JP2007161701A - Aryloxy-n-(oxyiminoalkyl)alkanoic acid amino derivative and use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new aryloxy-N-(oxyiminoalkyl)alkanoic acid amide derivative which exhibits acaricidal activity, excellent herbicidal activity at a low dose, excellent selective herbicidal activity between crops and weeds, high safety to crops and human beings and animals and is useful for wide objects such as weeds of paddy rice, field crop, etc., and a herbicide and an acaricide containing the same. <P>SOLUTION: The aryloxy-N-(oxyiminoalkyl)alkanoic acid amide derivative is represented by general formula (I). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative, a herbicide containing it as a herbicidal active ingredient, and an acaricide containing it as an acaricidal active ingredient.

  Herbicides are mainly used to control weeds that grow on farmland and create an environment suitable for crop cultivation. So far, phenoxy, benzoic acid or phenylacetic acid, halogenated carboxylic acid, carbamate, Various herbicides having various structures such as urea, acid amide, heterocyclic, phenol, diphenyl ether, and pyridinium have been proposed and put into practical use.

  Among the above examples, those included in the acid amide herbicide include aryloxyalkanoic acid amide derivatives and the like, and the following compounds are known so far.

  In addition, acaricides are mainly used to control mites that grow on farmland and create an environment suitable for cultivation of crops. So far, amidines, heterocyclics, carbamates, acid amides, Many acaricides having various structures such as macrolides and acrylic acids have been proposed and put into practical use.

［式（Ａ）中、Ｒ₁およびＲ_２は、ハロゲン原子またはＣ１〜Ｃ４アルキル基を示し、Ｒ_３は、Ｃ１〜Ｃ４アルキル基を示し、Ｒ_４は、Ｃ１〜Ｃ７アルキル基を示す。］で表わされるアリールオキシアルカン酸アミド誘導体が記載され、この誘導体は除草活性を有することが記載されている（特許文献１参照。）。
（２）一般式（Ｂ）

［式（Ｂ）中、Ｒ_１およびＲ_２は、それぞれ独立にハロゲン原子またはＣ１〜Ｃ４アルキル基を示し、Ｒ_３は、Ｃ１〜Ｃ４アルキル基を示し、Ｒ_４およびＲ_５は、それぞれ独立に水素原子またはＣ１〜Ｃ３アルキル基を示す。］で表わされるアリールオキシアルカン酸アミド誘導体が記載され、この誘導体は除草活性を有することが記載されている（特許文献２参照。）。 Among the above examples, the acid amide acaricide includes phenoxyalkanoic acid amide derivatives and the like, and the compounds belonging to the phenoxyalkanoic acid amide derivatives so far include the compounds described below, etc. It has been known.
(1) General formula (A)

[In Formula (A), R ₁ and R ₂ represent a halogen atom or a C1-C4 alkyl group, R ₃ represents a C1-C4 alkyl group, and R ₄ represents a C1-C7 alkyl group. The aryloxyalkanoic acid amide derivative represented by the above formula is described, and it is described that this derivative has herbicidal activity (see Patent Document 1).
(2) General formula (B)

[In Formula (B), R ₁ and R ₂ each independently represent a halogen atom or a C1-C4 alkyl group, R ₃ represents a C1-C4 alkyl group, and R ₄ and R ₅ each independently represent A hydrogen atom or a C1-C3 alkyl group is shown. The aryloxyalkanoic acid amide derivative represented by the above formula is described, and it is described that this derivative has herbicidal activity (see Patent Document 2).

［式（Ｃ）中、Ｘは、原子またはトリフルオロメチル基を示し、Ｙは、水素原子または塩素原子を示し、Ｒ_１は、メチル基またはエチル基を示し、Ｘがフッ素原子の場合、Ｒ_２は水素原子およびＲ_３はメチル基を示し、Ｘがトリフルオロメチル基の場合、Ｒ_２およびＲ_３は、それぞれ独立に水素原子またはメチル基を示す。］で表わされるアリールオキシアルカン酸アミド誘導体が記載され、この誘導体は殺ダニ活性を有することが記載されている（特許文献３参照。）。 (3) General formula (C)

[In the formula (C), X represents an atom or a trifluoromethyl group, Y represents a hydrogen atom or a chlorine atom, R ₁ represents a methyl group or an ethyl group, and when X is a fluorine atom, R represents ₂ represents a hydrogen atom and R ₃ represents a methyl group, and when X is a trifluoromethyl group, R ₂ and R ₃ each independently represent a hydrogen atom or a methyl group. Aryloxyalkanoic acid amide derivatives represented by the above formula are described, and this derivative is described to have acaricidal activity (see Patent Document 3).

［式（Ｄ）中、Ｒは、メチル基またはエチル基を示し、Ｘは、塩素原子またはフッ素原子を示し、Ｙは、２−メチル基または３−メチル基を示し、Ｙが２−メチル基の場合、Ｚは水素原子または５−メチル基を示し、Ｙが３−メチル基の場合、Ｚは５−メチル基を示す］で表わされるフェノキシアルカン酸アミド誘導体が記載され、この誘導体は殺ダニ活性を有することが記載されている（特許文献４参照。）。
オランダ出願公開第７２０７９７１号明細書 ベルギー特許第８５０１５４号明細書 米国特許第３９７１８５０号明細書 米国特許第４１１７１６６号明細書 (4) General formula (D)

[In the formula (D), R represents a methyl group or an ethyl group, X represents a chlorine atom or a fluorine atom, Y represents a 2-methyl group or a 3-methyl group, and Y represents a 2-methyl group. Z represents a hydrogen atom or a 5-methyl group, and when Y is a 3-methyl group, Z represents a 5-methyl group]. It is described as having activity (see Patent Document 4).
Netherlands Application Publication No. 7207971 Belgian Patent No. 850154 US Pat. No. 3,971,850 U.S. Pat. No. 4,117,166

  In general, in the development of herbicides, it is required to develop herbicides that exhibit high herbicidal effects even at low dosages, have herbicidal activity against a wide variety of weeds, and are excellent in safety. However, when the above aryloxyalkanoic acid amide derivatives are used as herbicidal active ingredients, the herbicidal effect is insufficient at low doses, and even if they exhibit herbicidal activity, the selection of crops and weeds The herbicidal activity is inferior, and the phytotoxicity of crops is large.

  In general, in the development of acaricides, a high acaricidal effect is exhibited even at a low dose, acaricidal activity against a wide variety of mites, and a highly safe acaricide. Development is required. However, when a phenoxyalkanoic acid amide derivative as described above is used as an acaricidal active ingredient, a low dose of the acaricidal effect is insufficient, or even if it exhibits acaricidal activity, it is harmful to crops. For example, it was not always satisfactory for use as a miticide.

  The present invention is intended to solve the above-described problems, and exhibits excellent herbicidal activity and acaricidal activity even at low dosages. With regard to herbicides, selective herbicidal activity between crops and weeds A novel aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative and herbicides and acaricides containing the same, which can be used for a wide range of subjects such as paddy rice and field crop weeds It is intended to provide.

[式中、Ｘは、ハロゲン原子、Ｃ１〜Ｃ６アルキル基あるいはＣ１〜Ｃ６ハロゲン化アルキル基を示し、Ｒ_１は、水素原子、Ｃ１〜Ｃ６アルキル基、Ｃ１〜Ｃ６アルキルオキシ基あるいはＣ１〜Ｃ６アルキルオキシＣ１〜Ｃ６アルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５は、それぞれ独立に水素原子あるいはＣ１〜Ｃ６アルキル基を示し、Ｒ_６は、水素原子、Ｃ１〜Ｃ６アルキル基、Ｃ３〜Ｃ６アルケニル基、Ｃ３〜Ｃ６アルキニル基、Ｃ１〜Ｃ６アルキルオキシＣ１〜Ｃ６アルキル基、Ｃ１〜Ｃ６ハロゲン化アルキル基あるいはベンジル基を示し、Ｒ_１およびＲ_６の一方あるいは両方がＣ１〜Ｃ６アルキルオキシＣ１〜Ｃ６アルキル基を示すときは、それぞれ独立にＣ１〜Ｃ６アルキルオキシＣ１〜Ｃ６アルキル基中の酸素原子の両端に結合している２本のアルキル鎖が結合し、この酸素原子を含めて５員環あるいは６員環を形成してもよく、ｎは、０ないし５の整数を示し、ｎが２以上のときそれぞれのＸは同一または相異なってもよい。］ The present inventors have intensively studied to solve the above-described problems. As a result, the compound represented by the following general formula (I) exhibits an acaricidal effect, and exhibits an excellent herbicidal effect at low doses against paddy rice and field crop weeds without causing phytotoxicity to the crop. As a result, the present invention has been completed. That is, the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative according to the present invention is characterized by being represented by the general formula (I).

