JP4529537B2 - Imidazole compounds and uses thereof - Google Patents

Description

  The present invention relates to an imidazole compound, a production intermediate thereof, and use thereof.

〔式中、R¹、R²、R³は、それぞれ独立に、水素または低級アルキルを表し、nは、5〜7の整数のいずれかを表す。〕
で示されるイミダゾール化合物に抗ウイルス活性があることが知られている。(例えば、特許文献１参照)。
また、下記式

〔式中、nは、2〜8の整数のいずれかを表す。〕
で示されるイミダゾール化合物に蚕の早熟変態活性があることが知られている。(たとえば、非特許文献１参照)
欧州特許出願公開第274867号明細書 日本農薬学会誌、1998年、第23巻、第2号、p.117-122 Conventionally, the following formula

[Wherein, R ¹ , R ² , and R ³ each independently represent hydrogen or lower alkyl, and n represents any of 5 to 7 integers. ]
It is known that the imidazole compound represented by the formula has antiviral activity. (For example, refer to Patent Document 1).
Also, the following formula

[Wherein, n represents an integer of 2 to 8. ]
It is known that the imidazole compound represented by the formula has an early maturation transformation activity of koji. (For example, see Non-Patent Document 1)
European Patent Application Publication No. 274867 Japanese Journal of Pesticide Science, 1998, Vol. 23, No. 2, p.117-122

  An object of the present invention is to provide a compound having an excellent plant disease control effect.

〔式中、AおよびEは独立して、ハロゲン原子またはハロゲン原子で置換されていてもよいC1〜C3アルキル基を表し、Gはハロゲン原子で置換されていてもよいC2〜C6アルキル基、OR¹、CH₂OR²またはC(=O)OR³を表し、R¹、R²およびR³は各々、ハロゲン原子で置換されていてもよいC1〜C6アルキル基、ハロゲン原子で置換されていてもよいC3〜C6アルケニル基、ハロゲン原子で置換されていてもよいC3〜C6アルキニル基またはハロゲン原子で置換されていてもよいベンジル基を表し、Xはハロゲン原子で置換されていてもよいC1〜C3アルキル基を表し、Zはハロゲン原子またはハロゲン原子で置換されていてもよいC1〜C3アルキル基を表し、ｋは０〜２のいずれかの整数を表し、mは０〜３のいずれかの整数を表し、nは４〜８のいずれかの整数を表す。〕で示されるイミダゾール化合物（以下、本発明化合物と記す。）、本発明化合物を有効成分として含有することを特徴とする植物病害防除剤及び本発明化合物の有効量を植物または土壌に処理することを特徴とする植物病害の防除方法を提供するものである。
本発明はまた、本発明化合物の製造上の有用な中間体である、
式（II）

〔式中、AおよびEは独立して、ハロゲン原子またはハロゲン原子で置換されていてもよいC1〜C3アルキル基を表し、Xはハロゲン原子で置換されていてもよいC1〜C3アルキル基を表し、Zはハロゲン原子またはハロゲン原子で置換されていてもよいC1〜C3アルキル基を表し、ｋは０〜２の整数のいずれかを表し、ｍは０〜３の整数のいずれかを表し、ｎは４〜８の整数のいずれかを表す。〕で示されるイミダゾール化合物（以下、本発明中間体と記す。）をも提供するものである。 As a result of intensive studies, the present inventors have found that an imidazole compound represented by the following formula (I) has an excellent plant disease control effect, and have reached the present invention. That is, the present invention
Formula (I)

[Wherein, A and E independently represent a halogen atom or a C1-C3 alkyl group optionally substituted with a halogen atom, G represents a C2-C6 alkyl group optionally substituted with a halogen atom, OR ^{1 represents} CH ₂ OR ² or C (═O) OR ³ , wherein R ¹ , R ² and R ³ are each a C1-C6 alkyl group which may be substituted with a halogen atom, or a halogen atom; Represents a C3-C6 alkenyl group, a C3-C6 alkynyl group which may be substituted with a halogen atom, or a benzyl group which may be substituted with a halogen atom, and X is a C1- Represents a C3 alkyl group, Z represents a halogen atom or a C1-C3 alkyl group optionally substituted with a halogen atom, k represents an integer of 0 to 2, and m represents any of 0 to 3 Represents an integer, and n represents an integer of 4 to 8. A plant disease control agent characterized by containing the compound of the present invention as an active ingredient, and an effective amount of the compound of the present invention is treated on a plant or soil. The present invention provides a method for controlling plant diseases characterized by the following.
The present invention is also a useful intermediate in the production of the compound of the present invention.
Formula (II)

[Wherein, A and E independently represent a halogen atom or a C1-C3 alkyl group which may be substituted with a halogen atom, and X represents a C1-C3 alkyl group which may be substituted with a halogen atom. , Z represents a halogen atom or a C1-C3 alkyl group which may be substituted with a halogen atom, k represents any integer of 0 to 2, m represents any integer of 0 to 3, n Represents any integer of 4-8. ] Is also provided (hereinafter referred to as the intermediate of the present invention).

  By using the compound of the present invention, plant diseases can be controlled.

  In the present invention, the “benzyl group optionally substituted with a halogen atom” means a benzyl group or substituent having one halogen atom or two or more independent halogen atoms as a substituent on the benzene ring. Represents a non-benzyl group.

In the present invention,
Examples of the halogen atom represented by A and E include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom,
Examples of the C1-C3 alkyl group optionally substituted with a halogen atom include a methyl group,
Examples of the C2-C6 alkyl group optionally substituted with a halogen atom represented by G include an ethyl group, a propyl group, and a tert-butyl group,
Examples of the C1-C6 alkyl group optionally substituted with a halogen atom represented by R ¹ , R ² and R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, and 2,2,2-trifluoropropyl. Groups,
Examples of the C3-C6 alkenyl group optionally substituted with a halogen atom include allyl group, 2-butenyl group, 3-chloro-2-propenyl group, 2-chloro-2-propenyl group, and 3,3-dichloro- 2-propenyl group,
Examples of the C3-C6 alkynyl group optionally substituted with a halogen atom include a propargyl group,
Examples of the benzyl group optionally substituted with a halogen atom include a benzyl group,
Examples of the C1-C3 alkyl group optionally substituted with a halogen atom represented by X include a methyl group,
Examples of the halogen atom represented by Y include a chlorine atom,
Examples of the C1-C3 alkyl group optionally substituted with a halogen atom include a methyl group.

In the present invention, as OR ¹ represented by G, for example, methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, 2,2,2-trifluoroethoxy group, allyloxy group, 2-butenyloxy group, 2 -Methyl-2-propenyloxy group, 2-chloro-2-propenyloxy group, 3-chloro-2-propenyloxy group, 3,3-dichloro-2-propenyloxy group, propargyloxy group and benzyloxy group And
CH ₂ OR ² includes, for example, a methoxymethyl group,
Examples of C (═O) OR ³ include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.

As an aspect of this invention compound, the following compounds are mentioned, for example.
An imidazole compound in which A is a halogen atom in formula (I);
An imidazole compound in which A is a chlorine atom in formula (I);
An imidazole compound represented by formula (I), wherein E is a halogen atom;
An imidazole compound represented by formula (I), wherein E is a chlorine atom;
An imidazole compound represented by formula (I), wherein G is OR ¹ ;
In the formula (I), G is OR ¹ , and R ¹ is substituted with a C1-C6 alkyl group optionally substituted with a halogen atom, a C3-C6 alkenyl group optionally substituted with a halogen atom, or a halogen atom An imidazole compound which is an optionally substituted C3-C6 alkynyl group;
An imidazole compound represented by formula (I), wherein G is OR ¹ and R ¹ is a C1-C6 alkyl group optionally substituted with a halogen atom;
An imidazole compound represented by formula (I), wherein G is OR ¹ and R ¹ is a C3 to C6 alkenyl group optionally substituted with a halogen atom;
An imidazole compound represented by formula (I), wherein G is OR ¹ and R ¹ is a C3 to C6 alkynyl group optionally substituted with a halogen atom;
In the formula (I), G is OR ¹ , and R ¹ is substituted with a C1-C6 alkyl group optionally substituted with a halogen atom, a C3-C6 alkenyl group optionally substituted with a halogen atom, or a halogen atom An imidazole compound which is an optionally substituted C3-C6 alkynyl group and k is 0;
An imidazole compound represented by formula (I), wherein n is 5 or 6;
An imidazole compound represented by formula (I), wherein m is 0 and n is 5 or 6;
An imidazole compound in which m is 1 in formula (I);
An imidazole compound represented by the formula (I), wherein m is 1 and X is a methyl group bonded to the 2-position on the imidazole;
An imidazole compound in which A and E are each a halogen atom in formula (I);
An imidazole compound represented by formula (I), wherein A and E are each a halogen atom and k is 0;
An imidazole compound represented by formula (I), wherein A and E are chlorine atoms;

〔式中、A、E、X、Z、R¹、k、m及びnは前述と同じ意味を表す。〕
で表される化合物は、｛製造法C｝にしたがって製造し得る。本発明中間体は下記｛製造法D｝にしたがって製造し得る。
これらの製造法においては、必要に応じ官能基を反応から保護するために保護基を用いることもできる。 The compound of the present invention can be produced according to the following {Production Method A} or {Production Method B}.
Further, among the compounds of the present invention, the formula (Ia) wherein G is OR ¹

[Wherein, A, E, X, Z, R ¹ , k, m, and n represent the same meaning as described above. ]
Can be produced according to {Production Method C}. The intermediate of the present invention can be produced according to {Production method D} below.
In these production methods, a protecting group can also be used as necessary to protect the functional group from the reaction.

〔式中、A、E、G、Z、k及びnは、前述と同じ意味を表し、L¹は、塩素原子、臭素原子等のハロゲン原子、メタンスルホニルオキシ基等の置換されていてもよいアルキルスルホニルオキシ基又はp-トルエンスルホニルオキシ基等の置換されていてもよいアリールスルホニルオキシ基を表す。〕
で表される化合物と、
式(IV)

〔式中、X及びmは、前述と同じ意味を表す。〕
で表されるイミダゾール化合物とを、反応させることにより製造する方法。
該反応は通常溶媒中で行われる。
該反応に用いられる溶媒としては例えば、トルエン、ヘキサン等の炭化水素類、テトラヒドロフラン、tert-ブチルメチル等のエーテル類、クロロベンゼン等のハロゲン化炭化水素類、ジメチルホルムアミド等の酸アミド類、メタノール、エタノール等のアルコール類、アセトン等のケトン類、ジメチルスルホキシド等の有機硫黄化合物類、水及びこれらの混合物が挙げられる。
反応に供される試剤の量は、式(III)で表される化合物1モルに対して、式(IV)で表されるイミダゾール化合物は、通常、1モル〜過剰量の割合、好ましくは1モル〜5モルの割合である。
反応時間の範囲は通常5分間〜72時間であり、反応温度の範囲は通常-20℃から反応に使用する溶媒の沸点または250℃までの範囲である。
該反応は、塩基の存在下で行うこともできる。その場合に用いられる塩基としては、カリウムtert-ブトキシド等のアルカリ金属アルコキシド、水酸化ナトリウム、炭酸カリウム、水素化ナトリウム等の無機塩基類が挙げられる。
反応終了後の反応液は、例えば有機溶媒抽出、濃縮等の後処理操作を行うことにより本発明化合物を単離することができる。単離された本発明化合物はクロマトグラフィー、再結晶等の操作により精製することもできる。 {Production method A}
Formula (III)

[Wherein, A, E, G, Z, k and n represent the same meaning as described above, and L ¹ may be substituted with a halogen atom such as a chlorine atom or a bromine atom, a methanesulfonyloxy group, or the like. Represents an optionally substituted arylsulfonyloxy group such as an alkylsulfonyloxy group or a p-toluenesulfonyloxy group; ]
A compound represented by
Formula (IV)

[Wherein, X and m represent the same meaning as described above. ]
The method of manufacturing by making the imidazole compound represented by these react.
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, methanol, ethanol, and the like. Alcohols, ketones such as acetone, organic sulfur compounds such as dimethyl sulfoxide, water, and mixtures thereof.
The amount of the reagent used for the reaction is usually 1 mol to an excess amount of the imidazole compound represented by the formula (IV) with respect to 1 mol of the compound represented by the formula (III), preferably 1 It is a ratio of mol to 5 mol.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 250 ° C.
The reaction can also be performed in the presence of a base. Examples of the base used in this case include alkali metal alkoxides such as potassium tert-butoxide, and inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydride.
After completion of the reaction, the compound of the present invention can be isolated by performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound of the present invention can also be purified by procedures such as chromatography and recrystallization.

