-butyllithium hexane solution (1.58 mol / L) (49.9 mL, 78.8 mmol) was added at −65 ° C., and the mixture was stirred under a nitrogen atmosphere. After 1 hour, methyl cyclohexanecarboxylate (10.2 g, 71.7 mmol) was added at −65 ° C. and stirred. After 1 hour, acetic anhydride (10.9 g, 107 mmol) was added at −65 ° C., and the mixture was stirred for 1 hour while gradually returning to room temperature. After completion of the reaction, the resulting reaction mixture was extracted with water and hexane, and further washed with water and saturated brine. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Next, the residue obtained above was dissolved in methanol (50 mL) in a 200 mL four-necked flask equipped with a separately prepared reflux condenser, stirrer, and thermometer, and potassium carbonate (11.9 g, 86.1 mmol) dissolved in water (50 mL) was added and stirred at room temperature for 3 hours. After completion of the reaction, methanol was distilled off under reduced pressure, extracted with toluene and water, and washed with water and saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 10.7 g (yield 81%) of the title object as a colorless transparent liquid.

Process D-3
Synthesis of methyl 1- (2-methyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylate Four 500 mL equipped with Dean-Stark tube, reflux condenser, stirrer, calcium chloride tube and thermometer In a neck flask, methyl 1-acetyl-1-cyclohexanecarboxylate (13 g, 70.6 mmol), ethylene glycol (17.5 g, 282 mmol), toluene (200 mL) and p-toluenesulfonic acid monohydrate obtained above were obtained. The product (0.33 g, 1.73 mmol) was added and refluxed for 6 hours. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane: Purification by ethyl acetate = 30: 1 (solvent volume ratio)} gave 13.7 g (yield 85%) of the title product as a colorless transparent liquid.

Process D-4
Synthesis of 1- (2-methyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid In a 100 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer, potassium hydroxide (7 .3 g, 130 mmol), water (10 mL), dimethyl sulfoxide (40 mL) and methyl 1- (2-methyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylate obtained above (10.0 g, 43.8 mmol) was added, and the mixture was stirred at 120 ° C. for 2 hours. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with water and toluene, acidified with 1N hydrochloric acid, extracted with toluene, and washed with water and saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 7.79 g (yield 83%) of the title object product as a white solid (melting point: 64-67 ° C.).

[Production method A]
Synthesis of 1- (2-methyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 4) 50 mL 4 equipped with reflux condenser, stirrer, and thermometer In a one-necked flask, 1- (2-methyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid (1.57 g, 7.33 mmol) obtained above, chloroform (15.0 mL) and Oxalyl chloride (0.93 g, 7.33 mmol) was added and stirred at room temperature. After 30 minutes, 2 drops of N, N-dimethylformamide was added, and the mixture was further stirred at room temperature. After 1 hour, the reaction solution was concentrated under reduced pressure, and the resulting residue was diluted with chloroform (5 mL). Next, 3-aminoquinoline (0.96 g, 6.66 mmol) and triethylamine (2.02 g, 20.0 mmol) were placed in a 50 mL four-necked flask equipped with a separately prepared reflux condenser, stirrer and thermometer. And chloroform (10 mL) was added. The above diluted chloroform solution was added thereto and stirred overnight at room temperature. After completion of the reaction, the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane : Ethyl acetate = 3: 1 (solvent volume ratio)} to give 1.89 g (yield 83%) of the title product as a colorless oil.

Preparation of 1- (2-methyl-trans-4,5-dimethyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 11)

[Production Method D]
Process D-3
Synthesis of methyl 1- (2-methyl-trans-4,5-dimethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylate Dean-Stark tube, reflux condenser, stirrer, calcium chloride tube and In a 200 mL four-necked flask equipped with a thermometer, methyl 1-acetyl-1-cyclohexanecarboxylate (5.0 g, 27.1 mmol), 2,3-butanediol (12.2 g, 135 mmol), toluene (100 mL) ) And p-toluenesulfonic acid monohydrate (0.52 g, 2.73 mmol) were added and refluxed for 7 hours. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane : Ethyl acetate = 40: 1 (solvent volume ratio)} to obtain 2.71 g (yield 39%) of the title object product as a white solid.