[Wherein, X represents a halogen atom, a C1-C6 alkyl group or a C1-C6 halogenated alkyl group, and R ₁ represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group or a C1-C6 alkyl group. Represents an oxy C1-C6 alkyl group, R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a C1-C6 alkyl group, and R ₆ represents a hydrogen atom, a C1-C6 alkyl group, C3 -C6 alkenyl group, C3-C6 alkynyl group, C1-C6 alkyloxy C1-C6 alkyl group, C1-C6 halogenated alkyl group or benzyl group, one or both of R ₁ and R ₆ are C1-C6 alkyloxy When representing a C1-C6 alkyl group, each independently represents an oxygen atom in the C1-C6 alkyloxy C1-C6 alkyl group. Two alkyl chains bonded to both ends may combine to form a 5-membered or 6-membered ring including this oxygen atom, n represents an integer of 0 to 5, and n is 2 or more In this case, each X may be the same or different. ]

  Further, the herbicide and acaricide according to the present invention contain the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the above general formula (I) as a herbicidal active ingredient and acaricide active ingredient. It is characterized by.

  In the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the above general formula (I), the halogen atom represented by X means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the above formula (1), the C1-C6 alkyl group represented by X, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is a linear or branched chain having 1 to 6 carbon atoms. -Like alkyl group. Examples of such a C1-C6 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, Isopentyl group, 2-methylbutyl group, neopentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 1-ethyl-2-methyl-propyl group or 1- Examples thereof include a methyl-1-ethylpropyl group.

In the above formula (I), the C1-C6 halogenated alkyl group represented by X or R ₆ is a straight chain having 1 to 6 carbon atoms in which at least one hydrogen atom in the alkyl group is substituted with a halogen atom. A chain or branched alkyl group is meant. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of such a C1-C6 halogenated alkyl group include a trifluoromethyl group, a chloromethyl group, a bromomethyl group, a dichloromethyl group, a difluoromethyl group, a trichloromethyl group, a 2-fluoroethyl group, a 2-chloroethyl group, Examples include 2-bromoethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-chloropropyl group, 3-iodopropyl group, and the like.

In the above formula (I), and the C3~C6 alkenyl group represented by R _6, it means a straight or branched alkenyl group having 3 to 6 carbon atoms. Examples of such a C3-C6 alkenyl group include a 2-propenyl group, a 1-methyl-2-propenyl group, a 2-methyl-2-propenyl group, a 2-ethyl-2-propenyl group, a 2-butenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-ethyl-2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-hexenyl Group, 3-hexenyl group, 4-hexenyl group and the like.

In the above formula (I), the C3-C6 alkynyl group represented by R ₆ means a linear or branched alkynyl group having 3 to 6 carbon atoms. Examples of such C3-C6 alkynyl group include 2-propynyl group, 1-methyl-2-propynyl group, 2-butynyl group, 1-methyl-2-butynyl group, 1-ethyl-2-butynyl group, Examples include 3-butynyl group, 2-methyl-3-butynyl group, 2-pentynyl group, 4-pentynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group and 5-hexynyl group.

In the above formula (I), the C1-C6 alkyloxy group represented by R ₁ means a linear or branched alkyloxy group having 1 to 6 carbon atoms. Examples of such C1-C6 alkyloxy groups include a methyloxy group, an ethyloxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, an s-butyloxy group, a t-butyloxy group, n-pentyloxy group, isopentyloxy group, 2-methylbutyloxy group, neopentyloxy group, n-hexyloxy group, 4-methylpentyloxy group, 3-methylpentyloxy group, 2-methylpentyloxy group, 3,3-dimethylbutyloxy group, 1,1-dimethylbutyloxy group, 1,3-dimethylbutyloxy group, 2,3-dimethylbutyloxy group, 1-ethylbutyloxy group, 1-ethyl-2-methyl -Propyloxy group, 1-methyl-1-ethylpropyloxy group, 1-methyl-2-ethyl Propyloxy group, and 2-methyl-1-ethylpropyl group and 2-methyl-2-ethylpropyl group and the like.

In the above formula (I), the C1-C6 alkyloxy C1-C6 alkyl group represented by R ₁ or R ₆ is carbon substituted with a linear or branched alkyloxy having 1 to 6 carbon atoms. This means a linear or branched alkyl group having 1 to 6 numbers. Examples of such C1-C6 alkyloxy C1-C6 alkyl groups include linear and branched groups such as methyloxymethyl group, ethyloxymethyl group, 1-methyloxyethyl, 2-methyloxy Examples include an ethyl group, 1-ethyloxyethyl group, 2-ethyloxyethyl group, t-butyloxymethyl group and the like.

Alternatively, when R ₁ or R ₆ represents a C1-C6 alkyloxy C1-C6 alkyl group, two alkyl chains bonded to both ends of the oxygen atom in the C1-C6 alkyloxy C1-C6 alkyl group are bonded. In addition, a 5-membered ring or a 6-membered ring may be formed including this oxygen atom. Examples of such oxygen-containing 5-membered or 6-membered ring include 2-tetrahydrofurfuryl group, 2-tetrahydropyranyl group, 2-tetrahydrofurfurylmethyl group and the like.

  Specific examples of the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the general formula (I) according to the present invention are illustrated in Table 1.

  In addition, the compound number in following Table 1 is referred also in Table 2-Table 8 mentioned later, an Example, and a test example.

  The aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) of the present invention exhibits excellent herbicidal activity at a low dose, is excellent in selective herbicidal activity between crops and weeds, and is safe for crops. Furthermore, it can be used as a novel herbicidal active ingredient that can be used for a wide range of subjects such as paddy rice and weeds of field crops.

  According to the herbicide of the present invention containing an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I), it is excellent in low dosage against paddy rice and field crop weeds without causing phytotoxicity to the crop. Since it exhibits a herbicidal effect, it is possible to obtain a high-quality crop with high safety.

  In addition, the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the general formula (I) of the present invention exhibits excellent acaricidal activity at a low dose, as shown in Test Examples described later, Moreover, it has excellent safety against the crops described later, and is useful as a novel acaricide active ingredient that can be used for a wide range of subjects such as fruit gardening scenes.

  According to the acaricide of the present invention comprising the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the general formula (I) of the present invention as an active ingredient, fruit orchard horticulture without causing phytotoxicity to crops Because it shows an excellent acaricidal effect at low doses against mites such as scenes, it is possible to obtain a safe and high quality crop.

  (Production Method) The aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the general formula (I) of the present invention is produced by any one of the following <Method A> or <Method B>. can do.

（上記一般式（Ｉ）〜（VIII）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６は、前記の一般式（Ｉ）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６と同様の意味を表す。） <Method A> The method consists of the following four steps.

(R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ in the above general formulas (I) to (VIII) are R ₁ , R ₂ , R ₃ , The same meaning as R ₄ , R ₅ and R ₆ is represented.)

  An outline of the production method of the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) by Method A is as follows. First, in the first step, phenols represented by the general formula (II) (phenols (II)) And α-bromoalkanoic acid esters represented by general formula (III) (α-bromoalkanoic acid esters (III)) in the presence of a base such as potassium tertiary butoxide, Hydrolysis using a base such as sodium hydroxide provides an aryloxyalkanoic acid derivative (aryloxyalkanoic acid derivative (IV)) represented by general formula (IV).

  In the second step, as a), the aryloxyalkanoic acid derivative (IV) obtained in the first step is converted into aminoalcohols (aminoalcohols (V)) represented by the general formula (V) and N, N -Reacting with a condensing agent such as 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate in the presence of a tertiary amine such as diisopropylethylamine, or as b) an aryloxyalkane When the acid derivative (IV) is converted to an acid chloride using an acid chlorinating agent such as oxalyl chloride and then reacted with an amino alcohol (V) in the presence of a base such as sodium hydroxide, the general formula (VI ) -Derived aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivatives (aryloxy-N- (hydrido Kishiarukiru) alkanoic acid amide derivatives (VI)) is obtained.

  In the third step, the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) obtained in the second step is oxidized by using various oxidizing agents, and is represented by the general formula (VII). An aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII)) is obtained.

  In the fourth step, the aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII) obtained in the third step is combined with hydroxylamines (hydroxylamines (VIII)) represented by the general formula (VIII). By reaction, an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) is obtained.

（上記一般式（Ｉ）〜（VIII）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６は、前記の一般式（Ｉ）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６と同様の意味を表す。） A preferred example of these steps will be specifically described.

(R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ in the above general formulas (I) to (VIII) are R ₁ , R ₂ , R ₃ , The same meaning as R ₄ , R ₅ and R ₆ is represented.)