〔式中、A、E、G、Z及びkは、前述と同じ意味を表す。〕
で表されるフェノール化合物と、
式(VI)

〔式中、X、ｎ及びmは前述と同じ意味を表し、L²は、塩素原子、臭素原子等のハロゲン原子、メタンスルホニルオキシ基等の置換されていてもよいアルキルスルホニルオキシ基又はp-トルエンスルホニルオキシ基等の置換されていてもよいアリールスルホニルオキシ基を表す。〕
で表されるイミダゾール化合物もしくはその酸との塩とを、反応させることにより製造する方法。
該反応は通常溶媒中で行われる。
該反応に用いられる溶媒としては例えば、トルエン、ヘキサン等の炭化水素類、テトラヒドロフラン、tert-ブチルメチル等のエーテル類、クロロベンゼン等のハロゲン化炭化水素類、ジメチルホルムアミド等の酸アミド類、メタノール、エタノール等のアルコール類、アセトン等のケトン類、ジメチルスルホキシド等の有機硫黄化合物類、水及びこれらの混合物が挙げられる。
反応に供される試剤の量は、式(V)で表されるフェノール化合物1モルに対して、式(VI)で表されるイミダゾール化合物もしくはその酸との塩は、通常、0.1モル〜過剰量の割合、好ましくは0.5モル〜2モルの割合である。
反応時間の範囲は通常5分間〜72時間であり、反応温度の範囲は通常-20℃から反応に使用する溶媒の沸点または250℃までの範囲である。
該反応は、塩基の存在下で行うこともできる。その場合に用いられる塩基としては、カリウムtert-ブトキシド等のアルカリ金属アルコキシド、水酸化ナトリウム、炭酸カリウム、炭酸セシウム、水素化ナトリウム等の無機塩基類が挙げられる。
反応終了後の反応液は、例えば有機溶媒抽出、濃縮等の後処理操作を行うことにより本発明化合物を単離することができる。単離された本発明化合物はクロマトグラフィー、再結晶等の操作により精製することもできる。 {Production method B}
Formula (V)

[Wherein, A, E, G, Z and k represent the same meaning as described above. ]
A phenolic compound represented by
Formula (VI)

[Wherein, X, n and m represent the same meaning as described above, and L ² represents a halogen atom such as a chlorine atom or a bromine atom, an optionally substituted alkylsulfonyloxy group such as a methanesulfonyloxy group, or p- Represents an optionally substituted arylsulfonyloxy group such as a toluenesulfonyloxy group; ]
The imidazole compound represented by these, or the salt with the acid is made to react.
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, methanol, ethanol, and the like. Alcohols, ketones such as acetone, organic sulfur compounds such as dimethyl sulfoxide, water, and mixtures thereof.
The amount of the reagent used for the reaction is usually 0.1 mol to excess of the imidazole compound represented by the formula (VI) or a salt thereof with respect to 1 mol of the phenol compound represented by the formula (V). A proportion of the amount, preferably a proportion of 0.5 mol to 2 mol.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 250 ° C.
The reaction can also be performed in the presence of a base. Examples of the base used in this case include alkali metal alkoxides such as potassium tert-butoxide, and inorganic bases such as sodium hydroxide, potassium carbonate, cesium carbonate, and sodium hydride.
After completion of the reaction, the compound of the present invention can be isolated by performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound of the present invention can also be purified by procedures such as chromatography and recrystallization.

{Production method C}
The intermediate of the present invention;
Formula (VII)
R ¹ -L ³ (VII)
[Wherein R ¹ represents the same meaning as described above, L ³ represents a halogen atom such as a chlorine atom or a bromine atom, an optionally substituted alkylsulfonyloxy group such as a methanesulfonyloxy group, and p-toluenesulfonyloxy. Represents an optionally substituted arylsulfonyloxy group such as a group; ]
The method of manufacturing by making the compound represented by these react.
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, methanol, ethanol, and the like. Alcohols, ketones such as acetone, organic sulfur compounds such as dimethyl sulfoxide, water, and mixtures thereof.
The amount of the reagent used for the reaction is usually 1 mol to an excess amount, preferably 1 mol to 2 mol of the compound represented by formula (VII) with respect to 1 mol of the intermediate of the present invention. is there.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 250 ° C.
The reaction can also be performed in the presence of a base. Examples of the base used in this case include alkali metal alkoxides such as potassium tert-butoxide, and inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydride.
After completion of the reaction, the compound of the present invention can be isolated by performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound of the present invention can also be purified by procedures such as chromatography and recrystallization.

〔式中、A、E、X、Z、k、m及びnは前述と同じ意味を表す。〕
で表される化合物を加水素分解する方法。
該反応は通常溶媒および加水素分解触媒の存在下で行われる。
該反応に用いられる溶媒としては例えば、トルエン、ヘキサン等の炭化水素類、テトラヒドロフラン、メチルtert-ブチルエーテル等のエーテル類、1,2-ジクロロエタン等のハロゲン化炭化水素類、酢酸エチル等のエステル類、メタノール、エタノール等のアルコール類、アセトン等のケトン類、水及びこれらの混合物が挙げられる。
加水素分解触媒とは、パラジウム、ニッケル等の遷移金属原子を含有する化合物若しくはその化合物を含んでなる混合物であり、具体的には例えばパラジウム/活性炭が挙げられる。
反応に用いられる加水素分解触媒の量は、式(I-b)で表される化合物1グラムに対して通常0.001〜1グラムの割合である。
該反応は、通常水素雰囲気下で行われる。この場合の水素の圧力は、通常1〜10気圧の範囲である。
該反応は酸の存在下で行うこともできる。その場合に用いられる酸としては、例えば塩酸、硫酸等の無機酸類、p-トルエンスルホン酸等の有機酸類及びこれらの混合物が挙げられる。
反応の終点は、例えば水素の吸収量の経時変化を測定し、水素の吸収速度を確認することにより決定することができる。
反応終了後の反応液は、例えば濾過した後、得られた濾液の抽出、濃縮等の後処理操作を行うことにより、本発明中間体を単離することができる。単離された本発明中間体はクロマトグラフィー、再結晶等の操作により精製することもできる。 {Production method D}
Of the compounds of the present invention, G is a benzyloxy group (Ib)

[Wherein, A, E, X, Z, k, m, and n represent the same meaning as described above. ]
The method of carrying out hydrogenolysis of the compound represented by these.
The reaction is usually performed in the presence of a solvent and a hydrogenolysis catalyst.
Examples of the solvent used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and methyl tert-butyl ether, halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, Examples thereof include alcohols such as methanol and ethanol, ketones such as acetone, water, and a mixture thereof.
The hydrogenolysis catalyst is a compound containing a transition metal atom such as palladium or nickel or a mixture containing the compound, and specifically includes palladium / activated carbon.
The amount of the hydrogenolysis catalyst used in the reaction is usually in a ratio of 0.001 to 1 gram with respect to 1 gram of the compound represented by the formula (Ib).
The reaction is usually performed under a hydrogen atmosphere. The hydrogen pressure in this case is usually in the range of 1 to 10 atmospheres.
The reaction can also be performed in the presence of an acid. Examples of the acid used in that case include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid, and mixtures thereof.
The end point of the reaction can be determined, for example, by measuring the change in hydrogen absorption over time and confirming the hydrogen absorption rate.
The intermediate of the present invention can be isolated by subjecting the reaction solution after completion of the reaction, for example, to filtration, and then performing post-treatment operations such as extraction and concentration of the obtained filtrate. The isolated intermediate of the present invention can also be purified by operations such as chromatography and recrystallization.

〔式中、A、E、R¹、Z、L¹、k及びnは、前述と同じ意味を表す。〕
で表される化合物は、｛製造法H｝にて製造し得る。 The compound represented by the formula (III) can be produced, for example, by {Production method E}, {Production method F} or {Production method G}.
Of the compounds represented by formula (III), the formula (III-a) wherein G is OR ¹

[Wherein, A, E, R ¹ , Z, L ¹ , k and n represent the same meaning as described above. ]
Can be produced by {Production Method H}.

{Production method E}
A compound represented by formula (V);
Formula (VIII)
L ^1- (CH ₂ ) _n -L ⁴ (VIII)
[Wherein L ¹ and n represent the same meaning as described above, and L ⁴ represents a halogen atom such as a chlorine atom or a bromine atom, an optionally substituted alkylsulfonyloxy group such as a methanesulfonyloxy group, or p-toluene. Of arylsulfonyloxy groups which may be substituted, such as a sulfonyloxy group, a group which is not less reactive than L ^{1 under} the reaction conditions described in {Production Method E}. ]
The method of manufacturing by making the compound represented by these react.
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, methanol, ethanol, and the like. Alcohols, ketones such as acetone, organic sulfur compounds such as dimethyl sulfoxide, water, and mixtures thereof.
The amount of the reagent used for the reaction is usually 1 mol to an excess amount, preferably 1 mol of the compound represented by the formula (VIII) with respect to 1 mol of the compound represented by the formula (V). It is a ratio of ˜2 mol.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 250 ° C.
The reaction can also be performed in the presence of a base. Examples of the base used in this case include alkali metal alkoxides such as potassium tert-butoxide, and inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydride.
The reaction liquid after completion of the reaction can be isolated from the compound represented by the formula (III) by performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound represented by the formula (III) can also be purified by operations such as chromatography and recrystallization.

〔式中、A、E、G、Z、k及びnは、前述と同じ意味を表す。〕
で表されるアルコール化合物と、ハロゲン化剤、アルキルスルホニル化剤若しくはアリールスルホニル化剤とを反応させることにより製造する方法。
該反応は通常溶媒中で行われる。
該反応に用いられる溶媒としては、トルエン、ヘキサン等の炭化水素類、テトラヒドロフラン、tert-ブチルメチル等のエーテル類、クロロベンゼン、1,2-ジクロロエタン等のハロゲン化炭化水素類、ジメチルホルムアミド等のアミド類、メタノール、エタノール等のアルコール類、アセトン等のケトン類、水及びこれらの混合物が挙げられる。
該反応に用いられるハロゲン化剤としては、例えば塩化チオニル及び四臭化炭素が挙げられ、アルキルスルホニル化剤としては、例えば塩化メタンスルホニルが挙げられ、アリールスルホニル化剤としては、例えば塩化 p-トルエンスルホニルが挙げられる。
反応に供される試剤の量は、式(IX)で表されるアルコール化合物1モルに対して、ハロゲン化剤、アルキルスルホニル化剤若しくはアリールスルホニル化剤は、通常、1モル〜過剰量の割合、好ましくは1モル〜2モルの割合であり、必要に応じて加えられる塩基は、0.001モル〜大過剰の割合である。
反応時間の範囲は通常5分間〜72時間であり、反応温度の範囲は通常-20℃から反応に使用する溶媒の沸点または250℃までの範囲である。
該反応は塩基の存在下で行うこともできる。その場合に用いられる塩基としては、トリエチルアミン等の第3級アミン類、ピリジン等の含窒素複素環化合物類の有機塩基類、炭酸カリウム等の無機塩基類等が挙げられる。
反応終了後の反応液は、例えば有機溶媒抽出、濃縮等の後処理操作を行うことにより式(III)で表される化合物を単離することができる。単離された式(III)で表される化合物はクロマトグラフィー、再結晶等の操作により精製することもできる。 {Production method F}
Formula (IX)

[Wherein, A, E, G, Z, k and n represent the same meaning as described above. ]
A method for producing the compound by reacting a halogenating agent, an alkylsulfonylating agent or an arylsulfonylating agent.
The reaction is usually performed in a solvent.
Solvents used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene and 1,2-dichloroethane, amides such as dimethylformamide, Examples thereof include alcohols such as methanol and ethanol, ketones such as acetone, water, and a mixture thereof.
Examples of the halogenating agent used in the reaction include thionyl chloride and carbon tetrabromide. Examples of the alkylsulfonylating agent include methanesulfonyl chloride. Examples of the arylsulfonylating agent include p-toluene chloride. And sulfonyl.
The amount of the reagent used for the reaction is usually 1 mol to an excess amount of the halogenating agent, alkylsulfonylating agent or arylsulfonylating agent with respect to 1 mol of the alcohol compound represented by the formula (IX). The base added as needed is preferably in a proportion of 0.001 mol to a large excess.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 250 ° C.
The reaction can also be performed in the presence of a base. Examples of the base used in this case include tertiary amines such as triethylamine, organic bases such as nitrogen-containing heterocyclic compounds such as pyridine, and inorganic bases such as potassium carbonate.
The reaction liquid after completion of the reaction can be isolated from the compound represented by the formula (III) by performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound represented by the formula (III) can also be purified by operations such as chromatography and recrystallization.

{Production method G}
A compound represented by formula (V);
Formula (X)
L ^1- (CH ₂ ) _n -OH (X)
[Wherein, n and L ¹ represent the same meaning as described above. ]
The manufacturing method by making the alcohol compound represented by these react.
The reaction is usually performed in the presence of a solvent and a condensing agent.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 150 ° C.
Solvents used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, and mixtures thereof. Can be mentioned.
Examples of the condensing agent include a reagent composed of diethyl azodicarboxylate and triphenylphosphine.
The amount of the reagent used for the reaction is usually 0.5 mol to excess amount, preferably 1 mol of the alcohol compound represented by the formula (X) with respect to 1 mol of the compound represented by the formula (V). The proportion of the condensing agent is usually 0.8 to 2 mol, preferably 1 to 2 mol.
The reaction liquid after completion of the reaction can be isolated from the compound represented by the formula (III) by performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound represented by the formula (III) can also be purified by operations such as chromatography and recrystallization.

〔式中、A、E、Z、k、n及びL¹は前述と同じ意味を表す。〕
で表される化合物と、
式(XII)
R¹-OH (XII)
〔式中、R¹は前述と同じ意味を表す。〕
で表されるアルコール化合物とを、反応させることにより製造する方法。
該反応は通常溶媒および縮合剤の存在下に行われる。
溶媒としては例えば、トルエン、ヘキサン等の炭化水素類、テトラヒドロフラン、tert-ブチルメチル等のエーテル類、クロロベンゼン等のハロゲン化炭化水素類、ジメチルホルムアミド等のアミド類及びこれらの混合物が挙げられる。
反応時間の範囲は通常5分間〜72時間であり、反応温度の範囲は通常-20℃から反応に使用する溶媒の沸点または150℃までの範囲である。
縮合剤としては、アゾジカルボン酸ジエチル及びトリフェニルホスフィンからなる試剤が挙げられる。
反応に供される試剤の量は、式(XI)で表される化合物 1モルに対して、式(XII)で表される化合物は、通常、0.5モル〜過剰量の割合、好ましくは1モル〜2モルの割合であり、縮合剤は、通常0.8〜2モルの割合、好ましくは1モル〜2モルの割合である。
反応終了後の反応液は、例えば有機溶媒抽出、濃縮等の後処理操作を行うことにより式(III-a)で表される化合物を単離することができる。単離された式(III-a)で表される化合物はクロマトグラフィー、再結晶等の操作により精製することもできる。 {Production method H}
Formula (XI)

[Wherein, A, E, Z, k, n and L ¹ represent the same meaning as described above. ]
A compound represented by
Formula (XII)
R ¹ -OH (XII)
[Wherein, R ¹ represents the same meaning as described above. ]
The method of manufacturing by making the alcohol compound represented by react.
The reaction is usually performed in the presence of a solvent and a condensing agent.
Examples of the solvent include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene, amides such as dimethylformamide, and mixtures thereof.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 150 ° C.
Examples of the condensing agent include a reagent composed of diethyl azodicarboxylate and triphenylphosphine.
The amount of the reagent used for the reaction is usually 0.5 mol to an excess amount, preferably 1 mol of the compound represented by the formula (XII) with respect to 1 mol of the compound represented by the formula (XI). The proportion of the condensing agent is usually 0.8 to 2 mol, preferably 1 to 2 mol.
After completion of the reaction, the compound represented by the formula (III-a) can be isolated by performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound represented by the formula (III-a) can also be purified by operations such as chromatography and recrystallization.