Process D-4
Synthesis of 1- (2-methyl-trans-4,5-dimethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid 50 mL four-necked flask equipped with reflux condenser, stirrer and thermometer In potassium t-butoxide (1.58 g, 14.1 mmol), water (2 mL), dimethyl sulfoxide (20 mL) and 1- (2-methyl-trans-4,5-dimethyl-1,3 obtained above -Dioxolan-2-yl) -1-cyclohexanecarboxylate (1.81 g, 7.06 mmol) was added, and the mixture was stirred at 100 ° C. for 1 hr. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with water and toluene, acidified with 1N hydrochloric acid, extracted with toluene, and washed with water and saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.52 g (yield 89%) of the title compound as a white solid (melting point: 106-109 ° C.).

[Production method A]
Synthesis of 1- (2-methyl-trans-4,5-dimethyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 11)
1- (2-Methyl-trans-4,5-dimethyl-1,3-dioxolan-2-yl) obtained above in a 30 mL four-necked flask equipped with a reflux condenser, stirrer, and thermometer -1-Cyclohexanecarboxylic acid (0.20 g, 0.83 mmol), chloroform (5.0 mL) and oxalyl chloride (0.15 g, 1.18 mmol) were added and stirred at room temperature. After 30 minutes, 2 drops of N, N-dimethylformamide was added, and the mixture was further stirred at room temperature. After 1 hour, the reaction solution was concentrated under reduced pressure, and the resulting residue was diluted with chloroform (1 mL). Next, in a 30 mL four-necked flask equipped with a separately prepared reflux condenser, stirrer, and thermometer, 3-aminoquinoline (0.1 g, 0.67 mmol), triethylamine (0.25 g, 2.47 mmol) were prepared. ) And chloroform (3 mL) were added. To this was added the chloroform solution diluted above and stirred overnight at room temperature. After completion of the reaction, the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane : Ethyl acetate = 3: 1 (solvent volume ratio)} to obtain 0.16 g (yield 64%) of the title target product as a white solid.

Preparation of 1- (2-ethyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 5)

[Production Method D]
Step D-1 Synthesis of methyl 1-propionyl-1-cyclohexanecarboxylate In a 100 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer, diisopropylamine (4.25 g, 42.0 mmol) and tetrahydrofuran ( (THF) (10 mL) was added. To this was added n-butyllithium hexane solution (1.58 mol / L) (24.4 mL, 38.6 mmol) at −65 ° C., and the mixture was stirred under a nitrogen atmosphere. After 1 hour, methyl cyclohexanecarboxylate (5.0 g, 35.2 mmol) was added at −65 ° C. and stirred. After 1 hour, propionic acid chloride (3.26 g, 35.2 mmol) was added at −65 ° C., and the mixture was stirred for 1 hour while gradually returning to room temperature. After completion of the reaction, the resulting reaction mixture was extracted with water and hexane, and further washed with water and saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane : Ethyl acetate = 40: 1 (solvent volume ratio)} to obtain 2.79 g (yield 40%) of the title object product as a colorless transparent liquid.

Step D-3 Synthesis of methyl 1- (2-ethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylate Equipped with a Dean-Stark tube, reflux condenser, stirrer, calcium chloride tube and thermometer In a 30 mL four-necked flask, methyl 1-propionyl-1-cyclohexanecarboxylate (1.0 g, 5.04 mmol) obtained above, ethylenedioxybis (trimethylsilane) (1.25 g, 6.06 mmol) And dichloromethane (10 mL) were added and stirred at room temperature overnight. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with a saturated aqueous sodium hydrogen carbonate solution, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane: Purification by ethyl acetate = 8: 1 (solvent volume ratio)} gave 0.90 g (yield 74%) of the title product as a colorless transparent liquid.