<First Step> In the first step, phenols (II) and α-bromoalkanoic acid esters (III) are first used in an organic solvent such as ethylene glycol dimethyl ether, for example, a base such as potassium tertiary butoxide. After the reaction, the ester moiety is hydrolyzed with a base such as sodium hydroxide in a mixed solvent of an organic solvent such as ethanol and water without any particular purification of the intermediate. The alkanoic acid derivative (IV) is obtained.
Examples of the organic solvent used when the phenol (II) and the α-bromoalkanoic acid ester (III) are reacted in the first step include, in addition to ethylene glycol dimethyl ether, for example, tetrahydrofuran, acetonitrile, N, N— Examples thereof include dimethylformamide and dimethyl sulfoxide. Examples of the base include sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, sodium hydride and the like in addition to potassium tertiary butoxide. Examples of the organic solvent used for hydrolyzing the ester moiety include, in addition to ethanol, methanol, n-propanol, isopropanol, tertiary butanol, tetrahydrofuran, 1,4-dioxane, and the base is water. In addition to sodium oxide, for example, potassium hydroxide and the like can be mentioned. In the above reaction, the amount of α-bromoalkanoic acid ester (III) and base such as potassium tertiary butoxide is 1 to 2 mol, preferably 1 to 1.5 mol, per mol of phenol (II). Used in The reaction is usually performed at a temperature of 20 to 100 ° C, preferably 20 to 60 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours.
When the ester moiety is hydrolyzed, a base such as sodium hydroxide is used in an amount of 1 to 2 equivalents, preferably 1 to 1.5 equivalents. The reaction is usually carried out at a temperature of 10 to 100 ° C, preferably 20 to 60 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours.
The aryloxyalkanoic acid derivative (IV), which is a reaction product of the above reaction, is made, for example, by adding water to the reaction solution containing the derivative (IV) and then acidifying it with hydrochloric acid, sulfuric acid, etc. It is obtained by extracting with an extraction solvent such as ethyl acetate, washing with water and saturated brine, and distilling off the solvent. The obtained target product (aryloxyalkanoic acid derivative (IV)) can be further purified by operations such as column chromatography or recrystallization, if necessary.

<Second Step> In the second step, as a), the aryloxyalkanoic acid derivative (IV) obtained in the first step and the aminoalcohol (V) are, for example, N, N-dimethylformamide or the like. Using a condensing agent such as 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate (BOP) in the presence of a tertiary amine such as N, N-diisopropylethylamine in an organic solvent. The reaction yields an aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI).
Alternatively, as b), the aryloxyalkanoic acid derivative (IV) obtained in the first step is converted into an acid chloride using an acid chlorinating agent such as oxalyl chloride in an organic solvent such as dichloromethane. After that, it is reacted with an aminoalcohol (V) in the presence of a base such as sodium hydroxide without any particular purification to obtain an aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI). .
Examples of the organic solvent used when the aryloxyalkanoic acid derivative (IV) and the amino alcohol (V) are reacted using a condensing agent in the second step include N, N-dimethylformamide, for example, N -Methyl-2-pyrrolidone, tetrahydrofuran, dichloromethane and the like. Examples of the tertiary amine include triethylamine, tri-n-propylamine and the like in addition to N, N-diisopropylethylamine. In addition to 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, 1,3-dicyclohexylcarbodiimide, 1,3-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and the like. In the above reaction, the amino alcohol (V) is used in an amount of 1 to 2 mol, preferably 1 mol, per mol of the aryloxyalkanoic acid derivative (IV). A tertiary amine such as N, N-diisopropylethylamine is used in an amount of 1 to 8 mol, preferably 2 to 4 mol. The condensing agent such as 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate is used in an amount of 1 to 2 mol, preferably 1 to 1.2 mol. The reaction is usually performed at a temperature of 5 to 50 ° C, preferably 20 to 40 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 12 hours.
As b), as the organic solvent used for converting the aryloxyalkanoic acid derivative (IV) into an acid chloride, 1,2-dichloroethane, chloroform, benzene, toluene, xylene and the like can be mentioned in addition to dichloromethane. Examples of the acid chlorinating agent include thionyl chloride, phosphorus trichloride, phosphorus pentachloride and the like in addition to oxalyl chloride. Examples of the organic solvent used when the obtained acid chloride is reacted with amino alcohols (V) include 1,2-dichloroethane, chloroform, tetrahydrofuran, benzene, toluene, xylene and the like in addition to dichloromethane. In some cases, it is used as a mixed solvent with water. Examples of the base used for reacting the acid chloride with amino alcohols (V) include potassium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine, tri-n-propylamine, N, in addition to sodium hydroxide. N-diisopropylethylamine etc. are mentioned. When the aryloxyalkanoic acid derivative (IV) is converted to an acid chloride, the acid chlorinating agent such as oxalyl chloride is used in an amount of 1 to 2 moles, preferably 1 to 1 per mole of the aryloxyalkanoic acid derivative (IV). Used in an amount of 5 moles. When the obtained acid chloride is reacted with the amino alcohol (V), the amino alcohol (V) is used in an amount of 1 to 2 mol, preferably 1 mol, per 1 mol of the acid chloride. A base such as sodium hydroxide is used in an amount of 1 to 2 mol, preferably 1 to 1.5 mol. The reaction is usually performed at a temperature of 0 to 80 ° C, preferably 20 to 60 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 12 hours.
The aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI), which is the reaction product of a) and b) above, is used for the extraction of ethyl acetate, toluene, etc. into the reaction solution containing the derivative (VI), for example. It is obtained by adding a solvent and water, followed by extraction, further washing with water and saturated brine, and distilling off the solvent. The obtained target product (aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI)) can be further purified by operations such as column chromatography or recrystallization, if necessary.

<Third Step> In the third step, the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) obtained in the second step is treated in an organic solvent such as dichloromethane, for example, Dess-Martin. The aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII) is obtained by oxidation using an oxidizing agent such as a reagent.
Examples of the organic solvent used for oxidizing the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) in the third step include 1,2-dichloroethane, chloroform, benzene and the like in addition to dichloromethane. Can be mentioned. In addition to the Dess-Martin reagent, examples of the oxidizing agent include metal oxidizing agents such as manganese dioxide and pyridinium chlorochromate, and Swern oxidizing agents by a combination of dimethyl sulfoxide and oxalyl chloride. In the above reaction, with respect to the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI), an oxidizing agent such as Dess-Martin reagent is used in an amount of 1 to 2 equivalents, preferably 1 to 1.5 equivalents. It is done. The reaction is usually carried out at a temperature of -70 to 60 ° C, preferably 0 to 20 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 12 hours.
The aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII), which is a reaction product of the above reaction, is prepared by adding, for example, an extraction solvent such as toluene or ethyl acetate, water, and the like to the reaction solution containing the derivative (VII). After washing with water, the solvent is distilled off. The obtained target product (aryloxy-N- (formylalkyl) alkanoic acid amide derivative (VII)) can be further purified by operations such as column chromatography or recrystallization, if necessary.

<Fourth Step> In the fourth step, the aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII) obtained in the third step and the hydroxylamine (VIII) are mixed with, for example, methanol. Reaction in an organic solvent yields an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I). As the organic solvent used when the aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII) and hydroxylamines (VIII) are reacted in the fourth step, in addition to methanol, for example, ethanol, tetrahydrofuran, etc. Is mentioned. In the above reaction, the hydroxylamine (VIII) is used in an amount of 1 to 10 mol, preferably 1 to 5 mol, per 1 mol of the aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII). The reaction is usually performed at a temperature of 20 to 80 ° C, preferably 20 to 60 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 12 hours.

  The reaction solution thus obtained contains the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) of the present invention, and the derivative (I) is added to the reaction solution, for example, It is obtained by adding a 5% aqueous sodium hydrogen carbonate solution, followed by extraction with an extraction solvent such as ethyl acetate and toluene, washing with water and saturated brine, and distilling off the solvent. The obtained aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) can be further purified by operations such as column chromatography or recrystallization, if necessary.

（上記一般式（Ｉ）〜（VIII）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６は、前記の一般式（Ｉ）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６と同様の意味を表す。） <Method B> The method consists of the following three steps.

(R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ in the above general formulas (I) to (VIII) are R ₁ , R ₂ , R ₃ , The same meaning as R ₄ , R ₅ and R ₆ is represented.)

An outline of the method for producing the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) by Method B will be described. First, in the first step, α-bromoalkanoic acid bromides and an amino acid represented by the general formula (V) are used. The α-bromoalkanoic acid-N- (hydroxyalkyl) amide obtained by reacting alcohols (V) in the presence of a base such as triethylamine is reacted with phenols (II) in the presence of a base. Then, an aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI)) represented by the general formula (VI) is obtained.
In the second step, the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) obtained in the first step is oxidized with various oxidizing agents, and is represented by the general formula (VII). An aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII)) is obtained.
In the third step, the aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII) obtained in the second step is combined with hydroxylamines (hydroxylamines (VIII)) represented by the general formula (VIII). By reaction, an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) is obtained.

（上記一般式（Ｉ）〜（VIII）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６は、前記の一般式（Ｉ）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６と同様の意味を表す。） Preferable examples of these steps will be described more specifically.

(R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ in the above general formulas (I) to (VIII) are R ₁ , R ₂ , R ₃ , The same meaning as R ₄ , R ₅ and R ₆ is represented.)