  The compound represented by the formula (IX) can be produced, for example, by {Production method I} or {Production method J}.

{Production method I}
A method for producing a compound represented by formula (V) by reacting a compound represented by formula (X).
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, methanol, ethanol, and the like. Alcohols, ketones such as acetone, organic sulfur compounds such as dimethyl sulfoxide, water, and mixtures thereof.
The amount of the reagent used for the reaction is usually 0.9 mol to an excess amount, preferably 0.9 mol of the compound represented by the formula (X) with respect to 1 mol of the compound represented by the formula (V). It is a ratio of ˜2 mol.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 250 ° C.
The reaction can also be performed in the presence of a base. Examples of the base used in this case include alkali metal alkoxides such as potassium tert-butoxide, and inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydride.
After completion of the reaction, the compound represented by the formula (IX) can be isolated by performing post-treatment operations such as organic solvent extraction and concentration. The isolated compound represented by the formula (IX) can also be purified by operations such as chromatography and recrystallization.

〔式中、A、E、Z、k及びnは前述と同じ意味を表す。〕
で表される化合物と式(VII)で表される化合物とを、反応させることにより製造する方法。
該反応は通常溶媒中で行われる。
該反応に用いられる溶媒としては例えば、トルエン、ヘキサン等の炭化水素類、テトラヒドロフラン、tert-ブチルメチル等のエーテル類、クロロベンゼン等のハロゲン化炭化水素類、ジメチルホルムアミド等の酸アミド類、メタノール、エタノール等のアルコール類、アセトン等のケトン類、ジメチルスルホキシド等の有機硫黄化合物類、水及びこれらの混合物が挙げられる。
反応に供される試剤の量は、式(XIII)で表される化合物1モルに対して、式(VII)で表される化合物は、通常、0.9モル〜過剰量の割合、好ましくは0.9モル〜2モルの割合である。
反応時間の範囲は通常5分間〜72時間であり、反応温度の範囲は通常-20℃から反応に使用する溶媒の沸点または250℃までの範囲である。
該反応は塩基の存在下行うこともできる。その場合に用いられる塩基としては、カリウムtert-ブトキシド等のアルカリ金属アルコキシド、水酸化ナトリウム、炭酸カリウム、水素化ナトリウム等の無機塩基類が挙げられる。
反応終了後の反応液は、例えば有機溶媒抽出、濃縮等の通常の後処理操作を行うことにより式(IX)で表される化合物を単離することができる。単離された式(IX)で表される化合物はクロマトグラフィー、再結晶等の操作により精製することもできる。 {Production method J}
Formula (XIII)

[Wherein, A, E, Z, k and n represent the same meaning as described above. ]
A method for producing a compound represented by formula (VII) by reacting the compound represented by formula (VII):
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and tert-butylmethyl, halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, methanol, ethanol, and the like. Alcohols, ketones such as acetone, organic sulfur compounds such as dimethyl sulfoxide, water, and mixtures thereof.
The amount of the reagent to be used for the reaction is usually 0.9 mol to excess amount, preferably 0.9 mol of the compound represented by formula (VII) with respect to 1 mol of the compound represented by formula (XIII). It is a ratio of ˜2 mol.
The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from -20 ° C to the boiling point of the solvent used in the reaction or 250 ° C.
The reaction can also be performed in the presence of a base. Examples of the base used in this case include alkali metal alkoxides such as potassium tert-butoxide, and inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydride.
From the reaction solution after completion of the reaction, the compound represented by the formula (IX) can be isolated by performing usual post-treatment operations such as organic solvent extraction and concentration. The isolated compound represented by the formula (IX) can also be purified by operations such as chromatography and recrystallization.

〔式中、A、E、Z、k及びnは、前述と同じ意味を表す。〕
で表される化合物を加水素分解する方法。
該反応は通常溶媒および加水素分解触媒の存在下に行われる。
加水素分解触媒とは、パラジウム、ニッケル等の遷移金属原子を含有する化合物若しくはその化合物を含んでなる混合物であり、具体的には例えばパラジウム/活性炭が挙げられる。
反応に用いられる加水素分解触媒の量は、式(IX-a)で表される化合物1グラムに対して通常0.001〜1グラムの割合である。
該反応は、通常水素雰囲気下で行われるが、さらに必要に応じて酸を加えることができる。この場合の水素の圧力は、通常1〜10気圧の範囲である。
該反応は酸の存在下で行うこともできる。その場合に用いられる酸としては、例えば塩酸、硫酸等の無機酸類、p-トルエンスルホン酸等の有機酸類及びこれらの混合物が挙げられる。
該反応に用いられる溶媒としては、トルエン、ヘキサン等の炭化水素類、テトラヒドロフラン、メチルtert-ブチルエーテル等のエーテル類、1,2-ジクロロエタン等のハロゲン化炭化水素類、酢酸エチル等のエステル類、メタノール、エタノール等のアルコール類、アセトン等のケトン類、水及びこれらの混合物が挙げられる。
反応の終点は、例えば水素の吸収量の経時変化を測定し、水素の吸収速度を確認することにより決定することができる。
反応終了後の反応液は、例えば濾過した後、得られた濾液の抽出、濃縮等の後処理操作を行うことにより、式(XIII)で表される化合物を単離することができる。単離された式(XIII)で表される化合物はクロマトグラフィー、再結晶等の操作により精製することもできる。 The compound represented by the formula (XIII) can be produced, for example, by {Production Method K}.
{Production method K}
Of the compounds represented by formula (IX), formula (IX-a) wherein G is a benzyloxy group

[Wherein, A, E, Z, k and n represent the same meaning as described above. ]
The method of carrying out hydrogenolysis of the compound represented by these.
The reaction is usually performed in the presence of a solvent and a hydrogenolysis catalyst.
The hydrogenolysis catalyst is a compound containing a transition metal atom such as palladium or nickel or a mixture containing the compound, and specifically includes palladium / activated carbon.
The amount of the hydrogenolysis catalyst used for the reaction is usually in a ratio of 0.001 to 1 gram with respect to 1 gram of the compound represented by the formula (IX-a).
The reaction is usually carried out in a hydrogen atmosphere, but an acid can be added as necessary. The hydrogen pressure in this case is usually in the range of 1 to 10 atmospheres.
The reaction can also be performed in the presence of an acid. Examples of the acid used in that case include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid, and mixtures thereof.
Solvents used in the reaction include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran and methyl tert-butyl ether, halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, methanol , Alcohols such as ethanol, ketones such as acetone, water, and mixtures thereof.
The end point of the reaction can be determined, for example, by measuring the change in hydrogen absorption over time and confirming the hydrogen absorption rate.
The reaction solution after completion of the reaction can be isolated by, for example, filtering and then performing post-treatment operations such as extraction and concentration of the obtained filtrate to isolate the compound represented by the formula (XIII). The isolated compound represented by the formula (XIII) can also be purified by procedures such as chromatography and recrystallization.

The imidazole compound represented by the formula (IV), the compound represented by the formula (VII), the compound represented by the formula (VIII), and the alcohol compound represented by the formula (X) are commercially available or commercially available. It can be manufactured from things.
The phenol compound represented by the formula (V) can be produced according to the method described in, for example, published patent publication 2003-183207, Heterocycles 1983, 20 (4), 653-660.
The imidazole compound represented by the formula (VI) can be produced, for example, according to the method described in Journal of Medicinal Chemistry 1981, 24 (10), 1139-1148.

式（ii）で示される化合物；

式（iii）で示される化合物；

式（iv）で示される化合物；

式（v）で示される化合物；

式（vi）で示される化合物；

式（vii）で示される化合物；

式（viii）で示される化合物；

式（ix）で示される化合物；

式（x）で示される化合物；

上記式（i）〜（ix）および（x）の各々の式中のＡ、ＥおよびＧの各置換基の組合せを、（表１）に表す。 Hereinafter, although the specific example of this invention compound is shown, this invention compound is not limited to these examples.
A compound of formula (i);

A compound of formula (ii);

A compound of formula (iii);

A compound of formula (iv);

A compound of formula (v);

A compound of formula (vi);

A compound of formula (vii);

A compound of formula (viii);

A compound of formula (ix);

A compound of formula (x);

The combinations of the substituents of A, E and G in the formulas (i) to (ix) and (x) are shown in (Table 1).

なお、表中のPhはフェニル基を表す。

In the table, Ph represents a phenyl group.

式中のＡ、Ｅ、ｎおよびＸ¹の各置換基の組合せを（表２）に表す。 Next, specific examples of the intermediate of the present invention are shown below, but the intermediate of the present invention is not limited to these examples.
A compound represented by formula (xi);

The combinations of the substituents A, E, n and X ^{1 in} the formula are shown in (Table 2).

  The plant disease control agent of the present invention may be the compound of the present invention itself, but usually mixed with a solid carrier, a liquid carrier, a surfactant, and other adjuvants for formulation, emulsion, wettable powder, granule Used in wettable powders, emulsion preparations, flowable preparations, powders, granules and the like. These preparations usually contain 0.1 to 90% by weight of the compound of the present invention as an active ingredient.

  Examples of solid carriers used in the formulation include kaolin clay, attapulgite clay, bentonite, montmorillonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite and other minerals, corn cob flour, walnut Examples include natural organic materials such as shell powder, synthetic organic materials such as urea, salts such as calcium carbonate and ammonium sulfate, and fine powders or granular materials such as synthetic inorganic materials such as synthetic silicon hydroxide. Examples of liquid carriers include xylene, Aromatic hydrocarbons such as alkylbenzene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, propylene glycol and cellosolve, ketones such as acetone, cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, petroleum aliphatic hydrocarbons , Esters, di Sulfoxide, acetonitrile, water and the like.

  Surfactants include, for example, alkyl sulfates, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphates, lignin sulfonates, naphthalene sulfonate formalin condensates, and the like. Nonionic surfactants such as ionic surfactants, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl polyoxypropylene block copolymers, sorbitan fatty acid esters and the like can be mentioned.

  Other formulation adjuvants include, for example, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, gum arabic, alginic acid and its salts, polysaccharides such as CMC (carboxymethylcellulose) and xanthan gum, aluminum magnesium silicate, alumina sol and the like. Examples include inorganic substances, preservatives, colorants, PAP (isopropyl acid phosphate), and stabilizers such as BHT.

  The plant disease control agent of the present invention is used, for example, to protect the plant from plant diseases by treating the plant body with foliage, and from the plant diseases, the plant growing in the soil by treating the soil. Used to protect.

When the plant disease control agent of the present invention is used by treating foliage to a plant body or when it is used by treating the soil, the treatment amount is the type of crops, etc., the type of control target disease, control Although it can be changed depending on the degree of occurrence of the target disease, formulation form, treatment time, weather conditions, etc., it is usually 1 to 5000 g, preferably 5 to 1000 g as the compound of the present invention per 10,000 m ² .

  Emulsions, wettable powders and flowables are usually treated by diluting with water and spraying. In this case, the concentration of the compound of the present invention is usually 0.0001 to 3% by weight, preferably 0.0005 to 1% by weight. Powders, granules, etc. are usually processed without dilution.

  Moreover, the plant disease control agent of this invention can also be used by processing methods, such as seed disinfection. Examples of the method for seed disinfection include a method of immersing a plant seed in a plant disease control agent of the present invention prepared so that the concentration of the compound of the present invention is 1 to 1000 ppm, and the concentration of the compound of the present invention in a plant seed. Examples thereof include a method of spraying or smearing the plant disease control agent of the present invention in an amount of 1 to 1000 ppm and a method of dressing the plant disease control agent of the present invention formulated into a powder on plant seeds.

  In the plant disease control method of the present invention, the effective amount of the plant disease control agent of the present invention is usually treated to the plant where the occurrence of the disease is predicted or the soil where the plant grows, and / or the occurrence of the disease is confirmed. It is carried out by treating the plant or the soil where the plant grows.

  The compound of the present invention can be used as a plant disease control agent for fields, paddy fields, orchards, tea gardens, pastures, lawns, etc., and is used in combination with other agricultural and horticultural fungicides to enhance the control effect. Can also be expected. Other agricultural and horticultural fungicides that can be mixed include, for example, propiconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflate Azole fungicides such as lumizole, tetraconazole, microbutanyl, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, viteltanol, imazalil and flutriahol, fenpropimorph, tridemorph and fenpropidin Cyclic amine fungicidal compounds such as carbendazim, benomyl, thiabendazole, thiophanate methyl and other benzimidazole fungicidal compounds, procymidone, cyprodinil Pyrimethanyl, dietofencarb, thiuram, fluazinam, mancozeb, iprodione, vinclozolin, chlorothalonil, captan, mepanipyrim, fenpiclonyl, fludioxonil, diclofluanide, phorpet, cresoxime methyl, azoxystrobin, trifloxystrobin, picoxystrobin, N- Examples include methyl-α-methoxyimino-2-[(2,5-dimethylphenoxy) methyl] phenylacetamide, spiroxamine, quinoxyphene, fenhexamide, famoxadone, fenamidone (RP-407213), and iprovalib.