Step D-4 Synthesis of 1- (2-ethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid In a 30 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer, water was added. Potassium oxide (1.05 g, 18.7 mmol), water (1 mL), dimethyl sulfoxide (10 mL) and 1- (2-ethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid obtained above Methyl (1.52 g, 6.27 mmol) was added and stirred at 110 ° C. for 2 hours. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with water and toluene, acidified with 1N hydrochloric acid, extracted with toluene, and washed with water and saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.0 g (yield 70%) of the title object as a white solid.

[Production method A]
Synthesis of 1- (2-ethyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 5) 30 mL equipped with reflux condenser, stirrer, and thermometer 1- (2-Ethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid (0.33 g, 1.45 mmol), chloroform (5.0 mL) and oxalyl obtained above in a two-necked flask Chloride (0.20 g, 1.58 mmol) was added and stirred at room temperature. After 30 minutes, 2 drops of N, N-dimethylformamide was added, and the mixture was further stirred at room temperature. After 1 hour, the reaction solution was concentrated under reduced pressure, and the resulting residue was diluted with chloroform (1 mL). Then, in a 30 mL four-necked flask equipped with a separately prepared reflux condenser, stirrer, and thermometer, 5-aminofuro [2,3-b] pyridine (0.15 g, 1.12 mmol), triethylamine (0 .34 g, 3.36 mmol) and chloroform (3 mL) were added. Further, the chloroform solution diluted above was added and stirred overnight at room temperature. After completion of the reaction, the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane: Purification by ethyl acetate = 3: 1 (solvent volume ratio)} gave 0.31 g (yield 82%) of the title product as a white solid.

Preparation of 1- (2-trifluoromethyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 9)

[Production Method E]
Step E-1 Synthesis of 1- (2-trifluoromethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylate in a 100 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer Was charged with sodium hydride (0.35 g, 14.6 mmol). To this was added methyl 1-trifluoroacetyl-1-cyclohexanecarboxylate (3.2 g, 13.4 mmol) under ice cooling, and the mixture was stirred for 30 minutes under a nitrogen atmosphere. After 30 minutes, 2-bromoethanol (33 g, 264 mol) was added under ice cooling, the temperature was returned to room temperature, and the mixture was stirred at 80 ° C. for 5 hours. The temperature was returned to room temperature, triethylamine (3.5 g, 34.6 mmol) was added, and the mixture was further stirred for 3 hours. After completion of the reaction, the reaction mixture obtained was extracted by adding water and hexane, and washed with 0.5N hydrochloric acid, water, and saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane: Purification with ethyl acetate = 10: 1 (solvent volume ratio)} gave 2.20 g (yield 58%) of the title product as a colorless transparent liquid.

Step E-2 Synthesis of 1- (2-trifluoromethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid In a 30 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer , Potassium hydroxide (0.6 g, 10.7 mmol), water (1 mL), dimethyl sulfoxide (5 mL) and 1- (2-trifluoromethyl-1,3-dioxolan-2-yl) -1 obtained above -Methyl cyclohexanecarboxylate (1.0 g, 3.54 mmol) was added and stirred at 110 ° C. for 9 hours. After completion of the reaction, the temperature was returned to room temperature, and the resulting reaction mixture was washed with water and hexane, acidified with 1N hydrochloric acid, extracted with toluene, and washed with water and saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 0.4 g (yield 42%) of the title product as a white solid.