<First Step> In the first step, α-bromoalkanoic acid bromide and amino alcohol (V) are obtained by reacting in an organic solvent such as chloroform in the presence of a base such as triethylamine. , Α-bromoalkanoic acid-N- (hydroxyalkyl) amides are reacted with phenols (II) using an organic solvent such as ethylene glycol dimethyl ether with a base such as potassium tertiary butoxide. Oxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) is obtained.
Examples of the organic solvent used when the α-bromoalkanoic acid bromide is reacted with the amino alcohol (V) include dichloromethane, 1,2-dichloroethane, tetrahydrofuran, benzene, toluene, xylene and the like in addition to chloroform. . Examples of the base include tri-n-propylamine, N, N-diisopropylethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like in addition to triethylamine.
When the α-bromoalkanoic acid bromide is reacted with the aminoalcohol (V), the amount of the aminoalcohol (V) is 1 to 2 mol, preferably 1 mol, per mol of the α-bromoalkanoic acid bromide. Used in A base such as triethylamine is used in an amount of 1 to 2 equivalents, preferably 1 to 1.5 equivalents. The reaction is usually performed at a temperature of 0 to 80 ° C, preferably 20 to 60 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 12 hours.
Examples of organic solvents used in the reaction of α-bromoalkanoic acid-N- (hydroxyalkyl) amides with phenols (II) include, for example, tetrahydrofuran, acetonitrile, N, N-dimethyl in addition to ethylene glycol dimethyl ether. Examples include formamide and dimethyl sulfoxide. Examples of the base include sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, sodium hydride and the like in addition to potassium tertiary butoxide. When α-bromoalkanoic acid-N- (hydroxyalkyl) amides are reacted with phenols (II), α-bromoalkanoic acid-N- (hydroxyalkyl) amides per mole of phenols (II) And bases such as potassium tertiary butoxide are each used in an amount of 1 to 2 mol, preferably 1 to 1.5 mol. The reaction is usually performed at a temperature of 20 to 100 ° C, preferably 20 to 60 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours.

<Second Step> In the second step, the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) obtained in the first step is treated with, for example, Dess-Martin in an organic solvent such as dichloromethane. The aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII) is obtained by oxidation using an oxidizing agent such as a reagent.
Examples of the organic solvent used for oxidizing the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) in the second step include 1,2-dichloroethane, chloroform, benzene and the like in addition to dichloromethane. Can be mentioned. In addition to the Dess-Martin reagent, examples of the oxidizing agent include metal oxidizing agents such as manganese dioxide and pyridinium chlorochromate, and Swern oxidizing agents by a combination of dimethyl sulfoxide and oxalyl chloride. In the above reaction, with respect to the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI), an oxidizing agent such as Dess-Martin reagent is used in an amount of 1 to 2 equivalents, preferably 1 to 1.5 equivalents. It is done. The reaction is usually carried out at a temperature of -70 to 60 ° C, preferably 0 to 20 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 12 hours.
The aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII), which is a reaction product of the above reaction, is prepared by adding, for example, an extraction solvent such as toluene or ethyl acetate, water, and the like to the reaction solution containing the derivative (VII). After washing with water, the solvent is distilled off. The obtained target product (aryloxy-N- (formylalkyl) alkanoic acid amide derivative (VII)) can be further purified by operations such as column chromatography or recrystallization, if necessary.

<Third Step> In the third step, the aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII) obtained in the second step and the hydroxylamine (VIII) are mixed with, for example, methanol. Reaction in an organic solvent yields an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I). Examples of the organic solvent used in the reaction of the aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII) with hydroxylamines (VIII) in the third step include, in addition to methanol, for example, ethanol, tetrahydrofuran, etc. Is mentioned. In the above reaction, the hydroxylamine (VIII) is used in an amount of 1 to 10 mol, preferably 1 to 5 mol, per 1 mol of the aryloxy-N- (carbonylalkyl) alkanoic acid amide derivative (VII). The reaction is usually performed at a temperature of 20 to 80 ° C, preferably 20 to 60 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 12 hours.

  The reaction solution thus obtained contains the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) of the present invention, and the derivative (I) is added to the reaction solution, for example, It is obtained by adding a 5% aqueous sodium hydrogen carbonate solution, followed by extraction with an extraction solvent such as ethyl acetate and toluene, washing with water and saturated brine, and distilling off the solvent. The obtained aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) can be further purified by operations such as column chromatography or recrystallization, if necessary.

  Examples of production of the compound (I) of the present invention obtained by the above <Method A> and <Method B> are shown in Examples 1 to 5 described later.

(Herbicide) Next, the herbicide according to the present invention will be described in detail. The herbicide according to the present invention contains an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the above general formula (I) as a herbicidal active ingredient. The aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) of the present invention has excellent herbicidal activity, as shown in the test examples described later, and includes the following weeds and crops: Since it exhibits excellent selective herbicidal activity, it can be used as a herbicide for controlling weeds or as a herbicidal active ingredient of a selective herbicide.

Therefore, the herbicide containing the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) having such characteristics as a herbicidal active ingredient exhibits an excellent herbicidal effect, and weeds between weeds and crops Since the selectivity is also excellent, when the herbicide of the present invention is used, a crop with excellent safety and good quality can be obtained. The herbicide of the present invention is effective, for example, for weeds or broadleaf weeds.
For example, Alopecurus, Avena, Bromus, Cyperus, Cygitus, Digitaria, Echinochloa, Eleocharis, Eleusine, Eleusine Monochoria), Paccum, Paspalum, Pleumum, Phleum, Poa, Sagittaria, Scirpus, Setaria, Johnsongrass (Sorghum).
Broad-leaved weeds include, for example, Abutilon, Amaranthus, Ambrosia, Bidens, Chenopodium, Galium, Ipomoea, Lindernia, Insade (Persicaria) ), Portulaca, Rotala, Stellaria, Viola, Xanthium and the like.
Examples of crops (useful cultivated plants) in the field where the herbicide of the present invention can be applied include barley (Hordeum), rice (Oryza), sugar cane (Saccharum), wheat (Triticum), corn (Zea), etc. Is mentioned. Examples of broad-leaved crops to which the herbicide of the present invention can be applied include peanut (Arachis), sugar beet (Beta), rape (Brassica), soybean (Glycine), cotton (Gossypium), tomato (Lycopersicon) and the like.

Since the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) of the present invention exhibits excellent selective herbicidal activity between weeds and crops as listed above, the derivative (I) The herbicide contained as a herbicidal active ingredient is effective as a selective herbicide between the above weeds and crops.
In addition, it cannot be overemphasized that application of the herbicide of this invention is not limited to the weeds and crops which were illustrated above.

(Acaricide) In addition, according to the acaricide of the present invention containing an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the general formula (I) of the present invention as an active ingredient, crop damage is caused. Therefore, a high-quality crop with high safety can be obtained. The acaricide of the present invention is effective for mites as shown below, for example.
Examples of the ticks include the spider mite (Tetranychus urticae), the Kanzawa spider mite (Tetranychus kanzawai), the citrus spider mite (Panonychus citri), the apple spider mite (Panonychus ulmi), and the red spider mite (Aculops pelekassi).
Examples of crops (useful cultivated plants) to which the acaricide of the present invention can be applied include, for example, apple (Malus), pear (Pyrus), peach (Prunus), mandarin (Citrus), tomato (Lycopersicum), cabbage (Brassica) , Cha (Camellia), Carnation (Dianthus).
The application of the acaricide of the present invention is not limited to the mites and crops exemplified above.

(Formulation) The herbicide or acaricide of the present invention can be used in various dosage forms, and when formulated, its active ingredient, that is, an aryloxy-N- which is an herbicidal active ingredient or acaricide active ingredient. The (oxyiminoalkyl) alkanoic acid amide derivative (I) is mixed with a carrier or diluent and, if necessary, at least one of an additive (eg, a surfactant) and an auxiliary agent by a known method. The herbicide or acaricide obtained in this way can be used in the form of pharmaceutical preparations usually used as agricultural chemicals, such as granules, fine granules, wettable powders, granular wettable powders, emulsions, aqueous solvents , Flowables, tablets, powders, microcapsules, pastes and the like.

  In addition, the herbicide or acaricide of the present invention includes other agricultural chemicals such as fungicides, insecticides, herbicides, acaricides, safeners, plant growth regulators, fertilizers or soil conditioners. They may be used as a mixture or in combination. In particular, when used in combination with other pesticides, the amount of herbicide used can be reduced and labor can be saved, and the application of herbicides (herbicidal spectrum) is expanded by the cooperative action of both agents. In addition, it can be expected to obtain a more powerful effect due to the synergistic action of both drugs. At this time, a plurality of known herbicides and safeners (safeners) can be combined at the same time.

  As a carrier to be used in the formulation, any solid or liquid carrier can be used as long as it is a carrier commonly used for agrochemical formulations. Although such a support | carrier is not limited to a specific thing, Specifically, the following are mentioned. Examples of solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, quartz, calcium carbonate, apatite, white carbon, slaked lime, silica sand, etc.), vegetable powder (soybean Flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, etc.), ammonium sulfate, urea, alumina, silicate, sugar polymer, high dispersibility Examples thereof include silicic acid and waxes.

  Examples of the liquid carrier include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, ethylbenzene, Methyl naphthalene), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, acetic acid) Amyl), acid amides (dimethylformamide, dimethylacetamide, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfo Cides (such as dimethyl sulfoxide), alcohol ethers (such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), aliphatic or alicyclic hydrocarbons (such as n-hexane, cyclohexane), industrial gasoline (petroleum ether, Solvent naphtha) and petroleum fractions (paraffins, kerosene, light oil, etc.).