  The compound of the present invention can be used in combination with or combined with other agricultural and horticultural insecticides, acaricides, nematicides, herbicides, plant growth regulators, and fertilizers. Such insecticides and / or acaricides and / or nematicides include, for example, fenitrothion, phenithione, diazinon, chlorpyrifos, acephate, metidathion, disulfoton, DDVP, sulprophos, cyanophos, dioxabenzophos, dimethoate, phentoate, malathion Organophosphorus compounds such as trichlorphone, azinephosmethyl, monocrotophos, ethion, phosthiazete; carbamate compounds such as BPMC benfuracarb, propoxyl, carbosulfan, carbaryl, mesomil, ethiophene carb, aldicarb, oxamyl, phenothiocarb, etc .; etofenprox, Fenvalerate, esfenvalerate, phenpropatoline, cypermethrin, permethrin, cyhalothrin, deltamethrin, cyclo Pyrethroid compounds such as rosrin, fulvalinate, bifenthrin, acrinathrin, 2-methyl-2- (4-bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, tralomethrin, and silafluorene; thiadiazine derivatives such as buprofezin; nitroimidazolidine derivatives; cartap , Thiocyclam, bensultap and other nereistoxin derivatives; N-cyano-N′-methyl-N ′-(6-chloro-3-pyridylmethyl) acetamidine and other N-cyanoamidine derivatives; endosulfan, gamma-BHC, 1 Chlorinated hydrocarbon compounds such as 1,2-bis (chlorophenyl) -2,2,2-trichloroethanol; Benzoylphenylurea compounds such as chlorfluazuron, teflubenzuron and flufenoxuron; Forms such as amitraz and chlordimeform Amidine derivatives; Thiourea derivatives such as afenthiuron; phenylpyrazole compounds; tebufenozide, 4-bromo-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile; bromopropylate; tetradiphone; quinomethionate Propargate; fenbutatin oxide; hexythiazox; clofentezine; pyridathioben; fenpyroximate; polynactin complex [tetranactin, dinactin, trinactin];

Examples of plant diseases that can be controlled by the compounds of the present invention include the following diseases.
Rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani); wheat powdery mildew (Erysiphe graminis), red mold (Gibberella zeae), rust (Puccinia striiformis) , P. graminis, P. recondita, P. hordei), snow rot (Typhula sp., Micronectriella nivalis), naked smut (Ustilago tritici, U. nuda), lintel scab (Tilletia caries), eye disease ( Pseudocercosporella herpotrichoides), cloud disease (Rhynchosporium secalis), leaf blight (Septoria tritici), blight (Leptosphaeria nodorum); citrus black spot (Diaporthe citri); , P. italicum); apple Moniria disease (Sclerotinia mali), rot disease (Valsa mali), powdery mildew (Podosphaera leucotricha), spotted leaf disease (Alternaria mali), black spot disease (Venturia inaequalis); pear black spot disease ( Venturia nashicola, V. pirina), black spot disease (Alternaria kikuchiana), red star disease (Gymnosporangium haraeanu) m), peach blight (Sclerotinia cinerea), black scab (Cladosporium carpophilum), phoropsis rot (Phomopsis sp.); grape black rot (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust disease (Phakopsora ampelopsidis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola); oyster anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycosphaerella nawae); Anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaerella melonis), vine split (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.) Blight (Pythium sp.); Tomato ring rot (Alternaria solani), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans); eggplant brown rot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum); Brassicaceae vegetable black spot (Alternaria japonica), white spot (Cercosporella br) assicae); leek rust (Puccinia allii); soybean purpura (Cercospora kikuchii), black scab (Elsinoe glycines), black spot (Diaporthe phaseolorum var. sojae); bean anthracnose (Colletotrichum lindemthianum); peanut Black astringency (Cercospora personata), brown spot (Cercospora arachidicola); pea powdery mildew (Erysiphe pisi); potato summer plague (Alternaria solani); plague (Phytophthora infestans); strawberry powdery mildew (Sphaerotheca humuli ); Chamodium blast (Exobasidium reticulatum), white scab (Elsinoe leucospila); tobacco scab (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina) ), Plague (Phytophthora nicotianae); brown spot of sugar beet (Cercospora beticola); black spot of rose (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa); brown spot of chrysanthemum (Septoria chrysanthemi-indici), white rust (Puccinia horiana); various crops Botrytis (Botrytis cinerea), Sclerotinia rot (Sclerotinia sclerotiorum).

  Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a formulation example, a test example, etc., this invention is not limited only to these examples.

First, production examples of the compounds of the present invention and intermediates of the present invention are shown in Production Examples and Intermediate Production Examples.
Unless otherwise specified, ¹ H-NMR was measured using tetramethylsilane (TMS) as an internal standard (0 [ppm]).

Production Example 1
4: 1 (molar ratio) mixture of 2,6-dichloro-4-methoxyphenol and 2,3,6-trichloro-4-methoxyphenol (0.40 g), 1- (6-chlorohexyl) -1H-imidazole A mixture of hydrochloride (0.30 g), dimethylformamide (2 ml), tetrabutylammonium bromide (0.06 g) and cesium carbonate (0.80 g) was stirred at 80 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-methoxyphenoxy) hexyl]- A 6: 1 (molar ratio) mixture of 1H-imidazole and 1- [6- (2,3,6-trichloro-4-methoxyphenoxy) hexyl] -1H-imidazole (present compound 1, 0.31 g) was obtained. It was.
Compound 1 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.35-1.43 (2H, m), 1.54-1.62 (2H, m), 1.77-1.87 (4H, m), 3.76 (2.6H, s), 3.85 ( 0.4H, s), 3.88-3.97 (4H, s), 6.81 (1.7H, s), 6.88 (1H, s), 6.91 (1H, s), 7.05 (1H, s), 7.47 (1H, s) .

Production Example 2
4: 1 (molar ratio) of 1-chloro-6- (2,6-dichloro-4-ethoxyphenoxy) hexane and 1-chloro-6- (2,3,6-trichloro-4-ethoxyphenoxy) hexane A mixture of the mixture (0.40 g), imidazole (0.17 g), dimethylformamide (2 ml), potassium bromide (0.05 g) and potassium carbonate (0.5 g) was stirred at 90 ° C. for 6 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-ethoxyphenoxy) hexyl]- A 2: 3 (molar ratio) mixture of 1H-imidazole and 1- [6- (2,3,6-trichloro-4-ethoxyphenoxy) hexyl] -1H-imidazole (present compound 2, 0.30 g) was obtained. It was.
Compound 2 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.3-1.9 (11H, m), 3.91-3.98 (4.8H, m), 4.06 (1.2H, q, J = 7.1 Hz), 6.82 (0.8H, s), 6.86 (0.6H, s), 6.91 (1H, s), 7.06 (1H, s), 7.46 (1H, s).

Production Example 3
A mixture of 2,6-dichloro-4-propoxyphenol (0.25 g), 1-bromo-5-chloropentane (0.22 g), dimethylformamide (1.5 ml) and cesium carbonate (1.0 g) was stirred for 2 days. To the mixture were added imidazole (0.20 g) and potassium bromide (0.05 g), and the mixture was stirred at 90 ° C. for 2 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [5- (2,6-dichloro-4-propoxyphenoxy) pentyl]- 1H-imidazole (the present compound 3, 0.31 g) was obtained.
Compound 3 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.02 (3H, t, J = 7.4 Hz), 1.54-1.62 (2H, m), 1.73-1.93 (6H, m), 3.85 (2H, t, J = 6.6 Hz), 3.93 (2H, t, J = 6.2 Hz), 3.98 (2H, t, J = 7.2 Hz), 6.83 (2H, s), 6.92 (1H, s), 7.06 (1H, s), 7.48 (1H, s).

Production Example 4
2,6-dichloro-4-propoxyphenol (0.27 g), 1- (6-chlorohexyl) -1H-imidazole hydrochloride (0.25 g), dimethylformamide (1.5 ml), cesium carbonate (1.0 g) and bromide A mixture of potassium (0.05 g) was stirred at 90 ° C. for 2 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-propoxyphenoxy) hexyl]- 1H-imidazole (the present compound 4, 0.17 g) was obtained.
Compound 4 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.02 (3H, t, J = 7.6 Hz), 1.35-1.43 (2H, m), 1.54-1.62 (2H, m), 1.73-1.87 (6H, m ), 3.85 (2H, t, J = 6.6 Hz), 3.91-3.97 (4H, m), 6.83 (2H, s), 6.91 (1H, s), 7.06 (1H, s), 7.47 (1H, s) .

Production Example 5
1- [6- (2,6-dichloro-4-hydroxyphenoxy) hexyl] -1H-imidazole (0.30 g), cesium carbonate (0.7 g), dimethylformamide (1 ml) and butyl bromide (0.1 g) The mixture was stirred at 90 ° C. for 2 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-butoxyphenoxy) hexyl]- 1H-imidazole (the present compound 5, 0.27 g) was obtained.
Compound 5 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 0.97 (3H, t, J = 7.4 Hz), 1.35-1.86 (12H, m), 3.87-3.97 (6H, m), 3.82 (2H, s), 6.91 (1H, s), 7.05 (1H, s), 7.46 (1H, s).

The following compounds were obtained according to the method described in Production Example 5.
1- [6- (2,6-Dichloro-4-isopropoxyphenoxy) hexyl] -1H-imidazole (Compound 6 of the present invention)
Compound 6 of the present invention
¹ H-NMR (CDCl3) δ (ppm): 1.31 (6H, d, J = 6.0 Hz), 1.35-1.43 (2H, m), 1.54-1.62 (2H, m), 1.77-1.87 (4H, m) , 3.93 (2H, t, J = 6.4 Hz), 3.95 (2H, t, J = 7.2 Hz), 4.41 (1H, sept, J = 6.0 Hz), 6.81 (2H, s), 6.91 (1H, s) , 7.05 (1H, s), 7.47 (1H, s).
1- [6- (4-Allyloxy-2,6-dichlorophenoxy) hexyl] -1H-imidazole (Compound 7 of the present invention)
Compound 7 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.37-1.43 (2H, m), 1.54-1.62 (2H, m), 1.77-1.87 (4H, m), 3.93 (2H, t, J = 6.4 Hz ), 3.95 (2H, t, J = 7.2 Hz), 4.47 (2H, d, J = 5.2 Hz), 5.30 (1H, d, J = 10.8 Hz), 5.39 (1H, d, J = 16.6 Hz), 5.99 (1H, ddd, J = 16.6 Hz, 10.8 Hz, 5.2 Hz), 6.85 (2H, s), 6.91 (1H, s), 7.05 (1H, s), 7.47 (1H, s).

Production Example 8
1- [6- (2,6-dichloro-4-hydroxyphenoxy) hexyl] -1H-imidazole (0.30 g), potassium carbonate (0.4 g), dimethylformamide (1 ml) and trifluoromethanesulfonic acid 2,2, A mixture of 2-trifluoroethyl (0.24 g) was stirred at room temperature for 18 hours. Water was added to the reaction mixture, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4), and 1- [6- (2,6-dichloro-4- (2,2,2) -Trifluoroethoxy) phenoxy) hexyl] -1H-imidazole (the present compound 8, 0.35 g).
Compound 8 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.35-1.43 (2H, m), 1.54-1.62 (2H, m), 1.78-1.87 (4H, m), 3.94 (2H, t, J = 6.4 Hz ), 3.96 (2H, t, J = 6.8 Hz), 4.29 (2H, q, J = 8.0 Hz), 6.91 (3H, s), 7.06 (1H, s), 7.48 (1H, s).

The following compounds were obtained according to the method described in Production Example 8.
1- [6- (4-((E) -2-butenyloxy) -2,6-dichlorophenoxy) hexyl] -1H-imidazole and 1- [6- (4-((Z) -2-butenyloxy)- 2,6-dichlorophenoxy) hexyl] -1H-imidazole 4: 1 mixture (present compound 9)
Compound 9 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.37-1.42 (2H, m), 1.54-1.60 (2H, m), 1.72-1.85 (7H, m), 3.93 (2H, t, J = 6.4 Hz ), 3.95 (2H, t, J = 7.1 Hz), 4.38 (1.6H, d, J = 6.1 Hz), 4.52 (0.4H, d, J = 6.1 Hz), 5.6-5.9 (2H, m), 6.84 (2H, s), 6.91 (1H, s), 7.06 (1H, s), 7.47 (1H, s).
1- [6- (2,6-Dichloro-4-methallyloxyphenoxy) hexyl] -1H-imidazole (Compound 10 of the present invention)
Compound 10 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.3-1.9 (8H, m), 1.81 (3H, s), 3.89-3.99 (4H, m), 4.36 (2H, s), 5.00 (1H, s ), 5.06 (1H, s), 6.86 (2H, s), 6.93 (1H, s), 7.07 (1H, s), 7.49 (1H, s).

Production Example 11
4- (2-Chloro-2-propenyloxy) -2,6-dichloro-1- (6-methanesulfonyloxyhexyloxy) benzene (0.20 g), imidazole (0.07 g), potassium carbonate (0.5 g) and dimethyl A mixture of formamide (1 ml) was stirred at 80 ° C. for 2 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / chloroform = 1/4) to give 1- [6- (2,6-dichloro-4- (2-chloro-2- Propenyloxy) phenoxy) hexyl] -1H-imidazole (the present compound 11, 0.18 g) was obtained.
Compound 11 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.35-1.43 (2H, m), 1.54-1.62 (2H, m), 1.77-1.88 (4H, m), 3.94 (2H, t, J = 6.4 Hz ), 3.95 (2H, t, J = 7.3 Hz), 4.52 (2H, s), 5.46 (1H, s), 5.53 (1H, s), 6.87 (2H, s), 6.94 (1H, s), 7.06 (1H, s), 7.47 (1H, s).