[Production method A]
Synthesis of 1- (2-trifluoromethyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 9) Equipped with reflux condenser, stirrer, and thermometer In a 30 mL four-necked flask, 1- (2-trifluoromethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid (0.2 g, 0.75 mmol), chloroform (3.0 mL) and Oxalyl chloride (0.11 g, 0.87 mmol) was added and stirred at room temperature. After 30 minutes, 2 drops of N, N-dimethylformamide was added, and the mixture was further stirred at room temperature. After 1 hour, the reaction solution was concentrated under reduced pressure, and the resulting residue was diluted with chloroform (1 mL). Subsequently, 5-aminothieno [2,3-b] pyridine (0.1 g, 0.67 mmol) and triethylamine (0...) Were placed in a 30 mL four-necked flask equipped with a separately prepared reflux condenser, stirrer and thermometer. 2 g, 1.98 mmol) and chloroform (3 mL) were added. To this was added a solution diluted with chloroform, and the mixture was stirred overnight at room temperature. After completion of the reaction, the resulting reaction mixture was washed with water, and then washed with saturated brine. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane: Purification by ethyl acetate = 3: 1 (solvent volume ratio)} afforded 0.13 g (yield 53%) of the title product as a white solid.

Preparation of 1- (2-Isopropyl-1,3-dioxolan-2-yl) -N-quinolin-3-ylcyclohexanecarboxamide (Compound No. 10)

[Production method B]
1- (2-methoxymethyl-1,3-dioxolan-2-yl) -1-cyclohexanecarboxylic acid (70 mg, 0.29 mmol) in a 30 mL four-necked flask equipped with a reflux condenser, stirrer and thermometer ), Acetonitrile (3 mL) and triethylamine (0.12 g, 1.16 mmol) were added and cooled to 0 ° C. Further, methanesulfonyl chloride (40 mg, 0.35 mmol) was added at the same temperature under a nitrogen atmosphere and stirred. After 30 minutes, 3-aminoquinoline (42 mg, 0.29 mmol) was added and stirred while gradually returning to room temperature. After completion of the reaction, water was added to the resulting reaction mixture and extracted with toluene. The organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was subjected to chromatography using silica gel (trade name: Silica Gel 60H, manufactured by Merck) {developing solvent; hexane: Purification by ethyl acetate = 3: 1 (solvent volume ratio)} gave 47 mg (yield 44%) of the title compound as a white solid.

Regarding some of the compounds represented by the general formula (I) of the present invention, Table 2 shows analytical data by NMR.

Powder A mixture of compound No. 25 (2 parts by weight), PAP (isopropyl phosphate ester) (physical property improving agent) (1 part by weight) and clay (97 parts by weight) was uniformly pulverized and mixed to be active. A powder containing 2% by weight of the components can be obtained. Furthermore, it can replace with the compound number 25 and each powder agent can be obtained by the same method except using each compound of Table 1.

Wettable agent A mixture of compound No. 22 (20 parts by weight), sodium alkylbenzenesulfonate (3 parts by weight), polyoxyethylene nonylphenyl ether (5 parts by weight) and clay (72 parts by weight) was uniformly mixed. By pulverizing, a wettable powder containing 20% by weight of the active ingredient can be obtained. Furthermore, a wettable powder can be obtained in the same manner except that each compound shown in Table 1 is used instead of the compound of Compound No. 22.

Emulsion Compound No. 19 (30 parts by weight), methyl ethyl ketone (40 parts by weight) and polyoxyethylene nonylphenyl ether (30 parts by weight) are mixed and dissolved to obtain an emulsion containing 30% by weight of the active ingredient. Can do. Further, emulsions can be obtained in the same manner except that each compound shown in Table 1 is used instead of the compound of Compound No. 19.

Flowable agent Compound No. 4 (25 parts by weight), polyoxyethylene alkyl ether (1 part by weight), sodium alkylnaphthalene sulfonate (1 part by weight), carboxymethylcellulose (1 part by weight) and water (72 parts by weight) By uniformly mixing the mixture, a sol containing 25% by weight of the active ingredient can be obtained. Furthermore, each flowable agent can be obtained by the same method except using each compound shown in Table 1 instead of the compound of Compound No. 4.