  In addition, when formulating herbicides or acaricides into emulsions, wettable powders, flowables, etc., various interfaces for emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading, etc. An active agent is blended. Examples of such surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates, polysulfates, and the like. Anionic surfactants such as oxyethylene alkyl alkyl sulfates and aryl sulfonates, cationic amines such as alkyl amines (lauryl amine, stearyl trimethyl ammonium chloride, etc.), polyoxyethylene alkyl amines, carboxylic acids (betaine) Type) and amphoteric surfactants such as sulfate ester salts, but are not limited to these examples. In addition to these, various adjuvants such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, sodium alginate, gelatin, and tragacanth rubber can be used.

  In the herbicide of the present invention, the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) is 0.001 to 95% by weight, preferably 0.01 to 75% by weight, regardless of the dosage form. It is desirable to contain in the range of%. More specifically, generally, when the herbicide is a granule, the derivative (I) is in an amount of 0.01 to 10% by weight, and the herbicide is a wettable powder, a flowable agent, or a dry flowable agent. In the case of a solution or emulsion, the derivative (I) is in an amount of 1 to 75% by weight, and when the herbicide of the present invention is a powder, driftless powder or fine powder, the derivative (I) ) Can be contained in an amount of 0.01 to 5% by weight.

  For example, in the case of granules and flowables, the herbicides prepared in this way are in the range of about 0.3 to 300 g per 10 are as converted amounts of active ingredients on the soil surface, in the soil or in water. What is necessary is just to spread by quantity. In the case of wettable powder, emulsion, etc., dilute with water or an appropriate solvent, and spray the obtained diluted chemical solution in the range of about 0.3 g to 300 g per 10 are as the converted amount of the active ingredient. Good.

  When the compound of the present invention is used as an active ingredient of an acaricide, the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) is added in an amount of 0.1 to 90% by weight, regardless of the dosage form. It is desirable to contain the agrochemical adjuvant in the range of 10 to 99.9% by weight.

  The acaricide prepared in this way can be used as it is, or diluted to a predetermined concentration with a diluent such as water. Application of various preparations containing the compound of the present invention, or dilutions thereof, is usually performed by commonly used application methods such as spraying (for example, spraying, misting, atomizing, dusting, dusting, etc.), soil application (For example, mixing, irrigation, etc.), surface application (for example, application, powder coating, coating, etc.), immersion, poison bait, etc.

  The dosage of the acaricide of the present invention is not particularly limited, the active ingredient concentration, the form of the preparation, the type of target pests and crops, the degree of damage caused by the pests, the application location, the application method, the application timing, the drugs used in combination It can be appropriately selected from a wide range according to various conditions such as the amount and type of fertilizer used. For example, in the case of emulsions, wettable powders and flowables, it is diluted with water or a suitable solvent, and the resulting diluted solution is about 0.001 to 100 g per 10 ares, preferably 0.00. What is necessary is just to spray in the range of about 01-50g.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples at all.

  In the following production examples, examples, and test examples, room temperature refers to about 20 ° C. unless otherwise specified.

  Moreover, the structure determination of the compound in a following example was performed by NMR analysis (JEOL datum Co., Ltd. product JNM-LA300 type | mold nuclear magnetic resonance apparatus).

Synthesis of 2- (3,5-dichlorophenoxy) -N- (1-methoxyimino-2-methylpropan-2-yl) butyric acid amide (Synthesis of Compound No. 1 in Table 1 by <Method A>)
1) Synthesis of 2- (3,5-dichlorophenoxy) butyric acid A 100 ml four-necked flask was equipped with a stirrer, thermometer and Dimroth condenser to prepare a reaction vessel. In this, 5 g (0.031 mol) of 3,5-dichlorophenol was dissolved in 50 ml of 1,2-dimethoxyethane. The solution was cooled to 10 ° C., 4.8 g (0.043 mol) of potassium tert-butoxide was added, and the mixture was returned to room temperature and stirred at the same temperature for 10 minutes. Next, 8.4 g (0.043 mol) of ethyl 2-bromobutyrate was added at room temperature, and the mixture was stirred at 80 ° C. for 2 hours. After completion of the reaction, the reaction mixture was added to 150 ml of water, extracted with 150 ml of diethyl ether, and the organic layer was washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure to obtain an oily crude 2- (3,5-dichlorophenoxy) butyrate product. This crude product was dissolved in 50 ml of ethanol, a solution prepared by dissolving 2.6 g (0.046 mol) of potassium hydroxide in 10 ml of water at room temperature was added, and the mixture was stirred at the same temperature for 3 hours. After completion of the reaction, the reaction mixture was added to 200 ml of water, and concentrated hydrochloric acid was added to adjust to pH 1, followed by extraction with 200 ml of diethyl ether, and the organic layer was washed with 100 ml of saturated brine. The solid obtained by distilling off the solvent under reduced pressure was collected by filtration, washed with hexane, and dried to give 7.1 g of solid 2- (3,5-dichlorophenoxy) butyric acid (yield 93%). )

2) Synthesis of 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide (<Method of second step a)>)
A 50 ml four-necked flask was equipped with a stirrer, thermometer and Dimroth condenser to prepare a reaction vessel. Among these, 5 g (0.02 mol) of 2- (3,5-dichlorophenoxy) butyric acid was dissolved in 30 ml of N, N-dimethylformamide. To this solution, 3.6 g (0.04 mol) of 2-amino-2-methyl-1-propanol and 10.4 g (0.08 mol) of N, N-diisopropylethylamine were sequentially added at room temperature. Next, 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate 10.7 g (0.024 mol) was added at the same temperature, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture was added to 200 ml of water, extracted with 200 ml of ethyl acetate, and the organic layer was washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck), developing solvent toluene: acetone = 8: 1), and oily 2- ( There were obtained 6.3 g (98% yield) of 3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide.

3) Synthesis of 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide (<Method of second step b)>)
A 50 ml four-necked flask was equipped with a stirrer, thermometer and Dimroth condenser to prepare a reaction vessel. In this, 2.5 g (0.01 mol) of 2- (3,5-dichlorophenoxy) butyric acid was dissolved in 30 ml of dichloromethane, 1.9 g (0.015 mol) of oxalyl chloride and a catalytic amount of N, N-dimethylformamide. Were sequentially added at room temperature and stirred at the same temperature for 2 hours. After completion of the reaction, dichloromethane was distilled off under reduced pressure to obtain oily 2- (3,5-dichlorophenoxy) butyric acid chloride as a crude product. Subsequently, another 50 ml four-necked flask was equipped with a stirrer, a thermometer and a Dimroth condenser into a reaction vessel, in which 3.6 g (0.04 mol) of 2-amino-2-methyl-1-propanol and sodium hydroxide were added. 1.2 g (0.03 mol) was dissolved in a mixed solvent of 20 ml of dichloromethane and 10 ml of water. The solution was cooled to 0 ° C., and a solution of the 2- (3,5-dichlorophenoxy) butyric acid chloride crude product obtained previously dissolved in 10 ml of dichloromethane was added dropwise with vigorous stirring. After completion of the dropwise addition, the temperature was returned to room temperature, and the mixture was vigorously stirred at the same temperature for 30 minutes. After completion of the reaction, the dichloromethane layer was separated and washed with saturated brine. Dichloromethane was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck), developing solvent toluene: acetone = 8: 1), and oily 2- ( 3.1 g (yield 97%) of 3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide were obtained.

4) Synthesis of 2- (3,5-dichlorophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide A 50 ml four-necked flask equipped with a stirrer, thermometer and Dimroth condenser Reaction vessel. In this, 1.15 g (3.6 mmol) of 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide was dissolved in 20 ml of dichloromethane, and the mixture was cooled on ice. After adding 2.3 g (5.4 mmol) of Dess-Martin Periodate, the mixture was returned to room temperature and stirred at the same temperature for 1 hour. After completion of the reaction, the reaction mixture was added to 20 ml of 5% aqueous sodium hydrogen carbonate solution and extracted with 100 ml of diethyl ether. The organic layer was washed successively with 50 ml of 5% aqueous sodium thiosulfate solution and 50 ml of saturated brine. The mixture obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck & Co., Inc., developing solvent toluene: ethyl acetate = 12: 1). 1.0 g (yield 87%) of (3,5-dichlorophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide was obtained.

5) Synthesis of 2- (3,5-dichlorophenoxy) -N- (1-methoxyimino-2-methylpropan-2-yl) butyric acid amide A stirrer, thermometer and Dimroth condenser were placed in a 50 ml four-necked flask. A reaction vessel was provided. In this, 1.0 g (3.1 mmol) of 2- (3,5-dichlorophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide was dissolved in 20 ml of methanol, and methoxy at room temperature. Amine hydrochloride (1.3 g, 15.5 mmol) was added, and then the mixture was heated to reflux with stirring for 5 hours. After completion of the reaction, the reaction mixture was returned to room temperature, 20 ml of 5% aqueous sodium hydrogen carbonate solution was added thereto, extracted with 100 ml of ethyl acetate, and the organic layer was washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck & Co., Inc., developing solvent toluene: ethyl acetate = 30: 1). 0.9 g (yield 85%) of (3,5-dichlorophenoxy) -N- (1-methoxyimino-2-methylpropan-2-yl) butyric acid amide was obtained.