Production Example 12
In accordance with the method described in Production Example 11, 1- [6- (2,6-dichloro-4-((E) -3-chloro-2-propenyloxy) phenoxy) hexyl] -1H-imidazole and 1- [ A 1: 1 mixture (Compound 12 of the present invention) with 6- (2,6-dichloro-4-((Z) -3-chloro-2-propenyloxy) phenoxy) hexyl] -1H-imidazole was obtained.
Compound 12 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.37-1.43 (2H, m), 1.54-1.62 (2H, m), 1.77-1.87 (4H, m), 3.92 (2H, t, J = 6.4 Hz ), 3.96 (2H, t, J = 7.0 Hz), 4.45 (1H, dd, J = 5.8 Hz, 1.5 Hz), 4.69 (1H, dd, J = 5.6 Hz, 1.7 Hz), 6.01 (0.5H, dt , J = 5.8 Hz, 5.6 Hz), 6.12 (0.5H, dt, J = 13.4 Hz, 5.8 Hz), 6.28 (0.5H, dt, J = 5.8 Hz, 1.7 Hz), 6.37 (0.5H, dt, J = 13.4 Hz, 1.5 Hz), 6.84 (1H, s), 6.86 (1H, s), 6.91 (1H, s), 7.06 (1H, s), 7.47 (1H, s).

Production Example 13
1- (4-Bromobutoxy) -2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzene (0.20 g), potassium carbonate (0.30 g), imidazole (0.10 g), dimethylformamide A mixture of (1 ml) and tetrabutylammonium bromide (0.01 g) was stirred at room temperature for 24 hours. Water was added to the reaction mixture, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / chloroform = 1/4) to give 1- [4- (2,6-dichloro-4- (3,3-dichloro- 2-propenyloxy) phenoxy) butyl] -1H-imidazole (the present compound 13, 0.16 g) was obtained.
Compound 13 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.78-1.84 (2H, m), 1.80-1.85 (2H, m), 3.97 (2H, t, J = 5.8 Hz), 4.08 (2H, t, J = 7.0 Hz), 4.59 (2H, d, J = 6.4 Hz), 6.11 (1H, t, J = 6.4 Hz), 6.85 (2H, s), 6.95 (1H, s), 7.07 (1H, s), 7.51 (1H, s).

The following compounds were obtained according to the method described in Production Example 13.
1- [5- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) pentyl] -1H-imidazole (present compound 14)
Compound 14 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.54-1.62 (2H, m), 1.81-1.93 (4H, m), 3.94 (2H, t, J = 6.0 Hz), 3.98 (2H, t, J = 7.2 Hz), 4.58 (2H, d, J = 6.4 Hz), 6.11 (1H, t, J = 6.4 Hz), 6.84 (2H, s), 6.92 (1H, s), 7.07 (1H, s), 7.48 (1H, s).
1- [6- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) hexyl] -1H-imidazole (present compound 15)
Compound 15 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.35-1.87 (8H, m), 3.92-3.97 (4H, m), 4.58 (2H, d, J = 6.4 Hz), 6.11 (1H, t, J = 6.4 Hz), 6.84 (2H, s), 6.91 (1H, s), 7.06 (1H, s), 7.47 (1H, s).
1- [8- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) octyl] -1H-imidazole (present compound 16)
Compound 16 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.3-1.9 (12H, m), 3.90-3.97 (4H, m), 4.58 (2H, d, J = 6.2 Hz), 6.11 (1H, t, J = 6.2 Hz), 6.84 (2H, s), 6.90 (1H, s), 7.05 (1H, s), 7.46 (1H, s).

Production Example 17
1- [6- (2,6-dichloro-4-hydroxyphenoxy) hexyl] -1H-imidazole (0.30 g), potassium carbonate (0.4 g), dimethylformamide (1 ml) and 3-bromopropyne (0.12 g) The mixture was stirred at 65 ° C. for 1 hour. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-propargyloxyphenoxy) hexyl] -1H-imidazole (the present compound 17, 0.24 g) was obtained.
Compound 17 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.3-1.9 (8H, m), 2.56 (1H, t, J = 2.4 Hz), 3.94 (2H, t, J = 6.0 Hz), 3.95 (2H, t, J = 6.8 Hz), 4.64 (2H, d, J = 2.4 Hz), 6.91 (1H, s), 6.93 (2H, s), 7.06 (1H, s), 7.47 (1H, s).

Production Example 18
1-chloro-6- (2,6-dichloro-4-benzyloxyphenoxy) hexane (6.4 g), dimethylformamide (25 ml), imidazole (2.3 g), potassium carbonate (5.3 g) and potassium bromide (2.8 The mixture of g) was stirred at 90 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-benzyloxyphenoxy) hexyl] -1H-imidazole (the present compound 18, 3.90 g) was obtained.
Compound 18 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.35-1.43 (2H, m), 1.54-1.62 (2H, m), 1.77-1.87 (4H, m), 3.93 (2H, t, J = 6.4 Hz ), 3.95 (2H, t, J = 7.2 Hz), 4.99 (2H, s), 6.91 (1H, s), 6.92 (2H, s), 7.06 (1H, s), 7.33-7.40 (5H, m) , 7.47 (1H, s).

Production Example 19
1- (6-Chlorohexyloxy) -2,6-dichloro-4-ethylbenzene (0.70 g), dimethylformamide (2.5 ml), potassium carbonate (1.0 g), imidazole (0.30 g) and potassium bromide (0.05 g ) Was stirred at 90 ° C. for 6 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-ethylphenoxy) hexyl]- 1H-imidazole (the present compound 19, 0.69 g) was obtained.
Compound 19 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.20 (3H, t), 1.37-1.43 (2H, m), 1.55-1.63 (2H, m), 1.78-1.87 (4H, m), 2.56 (2H , q, J = 7.5 Hz), 3.95 (2H, t, J = 6.8 Hz), 3.97 (2H, t, J = 6.0 Hz), 6.91 (1H, s), 7.06 (2H, s), 7.11 (1H , s), 7.47 (1H, s).

Production Example 20
A mixture of 2,6-dichloro-4-propylphenol (0.30 g), 1-bromo-5-chloropentane (0.25 g), dimethylformamide (2 ml) and cesium carbonate (1.1 g) was stirred at room temperature for 3 hours. To the mixture were added imidazole (0.20 g) and potassium bromide (0.1 g), and the mixture was stirred at 80 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [5- (2,6-dichloro-4-propylphenoxy) pentyl]- 1H-imidazole (the present compound 20, 0.20 g) was obtained.
Compound 20 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 0.93 (3H, t, J = 7.4 Hz), 1.55-1.65 (4H, m), 1.82-1.93 (4H, m), 2.49 (2H, t, J = 7.4 Hz), 3.92-4.00 (4H, m), 6.87 (1H, s), 7.06 (2H, s), 7.09 (1H, s), 7.48 (1H, s).

Production Example 21
2,6-dichloro-4-propylphenol (0.30 g), 1- [6-chlorohexyl] -1H-imidazole hydrochloride (0.30 g), dimethylformamide (2 ml), cesium carbonate (1.0 g) and bromide A mixture of tetrabutylammonium (0.05 g) was stirred at 80 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-propylphenoxy) hexyl]- 1H-imidazole (the present compound 21, 0.30 g) was obtained.
Compound 21 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 0.93 (3H, t, J = 7.4 Hz), 1.35-1.43 (2H, m), 1.55-1.65 (4H, m), 1.78-1.87 (4H, m ), 2.49 (2H, t, J = 7.8 Hz), 3.95 (2H, t, J = 7.2 Hz), 3.97 (2H, t, J = 6.0 Hz), 6.91 (1H, s), 7.06 (1H, s ), 7.09 (2H, s), 7.47 (1H, s).

Production Example 22
4- (tert-butyl) -2,6-dichloro-1- (4-methanesulfonyloxybutoxy) benzene (0.14 g), imidazole (0.07 g), dimethylformamide (1 ml) and potassium carbonate (0.4 g) The mixture was stirred at 80 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4), and 1- [4- (4- (tert-butyl) -2,6-dichlorophenoxy ) Butyl] -1H-imidazole (the present compound 22, 0.13 g).
Compound 22 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.79-1.86 (2H, m), 2.04-2.15 (2H, m), 4.01 (2H, t, J = 6.0 Hz), 4.09 (2H, t, J = 7.2 Hz), 6.95 (1H, s), 7.07 (1H, s), 7.27 (2H, s), 7.51 (1H, s).

Production Example 23
4- (tert-butyl) -2,6-dichloro-1- (5-methanesulfonyloxypentyloxy) benzene (0.30 g), imidazole (0.15 g), dimethylformamide (2 ml) and potassium carbonate (0.7 g) The mixture was stirred at 80 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4), and 1- [5- (4- (tert-butyl) -2,6-dichlorophenoxy ) Pentyl] -1H-imidazole (present compound 23, 0.30 g).
Compound 23 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.55-1.63 (2H, m), 1.70-1.93 (4H, m), 3.89-4.09 (4H, m), 6.92 (1H , s), 7.06 (1H, s), 7.26 (2H, s), 7.48 (1H, s).

Production Example 24
Mixture of 4- (tert-butyl) -1- (6-bromohexyloxy) -2,6-dichlorobenzene (0.29 g), dimethylformamide (3 ml), potassium carbonate (0.7 g) and imidazole (1.2 g) Was stirred at room temperature for 24 hours. Water was added to the reaction mixture, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4), and 1- [6- (4- (tert-butyl) -2,6-dichlorophenoxy ) Hexyl] -1H-imidazole (Compound 24 of the present invention, 0.20 g) was obtained.
Compound 24 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.5-1.7 (4H, m), 1.78-1.87 (4H, m), 3.95 (2H, t, J = 7.4 Hz), 3.97 (2H, t, J = 6.6 Hz), 6.91 (1H, s), 7.06 (1H, s), 7.26 (2H, s), 7.47 (1H, s).

Production Example 25
4- (tert-butyl) -2,6-dichloro-1- (7-methanesulfonyloxyheptyloxy) benzene (0.30 g), imidazole (0.15 g), dimethylformamide (2 ml) and potassium carbonate (0.7 g) The mixture was stirred at 80 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4), and 1- [7- (4- (tert-butyl) -2,6-dichlorophenoxy ) Heptyl] -1H-imidazole (the present compound 25, 0.26 g) was obtained.
Compound 25 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.3-1.9 (10H, m), 3.94 (2H, t, J = 6.8 Hz), 3.97 (2H, t, J = 6.4 Hz), 6.91 (1H, s), 7.05 (1H, s), 7.27 (2H, s), 7.47 (1H, s).

Production Example 26
1,3-dichloro-2- (6-chlorohexyloxy) -5-methoxymethylbenzene (0.45 g), dimethylformamide (2 ml), imidazole (0.20 g), cesium carbonate (1.0 g) and potassium bromide ( 0.10 g) of the mixture was stirred at 90 ° C. for 30 minutes. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (4-methoxymethyl-2,6-dichlorophenoxy) hexyl] -1H-imidazole (the present compound 26, 0.13 g) was obtained.
Compound 26 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.36-1.43 (2H, m), 1.55-1.63 (2H, m), 1.79-1.87 (4H, m), 3.39 (3H, s), 3.93-4.00 (4H, m), 4.35 (2H, s), 6.91 (1H, s), 7.06 (1H, s), 7.26 (2H, s), 7.47 (1H, s).

Production Example 27
Ethyl 3,5-dichloro-4- (6-chlorohexyloxy) benzoate (0.40 g), imidazole (0.20 g), dimethylformamide (2 ml), cesium carbonate (0.7 g) and potassium bromide (0.1 g) The mixture was stirred at 90 ° C. for 3 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-ethoxycarbonylphenoxy) hexyl] -1H-imidazole (present compound 27, 0.14 g) was obtained.
Compound 27 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.36-1.44 (5H, m), 1.56-1.64 (2H, m), 1.80-1.88 (4H, m), 3.96 (2H, t, J = 7.2) , 4.06 (2H, t, J = 6.4), 4.12 (2H, q, J = 7.2), 6.91 (1H, s), 7.06 (1H, s), 7.47 (1H, s), 7.97 (2H, s) .

Production Example 28
To a mixed solution of 4- (tert-butyl) -2-chloro-6-methylphenol (0.30 g), 1-bromo-4-chlorobutane (0.22 g) and dimethylformamide (1.5 ml), cesium carbonate (1.0 g) And stirred at room temperature. After 3 hours, imidazole (0.2 g) and potassium bromide (0.05 g) were added to the mixture and stirred at 90 ° C. for 2 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (4- (tert-butyl) -2-chloro-6- Methylphenoxy) hexyl] -1H-imidazole (the present compound 28, 0.20 g) was obtained.
Compound 28 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.27 (9H, s), 1.76-1.83 (2H, m), 2.04-2.12 (2H, m), 2.27 (3H, s), 3.90 (2H, t , J = 6.0 Hz), 4.08 (2H, t, J = 7.2 Hz), 6.95 (1H, s), 7.06 (1H, d, J = 2.4 Hz), 7.07 (1H, s), 7.19 (1H, d , J = 2.4 Hz), 7.50 (1H, s).