Granule Compound No. 4 (5 parts by weight), sodium lauryl sulfate (1 part by weight), calcium lignin sulfonate (5 parts by weight), bentonite (30 parts by weight) and clay (59 parts by weight) After adding water (15 parts by weight) and kneading with a kneader, the mixture is granulated with a granulator and dried with a fluid dryer to obtain a granule containing 5% by weight of the active ingredient. Furthermore, each granule can be obtained by the same method except that each compound shown in Table 1 is used instead of the compound of Compound No. 4.

(Test example)
Hereinafter, 1,3-dioxolane derivatives, 1,3-dithiosolane derivatives or 1,3-oxathiolane derivatives represented by the general formula (I) according to the present invention and useful agricultural and horticultural fungicides containing them as active ingredients About property, it clarifies with reference to Test Examples 1-6 below. However, the utility of the present invention is not limited to the utility revealed by these test examples. The test compound number represents the same number as the compound shown in Table 1.

(Test Example 1)
[Pest control effect test for rice blast disease by box treatment (flowable agent)]
According to Example 10, a 2.5 leaf stage seedling of paddy rice (variety: Asahi) grown in a greenhouse using a seedling box (1/10 area size of standard seedling box: 12 cm × 15 cm × height 4 cm) 50 mL of the prepared flowable diluent (5000 ppm) was irrigated. The paddy rice seedlings treated with the chemicals were immediately transplanted at 5 seedlings / pot into a pot (1/10000 are size) filled with paddy soil (brown water). After 4 weeks cultivation in a greenhouse, inoculate the rice blast fungus (Pyricularia grisea) conidia formed on another rice leaf in advance into the drug-treated rice and leave it in a 24 ° C inoculation box for 24 hours. After that, the disease was promoted in an artificial weather room at 24 ° C. Seven days after the inoculation, the number of rice blast lesions per one rice plant was investigated, the average number of lesions was determined, and the control value (%) was calculated by the following formula 1. And according to following Table 3, the control value was converted into the evaluation value. This test was conducted in a five-column system with one pot and one pot per drug group.

In addition, the degree of phytotoxicity to crops was investigated according to the following criteria.
Survey index of the degree of chemical damage
5: Excitement 4: 甚 3: Many 2: Slight 1: Slight 0: None The evaluation value of the control effect and the investigation index of the degree of chemical damage were also applied in Test Examples 2 to 5.

These results are shown in Table 4.
In addition, the comparative compound A in Tables 4 to 6 is the following compound described in International Publication No. WO04-005261.

(Test Example 2)
[Pest control effect test (granule) for rice blast disease by box treatment]
Grain prepared according to Example 11 to 2.5 leaf seedlings of paddy rice (variety: Asahi) grown in a greenhouse using a seedling box (1/10 area size of standard nursery box: 12 cm x 15 cm x height 4 cm) 5 g of the agent was sprayed from the upper part of the seedling box. The paddy rice seedlings treated with the chemicals were immediately transplanted at 5 seedlings / pot into a pot (1/10000 are size) filled with paddy soil (brown water). After cultivating in a greenhouse for 6 weeks, inoculate the rice blast fungus (Pyricularia grisea) conidia grown on another rice leaf in advance into the drug-treated rice and leave it in a 24 ° C inoculation box for 24 hours. After that, the disease was promoted in an artificial weather room at 24 ° C. Seven days after the inoculation, the number of lesions of rice blast disease per one rice paddy was investigated, the average number of lesions was determined, and the control value (%) was calculated by Formula 1. And according to Table 3, the control value was converted into the evaluation value. This test was conducted in a five-column system with one pot and one pot per drug group.
These results are shown in Table 5.