Synthesis of 2- (3,5-dichlorophenoxy) -N- [1- (2-propyn-1-yloxy) imino-2-methylpropan-2-yl)] butyric acid amide according to <Method B><Table 1 Synthesis of Compound No. 30>
1) Synthesis of 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide A 300 ml four-necked flask equipped with a stirrer, thermometer and Dimroth condenser Reaction vessel. Among them, 9.3 g (0.11 mol) of 2-amino-2-methyl-1-propanol was dissolved in 100 ml of chloroform, and 11.5 g (0.05 mol) of 2-bromobutyric acid bromide was dissolved in 20 ml of chloroform at 0 ° C. The solution was added dropwise. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour. After completion of the reaction, the chloroform layer was washed successively with 50 ml of water and 50 ml of saturated brine. Chloroform was distilled off under reduced pressure to obtain oily 2-bromo-N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide as a crude product. Subsequently, a 200 ml four-necked flask was equipped with a stirrer, thermometer and Dimroth condenser to make a reaction vessel, in which 5.9 g (0.036 mol) of 3,5-dichlorophenol was added to 80 ml of 1,2-dimethoxyethane. After dissolving, 4.3 g (0.038 mol) of potassium tert-butoxide was added at 10 ° C., the mixture was returned to room temperature and stirred at the same temperature for 10 minutes. Next, 9.0 g (0.038 mol) of 2-bromo-N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide crude product was dissolved in 20 ml of 1,2-dimethoxyethane at the same temperature. After adding the solution, the mixture was stirred at 80 ° C. for 3 hours. After completion of the reaction, the reaction mixture was added to 200 ml of water, extracted with 200 ml of ethyl acetate, and the organic layer was washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck), developing solvent toluene: acetone = 8: 1), and oily 2- ( There was obtained 4.5 g (yield 60%) of 3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide.

2) Synthesis of 2- (3,5-dichlorophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide A 100 ml four-necked flask equipped with a stirrer, thermometer and Dimroth condenser Reaction vessel. In this, 2.3 g (7.2 mmol) of 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide was dissolved in 50 ml of dichloromethane, and the mixture was cooled on ice. After adding 4.6 g (10.8 mmol) of Dess-Martin Periodate, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was added to 50 ml of 5% aqueous sodium hydrogen carbonate solution and extracted with 150 ml of diethyl ether. The organic layer was washed sequentially with 70 ml of 5% aqueous sodium thiosulfate solution and 70 ml of saturated brine. The mixture obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck & Co., Inc., developing solvent toluene: ethyl acetate = 12: 1). 1.8 g (yield 81%) of (3,5-dichlorophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide were obtained.

3) Synthesis of 2- (3,5-dichlorophenoxy) -N- [1- (2-propyn-1-yloxy) imino-2-methylpropan-2-yl)] butyric acid amide in a 50 ml 4-neck flask A reaction vessel equipped with a stirrer, thermometer and Dimroth condenser was used as a reaction vessel, and 1.0 g (3.1 mmol) of 2- (3,5-dichlorophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide Was dissolved in 20 ml of methanol, 1.1 g (15.5 mmol) of propargyloxyamine was added at room temperature, and the mixture was heated to reflux with stirring for 5 hours. After completion of the reaction, the reaction mixture was added to 50 ml of water, extracted with 100 ml of ethyl acetate, and the organic layer was washed with 50 ml of saturated brine. The mixture obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck & Co., Inc., developing solvent toluene: ethyl acetate = 40: 1). 0.9 g (yield 78%) of (3,5-dichlorophenoxy) -N- [1- (2-propyn-1-yloxy) imino-2-methylpropan-2-yl] butyric acid amide was obtained.

Synthesis of 2- (3,5-dichlorophenoxy) -3-methoxy-N- (1-methoxyimino-2-methylpropan-2-yl) propanoic acid amide according to <Method A><Compound No. Synthesis of 14> 1) Synthesis of ethyl 2- (3,5-dichlorophenoxy) -3-methoxypropanoate A 100 ml four-necked flask was equipped with a stirrer, thermometer and Dimroth condenser, and was used as a reaction vessel. 14.5 g (0.056 mol) of ethyl propanoate was dissolved in 60 ml of methanol, 0.1 g of trimethylamine oxide having a catalytic amount was added, and the mixture was cooled to −10 ° C. At the same temperature, a solution of 3.3 g (0.061 mol) of sodium methoxide in 20 ml of methanol was slowly added dropwise, followed by stirring at −5 ° C. for 1 hour. After adding 0.5 g of acetic acid and 50 ml of diethyl ether to the reaction mixture and stirring vigorously, the precipitated inorganic salt was removed by filtration, and the filtrate was concentrated under reduced pressure. The resulting residue was extracted with 100 ml of ethyl acetate and washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure to obtain oily ethyl 2-bromo-3-methoxypropanoate as a crude product.
Subsequently, a 200 ml four-necked flask was equipped with a stirrer, a thermometer, and a Dimroth condenser to make a reaction vessel, and 5.9 g (0.036 mol) of 3,5-dichlorophenol was dissolved in 80 ml of 1,2-dimethoxyethane. After adding 4.3 g (0.038 mol) of potassium tert-butoxide, the mixture was stirred at room temperature for 10 minutes. Next, a solution of 8.0 g (0.038 mol) of crude 2-bromo-3-methoxypropanoate in 20 ml of 1,2-dimethoxyethane was added at the same temperature, and the mixture was stirred at 80 ° C. for 3 hours. did. After completion of the reaction, the reaction mixture was added to 200 ml of water, extracted with 200 ml of diethyl ether, and the organic layer was washed with 50 ml of saturated brine. The mixture obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck), developing solvent hexane: acetone = 50: 1 → 25: 1), oily Of ethyl 2- (3,5-dichlorophenoxy) -3-methoxypropanoate (62% yield).

2) Synthesis of 2- (3,5-dichlorophenoxy) -3-methoxy-N- (1-hydroxy-2-methylpropan-2-yl) propanoic acid amide In a 100 ml four-necked flask, a stirrer, thermometer, A reaction vessel equipped with a Dimroth condenser was used, and 6.5 g (0.022 mol) of ethyl 2- (3,5-dichlorophenoxy) -3-methoxypropanoate was dissolved in 50 ml of methanol, and 1.8 g of sodium hydroxide (0 0.044 mol) in 10 ml of water was added and stirred at the same temperature for 3 hours. After completion of the reaction, the reaction mixture was poured into water and concentrated hydrochloric acid was added to adjust to pH 1, followed by extraction with 200 ml of diethyl ether, and the organic layer was washed with 100 ml of saturated brine. The solid obtained by distilling off the solvent under reduced pressure was collected by filtration, washed with hexane, and dried to obtain 5.4 g of solid 2- (3,5-dichlorophenoxy) -3-methoxypropanoic acid. (93% yield) was obtained.
Subsequently, a 50 ml four-necked flask was equipped with a stirrer, thermometer, and Dimroth condenser and used as a reaction vessel, and 3.0 g (0.011 mol) of 2- (3,5-dichlorophenoxy) -3-methoxypropanoic acid was added to 30 ml of dichloromethane. After dissolution, 1.9 g (0.015 mol) of oxalyl chloride and a catalytic amount of N, N-dimethylformamide were sequentially added at room temperature and stirred at the same temperature for 2 hours. After completion of the reaction, dichloromethane was distilled off under reduced pressure to obtain oily 2- (3,5-dichlorophenoxy) -3-methoxypropanoic acid chloride as a crude product. Subsequently, another 50 ml four-necked flask was equipped with a stirrer, thermometer, and Dimroth condenser to prepare a reaction vessel, and 2.2 g (0.024 mol) of 2-amino-2-methyl-1-propanol and 1.2 g of sodium hydroxide ( 0.03 mol) was dissolved in a mixed solvent of 40 ml of dichloromethane and 20 ml of water. While this solution was cooled to 0 ° C. and vigorously stirred, a solution of the 2- (3,5-dichlorophenoxy) -3-methoxypropanoic acid chloride obtained previously in 10 ml of dichloromethane was added dropwise. After completion of dropping, the mixture was vigorously stirred at room temperature for 30 minutes. After completion of the reaction, the dichloromethane layer was separated and washed with 20 ml of saturated brine. Dichloromethane was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck & Co., Inc., developing solvent toluene: ethyl acetate = 5: 1). There were obtained 3.0 g (81% yield) of (3,5-dichlorophenoxy) -3-methoxy-N- (1-hydroxy-2-methylpropan-2-yl) propanoic acid amide.

3) Synthesis of 2- (3,5-dichlorophenoxy) -3-methoxy-N- (2-methyl-1-propanaldehyde-2-yl) propanoic acid amide A stirrer, thermometer, 2- (3,5-dichlorophenoxy) -3-methoxy-N- (1-hydroxy-2-methylpropan-2-yl) propanoic acid amide 1.0 g (3.0 mmol) as a reaction vessel equipped with a Dimroth condenser Was dissolved in 20 ml of dichloromethane, 1.5 g (3.6 mmol) of Dess-Martin Periodate was added under ice cooling, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was added to 20 ml of 5% aqueous sodium hydrogen carbonate solution and extracted with 100 ml of diethyl ether. The organic layer was washed successively with 50 ml of 5% aqueous sodium thiosulfate solution and 50 ml of saturated brine. The mixture obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck & Co., Inc., developing solvent toluene: ethyl acetate = 10: 1). 0.85 g (yield 85%) of (3,5-dichlorophenoxy) -3-methoxy-N- (2-methyl-1-propanaldehyde-2-yl) propanoic acid amide was obtained.