The following compounds were obtained according to the method described in Production Example 28.
1- [6- (4- (tert-butyl) -2-chloro-6-methylphenoxy) hexyl] -1H-imidazole (present compound 29)
Compound 29 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.27 (9H, s), 1.52-1.60 (2H, m), 1.80-1.93 (4H, m), 2.27 (3H, s), 3.87 (2H, t , J = 6.2 Hz), 3.98 (2H, t, J = 7.2 Hz), 6.92 (1H, s), 7.05 (1H, d, J = 2.4 Hz), 7.06 (1H, s), 7.19 (1H, d , J = 2.4 Hz), 7.48 (1H, s).
1- [6- (4- (tert-butyl) -2-chloro-6-methylphenoxy) hexyl] -1H-imidazole (present compound 30)
Compound 30 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.27 (9H, s), 1.3-1.87 (8H, m), 2.27 (3H, s), 3.86 (2H, t, J = 6.4), 3.95 (2H , t, J = 7.2 Hz), 6.91 (1H, s), 7.05 (1H, d, J = 2.4 Hz), 7.06 (1H, s), 7.18 (1H, d, J = 2.4 Hz), 7.47 (1H , s).

Production Example 31
1-bromo-6- [4- (3,3-dichloro-2-propenyloxy) -2,6-dimethylphenoxy] hexane (0.31 g), potassium carbonate (0.25 g), imidazole (0.16 g) and dimethylformamide (2 ml) of the mixture was stirred at room temperature for 24 hours. Water was added to the reaction mixture, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/10) to give 1- [6- (2,6-dimethyl-4- (3,3-dichloro). -2-propenyloxy) phenoxy) hexyl] -1H-imidazole (the present compound 31, 0.24 g) was obtained.
Compound 31 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.34-1.42 (2H, m), 1.51-1.58 (2H, m), 1.73-1.87 (4H, m), 2.23 (6H, s), 3.68 (2H , t, J = 6.4 Hz), 3.95 (2H, t, J = 6.4 Hz), 4.57 (2H, t, J = 6.2 Hz), 6.14 (1H, t, J = 6.2 Hz), 6.53 (2H, s ), 6.91 (1H, s), 7.06 (1H, s), 7.47 (1H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.28 (9H, s), 1.57-1.90 (6H, m), 2.39 (3H, s), 3.87 (2H, t, J = 7.2 Hz), 3.98 (2H, t, J = 6.2 Hz), 6.82 (1H, s), 6.91 (1H, s), 7.26 (2H, s).
1-[6-(4-(tert-ブチル)-2,6-ジクロロフェノキシ)ヘキシル]-1H-イミダゾール(本発明化合物34)

¹H-NMR(CDCl₃) δ (ppm): 1.28(9H, s), 1.3-1.9 (8H, m), 2.38 (3H, s), 3.84 (2H, t, J = 7.2 Hz), 3.98 (2H, t, J = 6.4 Hz), 6.81 (1H, s), 6.90 (1H, s), 7.26 (2H, s). The following compounds were produced according to the method described in Production Example 31.
1- [6- (2,6-dichloro-((E) -3-chloro-2-propenyloxy) phenoxy) hexyl] -2-methyl-1H-imidazole and 1- [6- (2,6-dichloro 1: 1 mixture with-((Z) -3-chloro-2-propenyloxy) phenoxy) hexyl] -2-methyl-1H-imidazole (invention compound 32)
Compound 32 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.39-1.45 (2H, m), 1.55-1.59 (2H, m), 1.74-1.84 (4H, m), 2.38 (3H, s), 3.92 (2H , t, J = 6.4 Hz), 3.96 (2H, t, J = 7.0 Hz), 4.45 (0.5H, dd, J = 5.8 Hz, 1.5 Hz), 4.69 (0.5H, dd, J = 5.6 Hz, 1.7 Hz), 6.01 (0.5H, dt, J = 5.8 Hz, 5.6 Hz), 6.12 (0.5H, dt, J = 13.4 Hz, 5.8 Hz), 6.28 (0.5H, dt, J = 5.8 Hz, 1.7 Hz) , 6.37 (0.5H, dt, J = 13.4 Hz, 1.5 Hz), 6.84 (1H, s), 6.86 (1H, s), 6.91 (1H, s), 7.06 (1H, s), 7.47 (1H, s ).
1- [5- (4- (tert-butyl) -2,6-dichlorophenoxy) pentyl] -2-methyl-1H-imidazole (Compound 33 of the present invention)

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.57-1.90 (6H, m), 2.39 (3H, s), 3.87 (2H, t, J = 7.2 Hz), 3.98 ( 2H, t, J = 6.2 Hz), 6.82 (1H, s), 6.91 (1H, s), 7.26 (2H, s).
1- [6- (4- (tert-butyl) -2,6-dichlorophenoxy) hexyl] -1H-imidazole (Compound 34 of the present invention)

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.3-1.9 (8H, m), 2.38 (3H, s), 3.84 (2H, t, J = 7.2 Hz), 3.98 ( 2H, t, J = 6.4 Hz), 6.81 (1H, s), 6.90 (1H, s), 7.26 (2H, s).

Production Example 35
1: 3 (molar ratio) of 1-chloro-6- (2,6-dichloro-4-ethoxyphenoxy) hexane and 1-chloro-6- (2,3,6-trichloro-4-ethoxyphenoxy) hexane A mixture of the mixture (0.35 g), 4-methylimidazole, dimethylformamide (2.5 ml), cesium carbonate (0.7 g) and potassium bromide (0.07 g) was stirred at 90 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: methanol / ethyl acetate = 1/4) to give 1- [6- (2,6-dichloro-4-ethoxyphenoxy) hexyl]- 4-methyl-1H-imidazole and 1- [6- (2,3,6-trichloro-4-ethoxyphenoxy) hexyl] -4-methyl-1H-imidazole and 1- [6- (2,6-dichloro- 4-ethoxyphenoxy) hexyl] -5-methyl-1H-imidazole and 1- [6- (2,3,6-trichloro-4-ethoxyphenoxy) hexyl] -5-methyl-1H-imidazole : 2: 3 (molar ratio) mixture (the present compound 35, 0.25 g) was obtained.
Compound 35 of the present invention
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.37-1.83 (8H, m), 2.20 (1H, s), 2.22 (2H, s), 3.82-3.97 (4.8H, m), 4.06 (1.2H , q, J = 7.2 Hz), 6.62 (0.7H, s), 6.76 (0.3H, s), 6.83 (0.8H, s), 6.87 (0.6H, s), 7.34 (0.7H, s), 7.40 (0.3H, s).

¹H-NMR(ジメチルスルホキシド-d₆, 残留溶媒ピーク = 2.50 ppm) δ (ppm): 1.23-1.30 (2H, m), 1.43-1.50 (2H, m), 1.66-1.77 (4H, m), 3.83 (2H, t, J = 6.4 Hz), 3.97 (2H, t, J = 7.2 Hz), 6.86 (2H, s), 6.95 (1H, s), 7.21 (1H, s), 7.75 (1H, s). Intermediate production example 1
A mixture of 6- (2,6-dichloro-4-benzyloxyphenoxy) hexyl-1H-imidazole (3.50 g), ethanol (40 ml), concentrated hydrochloric acid (2 ml) and 10% palladium-activated carbon (0.6 g) The mixture was stirred at room temperature for 6 hours under a hydrogen atmosphere. The reaction mixture was filtered over celite, the filtrate was concentrated in vacuo, and the concentrate was added to saturated aqueous sodium bicarbonate. After extraction with ethyl acetate, the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 1- [6- (2,6-dichloro-4-hydroxyphenoxy) hexyl] -1H-imidazole (2.30 g, intermediate 1 of the present invention).

¹ H-NMR (dimethyl sulfoxide-d ₆ , residual solvent peak = 2.50 ppm) δ (ppm): 1.23-1.30 (2H, m), 1.43-1.50 (2H, m), 1.66-1.77 (4H, m), 3.83 (2H, t, J = 6.4 Hz), 3.97 (2H, t, J = 7.2 Hz), 6.86 (2H, s), 6.95 (1H, s), 7.21 (1H, s), 7.75 (1H, s ).

  About manufacture of the raw material compound used for the manufacture example and the intermediate body manufacture example, it shows in a reference manufacture example.

Reference production example 1
2: 3 (molar ratio) mixture of 2,6-dichloro-4-ethoxyphenol and 2,3,6-trichloro-4-ethoxyphenol (1.90 g), 1-bromo-6-chlorohexane (2.0 g) A mixture of dimethylformamide (20 ml) and potassium carbonate (3.0 g) was stirred at 90 ° C. for 4 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/10) to obtain 1-chloro-6- (2,6-dichloro-4-ethoxyphenoxy) hexane and A 2: 3 (molar ratio) mixture (2.4 g) with 1-chloro-6- (2,3,6-trichloro-4-ethoxyphenoxy) hexane was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.38 (1.2H, t, J = 7.0 Hz), 1.46 (1.8H, t, J = 7.0 Hz), 1.5-1.6 (4H, m), 1.7- 1.9 (4H, m), 3.56 (2H, t, J = 6.8 Hz), 3.93-3.98 (2.8H, m), 4.06 (1.2H, q, J = 6.9 Hz), 6.82 (0.8H, s), 6.86 (0.6H, s).

Reference production example 2
Mix a mixture of ethyl 3,5-dichloro-4-hydroxybenzoate (4.7 g), 1-bromo-6-chlorohexane (5.0 g), dimethylformamide (30 ml) and potassium carbonate (3 g) at 90 ° C. Stir for hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/10), and ethyl 3,5-dichloro-4- (6-chlorohexyloxy) benzoate (5.9 g) was obtained.

Reference production example 3
A tetrahydrofuran solution of ethyl 3,5-dichloro-4- (6-chlorohexyloxy) benzoate (1.8 g) was cooled to 0 ° C., and lithium aluminum hydride (0.27 g) was added to the solution. After 15 minutes, diluted hydrochloric acid was added to the reaction mixture, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/2), and 3,5-dichloro-4- (6-chlorohexyloxy) benzyl alcohol (1.18 g )

Reference production example 4
Add thionyl chloride (5 g) to a mixture of 3,5-dichloro-4- (6-chlorohexyloxy) benzyl alcohol (0.98 g), hexane (10 ml), toluene (20 ml) and dimethylformamide for 30 minutes. And heated to reflux. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 1,3-dichloro-2- (6-chlorohexyloxy) -5-chloromethylbenzene (0.99 g).

Reference production example 5
To a mixture of 1,3-dichloro-2- (6-chlorohexyloxy) -5-chloromethylbenzene (0.3 g) and methanol (10 ml) was added sodium methoxide (28% (W / W) methanol at room temperature). Solution) (2 ml) was added and heated to reflux. After 30 minutes, water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/10) to obtain 1,3-dichloro-2- (6-chlorohexyloxy) -5-methoxymethyl. Benzene (0.25 g) was obtained.

Reference production example 6
To a mixed solution of 2,6-dichloro-4-benzyloxyphenol (8.1 g) and 1-bromo-6-chlorohexane (6.3 g) dissolved in dimethylformamide (40 ml), sodium hydride ( 60% oil, 1.3 g) was added. The mixture was stirred at room temperature for 3 hours and at 100 ° C. for 2 hours. Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with hexane was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/10), and 1-chloro-6- (2,6-dichloro-4-benzyloxyphenoxy) hexane (9.4 g) was obtained.

¹H-NMR(CDCl₃) δ (ppm): 1.19 (3H, t, J = 7.7 Hz), 1.48-1.62 (4H, m), 1.79-1.93 (4H, m), 2.56 (2H, q, J = 7.7 Hz), 3.56 (2H, t, J = 6.6 Hz), 3.98 (2H, t, J = 6.6 Hz), 7.10 (2H, s). Reference production example 7
A mixture of 2,6-dichloro-4-ethylphenol (1.56 g), 1-bromo-6-chlorohexane (1.73 g), dimethylformamide (7 ml) and potassium carbonate (2.5 g) was stirred at 70 ° C. for 6 hours. . Water was added to the reaction mixture cooled to room temperature, and the organic layer obtained by extraction with hexane was dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent: hexane) to obtain 1-chloro-6- (2,6-dichloro-4-ethylphenoxy) hexane (2.40 g).

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.19 (3H, t, J = 7.7 Hz), 1.48-1.62 (4H, m), 1.79-1.93 (4H, m), 2.56 (2H, q, J = 7.7 Hz), 3.56 (2H, t, J = 6.6 Hz), 3.98 (2H, t, J = 6.6 Hz), 7.10 (2H, s).