(Test Example 3)
[Control effect test by applying water to rice blast disease (flowable agent)]
Example 10 was applied to five-leaf seedlings (5 seedlings / strain, 1 strain / pot) of paddy rice (variety: Asahi) cultivated in a pot (1/10000 are size) filled with paddy soil (brown water) in a greenhouse. 1 mL of a diluent (1000 ppm) of a flowable agent prepared according to the above was instilled into Ta surface water. After cultivating in a greenhouse for 1 week, inoculate rice plants treated with chemicals with rice blast fungus (Pyricularia grisea) conidia formed on another rice leaf in advance, and leave them in a 24 ° C inoculation box for 24 hours. After that, the disease was promoted in an artificial weather room at 24 ° C. Seven days after the inoculation, the number of rice blast lesions per rice strain was investigated, the average number of lesions was determined, and the control value (%) was calculated according to the following equation (1). And according to Table 3, the control value was converted into the evaluation value. This test was conducted in a five-column system with one pot and one pot per drug group.
These results are shown in Table 6.

(Test Example 4)
[Cucumber gray mold control effect test]
A 1.5 wt. Seedling of cucumber (variety: Sagamihanjiro) cultivated in a plastic pot with a diameter of 6 cm in a greenhouse is diluted with a dilute solution (500 ppm) of a wettable powder prepared according to Example 8. 10 mL was sprayed per pot (stem and leaf spraying). The day after the drug treatment, inoculated on the first leaf of cucumber treated with the drug agar-containing agar pieces (diameter 5 mm) of cucumber gray mold (Botrytis cinerea) that had been cultured in advance on a potato broth medium. Put it inside. Four days after the inoculation, the lesion diameter (cm) was measured, and the control value (%) was calculated by the following formula 2. And according to Table 3, the control value was converted into the evaluation value. This test was conducted in a triple system of 1 pot per 1 chemical solution concentration. The average evaluation value of the control effect was obtained.

These results are shown in Table 7.

(Test Example 5)
[Wheat red rust control effect test]
A 1.5 wt. Seedling of wheat (variety: Norin 61) grown in a plastic pot with a diameter of 6 cm in a greenhouse is diluted with a wettable powder dilute solution (500 ppm) prepared according to Example 8. 10 mL was sprayed per pot (stem and leaf spraying). The day after the drug treatment, per spore suspension of a summer spore suspension of wheat rust (Puccinia recondita) formed on another wheat leaf in advance (spore concentration 5X10 ⁵ / mL) per pot 5 mL of spray was inoculated, and the onset was controlled in an artificial weather chamber at 20 ° C. Ten days after the inoculation, the number of lesions on the first leaf was examined, and the control value (%) was calculated according to Formula 1. And according to Table 3, the control value was converted into the evaluation value. This test was conducted in a triple system of 1 pot per 1 chemical solution concentration. The average evaluation value of the control effect was obtained.
These results are shown in Table 8 below.

注１） 無散布区の
( ) 内の数値は、１葉当りの病斑数を示す。

Note 1) In the non-spray area
Figures in () indicate the number of lesions per leaf.

Claims (3)

Formula (I)

[In General Formula (I), X and Y each independently represent an oxygen atom or a sulfur atom, R ₁ represents a hydrogen atom, an alkyl group, an alkoxyalkyl group or a haloalkyl group, and R ₂ and R ₃ represent Each independently represents a hydrogen atom or an alkyl group, and A represents a cyclohexane ring or a cyclopentane ring. ] A 1,3-dioxolane derivative, a 1,3-dithiolane derivative or a 1,3-oxathiolane derivative represented by the formula: In the general formula (I), X and Y each independently represent an oxygen atom or a sulfur atom, and R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. The 1,3-dioxolane derivative, 1,3-dithiolane derivative or 1,3-oxathiolane derivative according to claim 1, wherein A represents a cyclohexane ring.   Agricultural and horticultural use characterized by containing a 1,3-dioxolane derivative, 1,3-dithiolane derivative or 1,3-oxathiolane derivative represented by the general formula (I) according to claim 1 or 2 Fungicide