4) Synthesis of 2- (3,5-dichlorophenoxy) -3-methoxy-N- (1-methoxyimino-2-methylpropan-2-yl) propanoic acid amide A stirrer and thermometer in a 50 ml four-necked flask , A reaction vessel equipped with a Dimroth condenser, and 0.85 g (2.5 mmol) of 2- (3,5-dichlorophenoxy) -3-methoxy-N- (2-methyl-1-propanaldehyde-2-yl) propanoic acid amide ) Was dissolved in 20 ml of methanol, 1.0 g (12.5 mmol) of methoxyamine hydrochloride was added at room temperature, and the mixture was heated to reflux with stirring for 5 hours. After completion of the reaction, 20 ml of 5% aqueous sodium hydrogen carbonate solution was added to the reaction mixture, followed by extraction with 100 ml of ethyl acetate, and the organic layer was washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel Silica gel 60H (trade name, manufactured by Merck & Co., Ltd., developing solvent toluene: ethyl acetate = 20: 1). 0.79 g (yield 85%) of (3,5-dichlorophenoxy) -3-methoxy-N- (1-methoxyimino-2-methylpropan-2-yl) propanoic acid amide was obtained.

Synthesis of 2- (3,5-dibromophenoxy) -N- (1-methoxyimino-2-methylpropan-2-yl) butyric acid amide (Synthesis of <No. 3 in Table 1> by <Method A>)
1) Synthesis of 2- (3,5-dibromophenoxy) butyric acid A four-necked flask with a capacity of 100 ml was equipped with a stirrer, a thermometer and a Dimroth condenser to prepare a reaction vessel. In this, 5.0 g (0.02 mol) of 3,5-dibromophenol was dissolved in 50 ml of 1,2-dimethoxyethane. The solution was cooled to 10 ° C., 3.1 g (0.028 mol) of potassium tert-butoxide was added, and the mixture was returned to room temperature and stirred at the same temperature for 10 minutes. Subsequently, 5.5 g (0.028 mol) of ethyl 2-bromobutyrate was added at room temperature, followed by stirring at 80 ° C. for 2 hours. After completion of the reaction, the reaction mixture was added to 150 ml of water, extracted with 150 ml of diethyl ether, and the organic layer was washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure to obtain crude oily 2- (3,5-dibromophenoxy) butyric acid ethyl product. This crude product was dissolved in 50 ml of ethanol, a solution of 1.7 g (0.03 mol) of potassium hydroxide in 10 ml of water was added at room temperature, and the mixture was stirred at the same temperature for 3 hours. After completion of the reaction, the reaction mixture was added to 200 ml of water, and concentrated hydrochloric acid was added to adjust to pH 1, followed by extraction with 200 ml of diethyl ether, and the organic layer was washed with 100 ml of saturated brine. The solid obtained by distilling off the solvent under reduced pressure was collected by filtration, washed with hexane, and dried to obtain 6.0 g of solid 2- (3,5-dibromophenoxy) butyric acid (yield 90%). )

2) Synthesis of 2- (3,5-dibromophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide (<Method of second step a)>)
A 50 ml four-necked flask was equipped with a stirrer, thermometer and Dimroth condenser to make a reaction vessel. In this, 5.0 g (0.015 mol) of 2- (3,5-dibromophenoxy) butyric acid was dissolved in 30 ml of N, N-dimethylformamide. To this solution, 2.7 g (0.03 mol) of 2-amino-2-methyl-1-propanol and 7.7 g (0.06 mol) of N, N-diisopropylethylamine were sequentially added at room temperature. Next, 8.0 g (0.018 mol) of 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate was added at the same temperature, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture was added to 200 ml of water, extracted with 200 ml of ethyl acetate, and the organic layer was washed with 50 ml of saturated brine. The mixture obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (silica gel: Silica gel 60H (trade name, manufactured by Merck & Co., Ltd., developing solvent toluene: acetone = 10: 1). 5.7 g (yield 95%) of (3,5-dibromophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide was obtained.

3) Synthesis of 2- (3,5-dibromophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide (<method of second step b)>)
A 50 ml four-necked flask was equipped with a stirrer, thermometer and Dimroth condenser to make a reaction vessel. In this, 2.5 g (7.4 mmol) of 2- (3,5-dibromophenoxy) butyric acid was dissolved in 30 ml of dichloromethane, 1.4 g (11.1 mmol) of oxalyl chloride and a catalytic amount of N, N-dimethylformamide. Were sequentially added at room temperature and stirred at the same temperature for 2 hours. After completion of the reaction, dichloromethane was distilled off under reduced pressure to obtain oily 2- (3,5-dibromophenoxy) butyric acid chloride as a crude product. Subsequently, another 50 ml four-necked flask was equipped with a stirrer, a thermometer and a Dimroth condenser into a reaction vessel, in which 1.3 g (14.8 mmol) of 2-amino-2-methyl-1-propanol and sodium hydroxide were added. 0.9 g (22.2 mmol) was dissolved in a mixed solvent of 20 ml of dichloromethane and 10 ml of water. The solution was cooled to 0 ° C., and a solution prepared by dissolving the 2- (3,5-dibromophenoxy) butyric acid chloride crude product obtained previously in 10 ml of dichloromethane was added dropwise with vigorous stirring. After completion of the dropwise addition, the temperature was returned to room temperature, and the mixture was vigorously stirred at the same temperature for 30 minutes. After completion of the reaction, the dichloromethane layer was separated and washed with saturated brine. Dichloromethane was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel: Silica gel 60H (trade name, manufactured by Merck), developing solvent: toluene: acetone = 10: 1). 2.9 g (95% yield) of-(3,5-dibromophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide was obtained.

4) Synthesis of 2- (3,5-dibromophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide A stirrer, thermometer and Dimroth condenser were equipped in a 50 ml four-necked flask. Reaction vessel. In this, 1.2 g (2.9 mmol) of 2- (3,5-dibromophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butyric acid amide was dissolved in 20 ml of dichloromethane, and the mixture was cooled on ice. After adding 1.9 g (4.4 mmol) of Dess-Martin Periodate, the mixture was returned to room temperature and stirred at the same temperature for 1 hour. After completion of the reaction, the reaction mixture was added to 20 ml of 5% aqueous sodium hydrogen carbonate solution and extracted with 100 ml of diethyl ether. The organic layer was washed successively with 50 ml of 5% aqueous sodium thiosulfate solution and 50 ml of saturated brine. The solvent was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel: Silica gel 60H (trade name, manufactured by Merck & Co., Inc., developing solvent: toluene: ethyl acetate = 15: 1). 1.0 g (yield 85%) of 2- (3,5-dibromophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide was obtained.

5) Synthesis of 2- (3,5-dibromophenoxy) -N- (1-methoxyimino-2-methylpropan-2-yl) butyric acid amide A stirrer, thermometer and Dimroth condenser were placed in a 50 ml four-necked flask. A reaction vessel was provided. In this, 1.0 g (2.5 mmol) of 2- (3,5-dibromophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide was dissolved in 20 ml of methanol, and methoxy at room temperature. Amine hydrochloride (1.0 g, 12.5 mmol) was added, and then the mixture was heated to reflux with stirring for 5 hours. After completion of the reaction, the reaction mixture was returned to room temperature, 20 ml of 5% aqueous sodium hydrogen carbonate solution was added thereto, extracted with 100 ml of ethyl acetate, and the organic layer was washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel: Silica gel 60H (trade name, manufactured by Merck & Co., Ltd., developing solvent: toluene: ethyl acetate = 40: 1). 0.9 g (yield 85%) of 2- (3,5-dibromophenoxy) -N- (1-methoxyimino-2-methylpropan-2-yl) butyric acid amide was obtained.

Synthesis of 2- (3,5-dichlorophenoxy) -N- [1- (2-propen-1-yloxy) imino-2-methylpropan-2-yl)] butyric acid amide (<Compound No. 29 in Table 1) > Synthesis)
A 50 ml four-necked flask was equipped with a stirrer, thermometer and Dimroth condenser to make a reaction vessel. Among these, 1.0 g (3.1 mmol) of 2- (3,5-dichlorophenoxy) -N- (2-methyl-1-propanaldehyde-2-yl) butyric acid amide synthesized by 4) of Example 1 was used. ) Was dissolved in 20 ml of methanol, 1.1 g (15.5 mmol) of allyloxyamine was added at room temperature, and the mixture was heated to reflux with stirring for 5 hours. After completion of the reaction, the reaction mixture was added to 50 ml of water, extracted with 100 ml of ethyl acetate, and the organic layer was washed with 50 ml of saturated brine. The solvent was distilled off under reduced pressure, and the resulting mixture was purified by silica gel column chromatography (silica gel: Silica gel 60H (trade name, manufactured by Merck & Co., Inc., developing solvent: toluene: ethyl acetate 40: 1). -(3,5-dichlorophenoxy) -N- [1- (2-propen-1-yloxy) imino-2-methylpropan-2-yl)] butyric acid amide 0.9 g (yield 78%) was obtained. .