Reference production example 8
To a mixture of 6- [4- (tert-butyl) -2,6-dichlorophenoxy] hexanol (0.50 g), triphenylphosphine (0.5 g) and dichloromethane (3 ml), carbon tetrabromide (0.9 g) was added. added. After 15 minutes, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/10) to give 1-bromo-6- (4- (tert- Butyl) -2,6-dichlorophenoxy) hexane (0.19 g) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.4-2.0, 8H, m), 3.44 (2H, t, J = 6.8 Hz), 3.99 (2H, t, J = 7.5 Hz), 7.28 (2H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.51-1.60 (4H, m), 1.80-1.95 (4H, m), 3.43 (2H, t, J = 6.9 Hz), 3.95 (2H, t, J = 6.5 Hz), 4.45 (1H, dd, J = 6.0 Hz, 1.6 Hz), 4.69 (1H, dd, J = 5.9 Hz, 2.0 Hz), 6.01 (0.5H, dt, J = 7.4 Hz, 5.9 Hz), 6.13 (0.5H, dt, J = 13.4 Hz, 6.0 Hz), 6.28 (0.5H, dt, J = 7.4 Hz, 2.0 Hz), 6.37 (0.5H, dt, J = 13.4 Hz, 1.6 Hz), 6.84 (1H, s), 6.86 (1H, s) Reference production example 9
6- (2,6-dichloro-4-((E) -3-chloro-2-butenyloxy) phenoxy) hexanol and 6- (2,6-dichloro-4-((Z) -3-chloro-2- To a mixture of 1: 1 mixture (butenyloxy) phenoxy) hexanol (0.66 g), triphenylphosphine (0.5 g) and dichloromethane (3 ml) was added carbon tetrabromide (0.9 g). After 15 minutes, the residue obtained by concentrating the reaction mixture under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/10) to give 1-bromo-6- (2,6-dichloromethane). -4-((E) -3-chloro-2-butenyloxy) phenoxy) hexane and 1-bromo-6- (2,6-dichloro-4-((Z) -3-chloro-2-butenyloxy) phenoxy) A 1: 1 mixture with hexane (0.55 g) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.51-1.60 (4H, m), 1.80-1.95 (4H, m), 3.43 (2H, t, J = 6.9 Hz), 3.95 (2H, t, J = 6.5 Hz), 4.45 (1H, dd, J = 6.0 Hz, 1.6 Hz), 4.69 (1H, dd, J = 5.9 Hz, 2.0 Hz), 6.01 (0.5H, dt, J = 7.4 Hz, 5.9 Hz) , 6.13 (0.5H, dt, J = 13.4 Hz, 6.0 Hz), 6.28 (0.5H, dt, J = 7.4 Hz, 2.0 Hz), 6.37 (0.5H, dt, J = 13.4 Hz, 1.6 Hz), 6.84 (1H, s), 6.86 (1H, s)

Reference production example 10
Mixture of 8-bromooctanol (5.0 g), 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenol (6.9 g), triphenylphosphine (6.6 g) and tetrahydrofuran (100 ml) Was added diethyl azodicarboxylate (10.4 ml) at room temperature. After 2 hours, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: hexane) to give 1-bromo-8- [2,6-dichloro-4- (3,3 -Dichloro-2-propenyloxy) phenoxy] octane (1.0 g) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.33-1.56 (8H, m), 1.78-1.90 (4H, m), 3.41 (2H, t, J = 6.6 Hz), 3.95 (2H, t, J = 6.4 Hz), 4.58 (2H, d, J = 6.0 Hz), 6.11 (1H, t, J = 6.0 Hz), 6.84 (2H, s).

Reference production example 11
Stirring a mixture of 6- [4- (3,3-dichloro-2-propenyloxy) -2,6-dimethylphenoxy] hexanol (0.7 g), triphenylphosphine (0.6 g) and dichloromethane (3 ml); Carbon tetrabromide (0.8 g) was added. After 15 minutes, water was added to the reaction mixture, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/20) to give 1-bromo-6- [4- (3,3-dichloro-2-propenyloxy). ) -2,6-dimethylphenoxy] hexane (0.7 g).
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.46-1.95 (8H, m), 2.25 (6H, s), 3.43 (2H, t, J = 6.8 Hz), 3.71 (2H, t, J = 6.4 Hz), 4.58 (2H, d, J = 6.0 Hz), 6.14 (1H, t, J = 6.0 Hz), 6.54 (2H, s).

Reference production example 12
4 of 6- (4-((E) -2-butenyloxy) -2,6-dichlorophenoxy) hexanol and 6- (4-((Z) -2-butenyloxy) -2,6-dichlorophenoxy) hexanol A mixture of 1 mixture (0.27 g), tetrahydrofuran (5 ml) and methanesulfonyl chloride (0.30 g) was stirred and triethylamine (1.0 g) was added at room temperature. After 1 hour, water was added to the reaction mixture, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/4) to give 4-((E) -2-butenyloxy) -3,5-dichloro-1- 4: 1 mixture of (6-methanesulfonyloxyhexyl) benzene and 4-((Z) -2-butenyloxy) -3,5-dichloro-1- (6-methanesulfonyloxyhexyloxy) benzene (0.23 g) Got.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.4-1.9 (11H, m), 3.01 (3H, s), 3.95 (2H, t, J = 5.9 Hz), 4.25 (2H, t, J = 6.5 Hz), 4.39 (1.6H, d, J = 6.1 Hz), 4.53 (0.4H, d, J = 6.1 Hz), 5.6-5.9 (2H, m), 6.85 (2H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.49 (4H, m), 1.77-1.87 (4H, m), 3.01 (3H, s), 3.96 (2H, t, J = 6.4 Hz), 4.25 (2H, t, J = 6.6 Hz), 4.52 (2H, s), 5.46 (1H, s), 5.54 (1H, s), 6.87 (2H, s).
4-(tert-ブチル)-2,6-ジクロロ-1-(4-メタンスルホニルオキシブトキシ)ベンゼン

¹H-NMR(CDCl₃) δ (ppm): 1.28 (9H, s), 1.92-1.99 (2H, m), 2.04-2.13 (2H, m), 3.02 (3H, s), 4.03 (2H, t, J = 5.9 Hz), 4.38 (2H, t, J = 6.4 Hz), 7.27 (2H, s).
4-(tert-ブチル)-2,6-ジクロロ-1-(5-メタンスルホニルオキシペンチルオキシ)ベンゼン

¹H-NMR(CDCl₃) δ (ppm): 1.28 (9H, s), 1.66-1.74 (2H, m), 1.84-1.91 (4H, m), 3.02 (3H, s), 4.00 (2H, t, J = 6.1 Hz), 4.28 (2H, t, J = 6.5 Hz), 7.26 (2H, s).
4-(tert-ブチル)-2,6-ジクロロ-1-(7-メタンスルホニルオキシペンチルオキシ)ベンゼン

¹H-NMR(CDCl₃) δ (ppm): 1.28 (9H, s), 1.4-1.9 (10H, m), 3.01 (3H, s), 3.99 (2H, t, J = 6.5 Hz), 4.24 (2H, t, J = 6.6 Hz), 7.26 (2H, s). The following compounds were obtained according to the method described in Reference Production Example 12.
4- (2-Chloro-2-propenyloxy) -2,6-dichloro-1- (6-methanesulfonyloxyhexyloxy) benzene

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.49 (4H, m), 1.77-1.87 (4H, m), 3.01 (3H, s), 3.96 (2H, t, J = 6.4 Hz), 4.25 ( 2H, t, J = 6.6 Hz), 4.52 (2H, s), 5.46 (1H, s), 5.54 (1H, s), 6.87 (2H, s).
4- (tert-Butyl) -2,6-dichloro-1- (4-methanesulfonyloxybutoxy) benzene

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.92-1.99 (2H, m), 2.04-2.13 (2H, m), 3.02 (3H, s), 4.03 (2H, t , J = 5.9 Hz), 4.38 (2H, t, J = 6.4 Hz), 7.27 (2H, s).
4- (tert-Butyl) -2,6-dichloro-1- (5-methanesulfonyloxypentyloxy) benzene

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.66-1.74 (2H, m), 1.84-1.91 (4H, m), 3.02 (3H, s), 4.00 (2H, t , J = 6.1 Hz), 4.28 (2H, t, J = 6.5 Hz), 7.26 (2H, s).
4- (tert-Butyl) -2,6-dichloro-1- (7-methanesulfonyloxypentyloxy) benzene

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.4-1.9 (10H, m), 3.01 (3H, s), 3.99 (2H, t, J = 6.5 Hz), 4.24 ( 2H, t, J = 6.6 Hz), 7.26 (2H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.43-1.85 (11H, m), 3.66 (2H, t, J = 6.5 Hz), 3.95 (2H, t, J = 6.5 Hz), 4.38 (1.6H, d, J = 6.3 Hz), 4.52 (0.4H, d, J = 6.3 Hz), 5.6-5.9 (2H, m), 6.84 (1.6H, s), 6.85 (0.4H, s). Reference production example 17
A mixture of 6- (2,6-dichloro-4-hydroxyphenoxy) hexanol (0.32 g), dimethylformamide (4 ml) and crotyl bromide (0.37 g) was stirred, and potassium carbonate (0.7 g) was added at room temperature. added. After 12 hours, water was added to the reaction mixture, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/1) to give 6- (4-((E) -2-butenyloxy) -2,6-dichloro. A 4: 1 mixture (0.37 g) of phenoxy) hexanol and 6- [4-((Z) -2-butenyloxy) -2,6-dichlorophenoxy] hexanol was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.43-1.85 (11H, m), 3.66 (2H, t, J = 6.5 Hz), 3.95 (2H, t, J = 6.5 Hz), 4.38 (1.6H , d, J = 6.3 Hz), 4.52 (0.4H, d, J = 6.3 Hz), 5.6-5.9 (2H, m), 6.84 (1.6H, s), 6.85 (0.4H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.43-1.88 (8H, m), 3.67 (2H, t, J = 6.4 Hz), 3.95 (2H, t, J = 6.6 Hz), 4.45 (1H, dd, J = 6.0 Hz, 1.6 Hz), 4.69 (1H, dd, J = 5.8 Hz, 1.8 Hz), 6.01 (0.5H, dt, J = 7.0 Hz, 5.8 Hz), 6.12 (0.5H, dt, J = 13.2 Hz, 6.0 Hz), 6.27 (0.5H, dt, J = 7.0 Hz, 1.8 Hz), 6.37 (0.5H, dt, J = 13.2 Hz, 1.6 Hz), 6.85 (2H, d, J = 7.6 Hz).
6-(2,6-ジクロロ-4-(2-クロロ-2-プロペニルオキシ)フェノキシ)ヘキサノール

¹H-NMR(CDCl₃) δ (ppm): 1.42-1.89 (8H, m), 3.67 (2H, t, J = 6.5 Hz), 3.96 (2H, t, J = 6.6 Hz), 4.52 (2H, s), 5.46 (1H, s), 5.53 (1H, s), 6.88 (2H, s).
6-[4-(3,3-ジクロロー2-プロペニルオキシ)-2,6-ジメチルフェノキシ]ヘキサノール

¹H-NMR(CDCl₃) δ (ppm): 1.41-1.83 (8H, m), 2.25 (6H, s), 3.67 (2H, m), 3.73 (2H, t, J = 6.8 Hz), 4.58 (2H, d, J = 6.4 Hz), 6.14 (1H, t, J = 6.4 Hz), 6.53 (2H, s). The following compounds were obtained according to the method described in Reference Production Example 17.
6- [2,6-dichloro-4-((E) -3-chloro-2-propenyloxy) phenoxy] hexanol and 6- [2,6-dichloro-4-((Z) -3-chloro-2 1: 1 mixture with -propenyloxy) phenoxy] hexanol

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.43-1.88 (8H, m), 3.67 (2H, t, J = 6.4 Hz), 3.95 (2H, t, J = 6.6 Hz), 4.45 (1H, dd, J = 6.0 Hz, 1.6 Hz), 4.69 (1H, dd, J = 5.8 Hz, 1.8 Hz), 6.01 (0.5H, dt, J = 7.0 Hz, 5.8 Hz), 6.12 (0.5H, dt, J = 13.2 Hz, 6.0 Hz), 6.27 (0.5H, dt, J = 7.0 Hz, 1.8 Hz), 6.37 (0.5H, dt, J = 13.2 Hz, 1.6 Hz), 6.85 (2H, d, J = 7.6 Hz ).
6- (2,6-dichloro-4- (2-chloro-2-propenyloxy) phenoxy) hexanol

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.42-1.89 (8H, m), 3.67 (2H, t, J = 6.5 Hz), 3.96 (2H, t, J = 6.6 Hz), 4.52 (2H, s), 5.46 (1H, s), 5.53 (1H, s), 6.88 (2H, s).
6- [4- (3,3-Dichloro-2-propenyloxy) -2,6-dimethylphenoxy] hexanol

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.41-1.83 (8H, m), 2.25 (6H, s), 3.67 (2H, m), 3.73 (2H, t, J = 6.8 Hz), 4.58 ( 2H, d, J = 6.4 Hz), 6.14 (1H, t, J = 6.4 Hz), 6.53 (2H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.4-1.9 (10H, m), 3.65 (2H, t, J = 6.6 Hz), 3.95 (2H, t, J = 6.6 Hz), 4.58 (2H, d, J = 6.4 Hz), 6.11 (1H, t, J = 6.4 Hz), 6.86 (2H, s). Reference production example 21
Of 7-bromoheptanol (2.5 g), 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenol (4.1 g), dimethylformamide (20 ml) and potassium carbonate (3.7 g) The mixture was stirred at room temperature for 24 hours. Water was added to the reaction mixture, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/2) to give 7- [2,6-dichloro-4- (3,3-dichloro-2- Propenyloxy) phenoxy] heptanol (4.30 g) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.4-1.9 (10H, m), 3.65 (2H, t, J = 6.6 Hz), 3.95 (2H, t, J = 6.6 Hz), 4.58 (2H, d, J = 6.4 Hz), 6.11 (1H, t, J = 6.4 Hz), 6.86 (2H, s).

The following compounds were obtained according to Reference Production Example 21.
6- (4-Benzyloxy-2,6-dichlorophenoxy) hexanol
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.42-1.87 (8H, m), 3.67 (2H, m), 3.95 (2H, t, J = 6.6 Hz), 4.99 (2H, s), 6.92 ( 2H, s), 7.32-7.42 (5H, m).
7- [4- (tert-Butyl) -2,6-dichlorophenoxy] heptanol
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.3-1.9 (10H, m), 3.65 (2H, m), 3.99 (2H, t, J = 6.5 Hz), 7.26 ( 2H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.28 (9H, s), 1.81-1.97 (4H, m), 3.76 (2H, m), 4.04 (2H, t, J = 6.0 Hz), 7.27 (2H, s). Reference production example 24
A mixture of 4- (tert-butyl) -2,6-dichlorophenol (1.5 g), ethyl 4-bromobutanoate (2.1 g), dimethylformamide (10 ml) and potassium carbonate (4 g) was stirred for 12 hours. Water was added to the reaction mixture, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was diluted with tetrahydrofuran (20 ml), stirred, and lithium aluminum hydride (0.8 g) was added at 0 ° C. After 15 minutes, water was added to the reaction mixture, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/2), and 4- (4- (tert-butyl) -2,6-dichlorophenoxy) butanol ( 0.60 g) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.81-1.97 (4H, m), 3.76 (2H, m), 4.04 (2H, t, J = 6.0 Hz), 7.27 ( 2H, s).

Reference production example 25
According to the method of Reference Production Example 24, 6- [4- (tert-butyl) -2,6-dichlorophenoxy] hexanol was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (9H, s), 1.4-1.9 (8H, m), 3.66 (2H, m), 3.99 (2H, t, J = 6.4 Hz), 7.26 ( 2H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.4-1.9 (8H, m), 3.68 (2H, t, J = 6.6 Hz), 3.94 (2H, t, J = 6.6 Hz), 6.79 (2H, s). Reference Production Example 26
A mixture of 6- (4-benzyloxy-2,6-dichlorophenoxy) hexanol (1.5 g), ethyl acetate (30 ml) and 10% palladium-activated carbon (0.3 g) was stirred under a hydrogen atmosphere for 4 hours. The reaction mixture was filtered over celite, and the resulting filtrate was concentrated under reduced pressure to give 6- (2,6-dichloro-4-hydroxyphenoxy) hexanol (1.1 g).

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.4-1.9 (8H, m), 3.68 (2H, t, J = 6.6 Hz), 3.94 (2H, t, J = 6.6 Hz), 6.79 (2H, s).

¹H-NMR(CDCl₃) δ (ppm): 1.41-1.83 (8H, m), 2.22 (6H, s), 3.66-3.71 (4H, m), 6.47 (2H, s). Reference Production Example 27
A mixture of 4-benzoyloxy-2,6-dimethylphenol (2.4 g), methyl 6-bromohexanoate (3 g), dimethylformamide (10 ml) and potassium carbonate (2 g) was stirred at room temperature for 2 hours. . Water was added to the reaction mixture, and the organic layer obtained by extraction with methyl tert-butyl ether was dried over anhydrous sodium sulfate. The concentrate obtained by concentration under reduced pressure was diluted with tetrahydrofuran (30 ml), stirred, and lithium aluminum hydride (1 g) was added at 0 ° C. After 15 minutes, water was added to the reaction mixture, and the organic layer obtained by extraction with ethyl acetate was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/1) to give 6- (4-hydroxy-2,6-dimethylphenoxy) hexanol (1.5 g). Obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.41-1.83 (8H, m), 2.22 (6H, s), 3.66-3.71 (4H, m), 6.47 (2H, s).

Reference Production Example 28
A mixed solution of 4-methoxyphenol (3.7 g), toluene (30 ml) and dicyclohexylamine (1.0 g) was stirred at 60 ° C., and sulfuryl chloride (9.0 g) was added dropwise over 30 minutes. After 4 hours, the mixture was heated to 100 ° C. After 2 hours, a 10% aqueous sodium sulfite solution was added to the reaction mixture cooled to room temperature, and the mixture was partitioned with methyl tert-butyl ether, and the organic layer was dried over anhydrous sodium sulfate. Concentrated under reduced pressure, and the resulting crystals were filtered to obtain a 4: 1 (molar ratio) mixture (4.0 g) of 2,6-dichloro-4-methoxyphenol and 2,3,6-trichloro-4-methoxyphenol. Obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 3.74 (2.4H, s), 3.86 (0.6H, s), 5.00 (1H br s), 6.84 (1.6H, s), 6.89 (0.2H, s ).

Reference Production Example 29
To a mixed solution of 4-ethoxyphenol (2.8 g), toluene (15 ml) and dicyclohexylamine (0.2 g), sulfuryl chloride (9.7 g) was added and stirred at 60 ° C. After 5 hours, water was added to the reaction mixture cooled to room temperature, followed by liquid separation with methyl tert-butyl ether, and the organic layer was dried over anhydrous sodium sulfate. Concentrate under reduced pressure and filter the resulting crystals to give a 2: 3 (molar ratio) mixture of 2,6-dichloro-4-ethoxyphenol and 2,3,6-trichloro-4-ethoxyphenol (3.1 g). Obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.38 (1.2H, t, J = 7.0 Hz), 1.46 (1.8H, t, J = 7.0 Hz), 3.95 (0.8H, q, J = 7.0 Hz ), 4.05 (1.2H, q, J = 7.0 Hz), 5.43 (0.4H, s), 5.57 (0.6H, s), 6.84 (0.8H, s), 6.89 (0.6H, s).

Reference production example 30
A mixed solution of 4-propoxyphenol (4.5 g), toluene (30 ml) and dicyclohexylamine (0.2 g) was stirred at 60 ° C., and sulfuryl chloride (8.1 g) was added dropwise over 2 hours. After 2 hours, the mixture was heated to 100 ° C. After 2 hours, a 10% aqueous sodium sulfite solution was added to the reaction mixture cooled to room temperature, and the mixture was partitioned with methyl tert-butyl ether, and the organic layer was dried over anhydrous sodium sulfate. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/4) to obtain 2,6-dichloro-4-propoxyphenol (1.0 g).
¹ H-NMR (CDCl ₃ δ (ppm): 1.02 (3H, t, J = 7.2 Hz), 1.77 (2H, qt, J = 7.2 Hz, 6.6 Hz), 3.84 (2H, t, J = 6.6 Hz) , 5.41 (1H, s), 6.84 (2H, s).

Reference production example 31
A mixed solution of 4-ethylphenol (2.4 g), toluene (20 ml) and dicyclohexylamine (0.2 g) was stirred at 65 ° C., and sulfuryl chloride (6.0 g) was added dropwise over 4 hours. After 4 hours, a 10% aqueous sodium sulfite solution was added to the reaction mixture cooled to room temperature, and the mixture was partitioned with methyl tert-butyl ether, and the organic layer was dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/10) to obtain 2,6-dichloro-4-ethylphenol (3.06 g, 80%). .
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.20 (3H, t, J = 7.6 Hz), 2.55 (2H, q, J = 7.6 Hz), 5.67 (1H, br s), 7.08 (2H, s ).

Reference production example 32
A mixed solution of 4-propylphenol (4.1 g), toluene (30 ml) and dicyclohexylamine (1.0 g) was stirred at 60 ° C., and sufluryl chloride (8.6 g) was added dropwise over 30 minutes. After 4 hours, the mixture was heated to 100 ° C. After 2 hours, a 10% aqueous sodium sulfite solution was added to the reaction mixture cooled to room temperature, and the mixture was partitioned with methyl tert-butyl ether, and the organic layer was dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 2,6-dichloro-4-propylphenol (5.9 g, 96%).
¹ H-NMR (CDCl ₃ ) δ (ppm): 0.92 (3H, t, J = 7.2), 1.60 (2H, tq, J = 7.8 Hz, 7.2 Hz), 2.48 (2H, t, J = 7.8 Hz) , 5.67 (1H, s), 7.07 (2H, s).

Reference Production Example 33
A solution of 4- (tert-butyl) -2-methylphenol (3.54 g), toluene (30 ml) and dicyclohexylamine (1.0 g) was stirred at 60 ° C., and over 30 minutes, sufluryl chloride (5.0 g) was added. It was dripped. After 4 hours, the mixture was heated to 100 ° C. After 2 hours, a 10% aqueous sodium sulfite solution was added to the reaction mixture cooled to room temperature, and the mixture was partitioned with methyl tert-butyl ether, and the organic layer was dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 4- (tert-butyl) -2-chloro-6-methylphenol (4.1 g).
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.27 (9H, s), 2.35 (3H, s), 5.43 (1H, br, s), 7.04 (1H, br s), 7.14 (1H, br s ).

  Next, formulation examples are shown. In addition, a part represents a weight part.

Formulation Example 1
Each wettable powder is obtained by thoroughly grinding and mixing 50 parts of each of the compounds 1 to 35 of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide.

Formulation Example 2
20 parts of each of the compounds 1 to 35 of the present invention and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol and finely pulverized by a wet pulverization method, and then 0.05 parts of xanthan gum and aluminum 40 parts of an aqueous solution containing 0.1 part of magnesium silicate is added, and further 10 parts of propylene glycol is added and stirred and mixed to obtain each flowable preparation.

Formulation Example 3
2 parts of each of the compounds 1 to 35 of the present invention, 88 parts of kaolin clay and 10 parts of talc are thoroughly pulverized and mixed to obtain each powder.

Formulation Example 4
Each emulsion is obtained by thoroughly mixing 5 parts of each of the compounds 1 to 35 of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.

Formulation Example 5
2 parts of each of the compounds 1 to 35 of the present invention, 1 part of synthetic hydrous oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay Each granule is obtained by drying the granule.

Formulation Example 6
Each flowable preparation is prepared by mixing 10 parts of each of the compounds 1 to 35 of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water, and finely pulverizing them by a wet pulverization method. Get.

Formulation Example 7
10 parts of each of the compounds 1 to 35 of the present invention and 5 parts of Sorpol 1200 (nonionic and anionic surfactant manufactured by Toho Chemical Industries) were mixed in 47 parts of dimethyl sulfoxide and 38 parts of xylene to dissolve each emulsion. Get.

Next, test examples show that the compounds of the present invention are useful as plant disease control agents. The control effect of the compound of the present invention is obtained by observing the area of the lesion on the test plant at the time of the survey, and comparing the area of the lesion in the untreated group with the area of the lesion in the compound-treated group. evaluated.
Moreover, about Test Example 2, the following imidazole compound was used together.
1- [6- (2-Chloro-4-methoxyphenoxy) hexyl] -1H-imidazole (hereinafter referred to as Comparative Compound A)
1- [6- (4-Ethylphenoxy) hexyl] -1H-imidazole (hereinafter referred to as Comparative Compound B)
Comparative compound A was produced according to the method described in EXAMPLE 1 (pages 27 to 28) of EP 274867, and comparative compound B was produced according to the method described in Non-Patent Document 1.

Test example 1
A plastic pot was stuffed with sand loam, sowed with wheat (Norin 73) and grown in a greenhouse for 10 days. Each of the formulations of the present compounds 1 to 11, 13 to 34 and 35 obtained according to Formulation Example 6 was diluted with water to a concentration of 500 ppm to prepare a spray solution. Each spray solution was sprayed on the foliage so as to adhere well to the wheat leaf surface. After spraying, the plants were air-dried to the extent that the spray on the leaf surface was dry, and inoculated with spores of wheat rust. After the inoculation, the control effect was observed with the naked eye after being placed at 23 ° C. under dark and humid conditions for 1 day and further under illumination for 6 days.
As a result, the lesion area of each wheat treated with the spray solution containing the compounds 1 to 11, 13 to 34 and 35 of the present invention was 30% or less of the lesion area in the untreated area.

Test example 2
A plastic pot was filled with sand loam, sown with cucumber (Sagamihanjiro), and grown in a greenhouse for 10 days. Each of the preparations of the present compounds 1-27, 30-35, comparative compound A and comparative compound B obtained according to Formulation Example 6 was diluted with water to a concentration of 500 ppm to prepare a spray solution. Each spray solution was sprayed on the foliage so that it sufficiently adhered to the cucumber cotyledon surface. After spraying, the plants were air-dried to the extent that the spray solution on the leaf surface was dry, and a PDA medium containing spores of gray mold was placed on the cotyledon surface of cucumber. The cucumber was allowed to stand at 12 ° C. and high humidity for 5 days, and then the lesion area of the plant was observed with the naked eye.
As a result, each lesion area of the cucumber treated with the spray liquid containing the present compounds 1-27, 30-34 and 35 as active ingredients was 30% or less of the lesion area in the untreated group. The lesion area of the cucumber treated with the spray solution containing Comparative Compound A and Comparative Compound B was 75% or more of the lesion area in the untreated section.

Claims (9)

Formula (I)

[Where,
A and E independently represent a halogen atom or a C1-C3 alkyl group which may be substituted with a halogen atom,
G represents optionally substituted C2~C6 alkyl group with a halogen atom, a OR ^1, CH ^₂ OR ₂ or C (= O) OR ^3,
R ¹ , R ² and R ³ may each be a C1-C6 alkyl group which may be substituted with a halogen atom, a C3-C6 alkenyl group which may be substituted with a halogen atom, or a halogen atom. Represents a C3-C6 alkynyl group or a benzyl group optionally substituted with a halogen atom,
X represents a C1-C3 alkyl group which may be substituted with a halogen atom,
Z represents a halogen atom or a C1-C3 alkyl group which may be substituted with a halogen atom;
k represents an integer of 0 to 2,
m represents an integer of 0 to 3,
n represents an integer of 4 to 8. ]
An imidazole compound represented by   The imidazole compound according to claim 1, wherein m is 0 in the formula (I).   The imidazole compound according to claim 1, wherein k is 0 in the formula (I).   The imidazole compound according to claim 1, wherein n is 5 in the formula (I).   The imidazole compound according to claim 1, wherein n is 6 in the formula (I).   The imidazole compound according to claim 1, wherein A and E in the formula (I) are chlorine atoms.   A plant disease control agent comprising the imidazole compound according to any one of claims 1 to 6 as an active ingredient.   A method for controlling plant diseases, comprising applying the imidazole compound according to any one of claims 1 to 6 to a plant or soil. Formula (II)

[Where,
A and E independently represent a halogen atom or a C1-C3 alkyl group which may be substituted with a halogen atom,
X represents a C1-C3 alkyl group which may be substituted with a halogen atom,
Z represents a halogen atom or a C1-C3 alkyl group which may be substituted with a halogen atom;
k represents an integer of 0 to 2,
m represents any integer of 0 to 3,
n represents any integer of 4 to 8. ]
An imidazole compound represented by