Tables 2 to 3 show the ¹ H-NMR analysis results of the compounds of the general formula (I) of the present invention produced according to Examples 1 to 5 above.

[Manufacture of herbicides or acaricides]
Furthermore, a method for formulating the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) of the present invention as a herbicide is described in Examples 6 to 11 below as a method for formulating it as an acaricide. This will be described more specifically as Example 12. However, the herbicide or the acaricide of the present invention is not limited to these Examples 6 to 12, but can be formulated by mixing with other various additives at an arbitrary ratio. Not too long.

  The compound numbers are those shown in Table 1, and in the following examples, “parts” are all parts by weight.

(Granule) No. 15 parts of water was added to 1 part of 1 compound, 1 part of calcium lignin sulfonate, 1 part of lauryl sulfate, 30 parts of bentonite and 67 parts of talc, kneaded with a kneader, and granulated with an extrusion granulator. This was dried with a fluid dryer to obtain granules containing 1% of a herbicidal active ingredient (Compound No. 1).

(Flowable agent) No. No. 9 compound 20.0 parts, sulfo-2-succinic acid di-2-ethylhexyl ester sodium salt 2.0 parts, polyoxyethylene nonylphenyl ether 2.0 parts, propylene glycol 5.0 parts, antifoaming agent 0.5 parts and water 70.5 parts was uniformly mixed and pulverized by a wet ball mill to obtain a flowable agent containing 20% of a herbicidal active ingredient (Compound No. 9).

(Dry flowable agent) No. No. 10 compound, 75 parts, isoban no. 1 [anionic surfactant: manufactured by Kuraray Isoprene Chemical Co., Ltd., trade name] 10 parts, Vanillex N [anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd., trade name] 5 parts, white carbon 5 parts, 5 parts of clay was uniformly mixed and pulverized to obtain a dry flowable (granular hydration) agent containing 75% of the herbicidal active ingredient (Compound No. 10).

(Wetting agent) No. Nineteen compounds of 15 parts, 15 parts of white carbon, 3 parts of calcium lignin sulfonate, 2 parts of polyoxyethylene nonylphenyl ether, 5 parts of diatomaceous earth and 60 parts of clay were mixed uniformly by a pulverizer and mixed, Compound No. 19) A wettable powder containing 15% is obtained.

(Emulsion) No. 36 parts of Compound 36, Solpol 700H [Emulsifier, trade name, manufactured by Toho Chemical Co., Ltd.] and 60 parts of xylene were mixed to obtain an emulsion containing 20% of a herbicidal active ingredient (Compound No. 36).

(Dust) No. 26 parts of compound No. 26, 0.5 parts of white carbon, 0.5 part of calcium stearate, 50.0 parts of clay and 48.5 parts of talc were uniformly mixed and ground to obtain a herbicidal active ingredient (Compound No. 26). A powder containing 0.5% was obtained.

(Emulsion) No. 10 parts of 30 compounds, 45 parts of 1,2-dimethyl-4-ethylbenzene, 35 parts of N-methyl-2-pyrrolidone and 10 parts of Solpol 3005X (trade name of surfactant manufactured by Toho Chemical Co., Ltd.) An emulsion containing 10% of an acaricidal active ingredient was obtained.

  All of the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivatives (I) represented by the general formula (I) are prepared in various dosage forms according to the preparation examples shown in Examples 6 to 12 above. Can be formulated.

  Next, Test Examples 1 to 5 are shown to illustrate the herbicidal effect and the acaricidal effect of the aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative (I) of the present invention.

<Test example 1> Herbicidal effect test by paddy rice soil treatment and phytotoxicity test for transplanted paddy rice Paddy field soil is filled in a 1 / 5,000 are wide Wagner pot, and water is added to a chemical fertilizer (N: P: K = 17:17:17) was mixed and scribing was performed. Thereafter, 30 seeds of Tainubier, broad-leaved weeds (Azena, Kogi), and firefly seeds were sown at a depth of 0 to 1 cm. Immediately after sowing, a two-leaf stage rice was transplanted. Immediately after transplanting rice, the water depth was kept at about 3 cm. Subsequent management was performed in a glass greenhouse. One day after rice transplantation, the wettable powder prepared according to Example 9 was diluted with water using the compounds shown in Table 4 below, and a predetermined amount of the water-diluted drug solution was added dropwise. When the application amount of the active ingredient was converted, it corresponded to 120 g or 30 g per 10 ares.
This test was carried out in two consecutive units per chemical solution concentration group, and the herbicidal rate (%) was determined by the following formula (Equation 1) 21 days after drug treatment.

オランダ出願公開第７２０７９７１号明細書に記載。

ベルギー特許第８５０１５４号明細書に記載。 The results are shown in Table 4 below.
In addition, the compound numbers in Table 4 are the same as those shown in Tables 1 to 3 above. Moreover, the wettable powder containing the comparison compound (E) and the comparison compound (F) which are shown by a following formula as a comparison chemical | medical agent was prepared according to Example 9, and the test was implemented similarly. The results are shown in Table 4. The comparative compound (E) and the comparative compound (F) used as the comparative agents are compounds represented by the following formulas (E) and (F), respectively.

It is described in the Dutch application publication No. 7207971.

Described in Belgian Patent No. 850154.

<Test example 2> Herbicidal effect test by paddy rice growing season treatment 1 / 5,000 are wide Wagner pot is filled with paddy field soil, water is added and chemical fertilizer (N: P: K = 17: 17: 17) ) Was mixed, and scavenging was performed. Thereafter, 30 seeds of Tainubier, broad-leaved weeds (Azena, Kogi), and firefly seeds were sown at a depth of 0 to 1 cm. Immediately after sowing, the water was submerged and the water depth was kept at about 3 cm. Subsequent management was performed in a glass greenhouse. Seven days after sowing, the wettable powder prepared according to Example 9 was diluted with water using the compounds shown in Table 5 below, and a predetermined amount of the water-diluted drug solution was added dropwise. When the application amount of the active ingredient was converted, it corresponded to 120 g or 30 g per 10 ares. The test was carried out in a two-ream system per chemical solution concentration group, and the herbicidal rate (%) was obtained from the formula (Equation 1) 21 days after the drug treatment. The results are shown in Table 5.

<Test Example 3> Herbicidal effect test and phytotoxicity test by field soil treatment 1) Herbicidal effect test for field crop weeds Field soil (alluvial loam) is packed in an unglazed pot with a size of 1/5000 are, and 1 cm surface soil and bark beetle 50 seeds each of Enocologosa, Shiroza and Inutade were mixed uniformly, and the surface layer was lightly pressed. One day after sowing, the emulsion prepared according to Example 10 was diluted with water using the compounds shown in Table 6 below, and the water-diluted drug solution was sprayed on the soil surface at a rate of 100 liters per 10 ares. When the application amount of the active ingredient was converted, it corresponded to 120 g or 30 g per 10 ares. The herbicidal effect was evaluated according to the same criteria as in Test Example 1 21 days after the drug treatment. The results are shown in Table 6.

2) Phytotoxicity test for crops Cultivate field soil (alluvial loam soil) in an unglazed pot with a size of 1 / 10,000 are and sow seeds of each crop (5 soybeans, 10 wheats) in separate pots. The surface layer was lightly pressed. One day after sowing, the emulsion prepared according to Example 10 was diluted with water using the compounds shown in Table 6 below, and the water-diluted drug solution was sprayed on the soil surface at a rate of 100 liters per 10 ares. When the application amount of the active ingredient was converted, it corresponded to 120 g or 30 g per 10 ares. The test was carried out in a two-ream system per chemical solution concentration group, and the herbicidal rate (%) was obtained from the formula (Equation 1) 21 days after the drug treatment. The results are shown in Table 6.

<Test Example 4> Herbicidal effect test and phytotoxicity test by field foliage treatment 1) Herbicidal effect test on field weeds Field soil (alluvial loam) is packed in an unglazed pot with a size of 1/5000 are, and 1 cm surface soil and bark 50 seeds each of Enocologosa, Shiroza and Inutade were mixed uniformly, and the surface layer was lightly pressed. Seven days after sowing, using the compounds shown in Table 7 below, the emulsion prepared according to Example 10 was diluted with water, and the water diluted chemical solution was sprayed on the soil surface at a rate of 100 liters per 10 ares. When the application amount of the active ingredient was converted, it corresponded to 120 g or 30 g per 10 ares. The herbicidal effect was evaluated according to the same criteria as in Test Example 1 21 days after the drug treatment. The results are shown in Table 7.

2) Phytotoxicity test for crops Cultivate field soil (alluvial loam soil) in an unglazed pot with a size of 1 / 10,000 are and sow seeds of each crop (5 soybeans, 10 wheats) in separate pots. The surface layer was lightly pressed. Seven days after sowing, the emulsion prepared according to Example 10 was diluted with water using the compounds shown in Table 7 below, and the water-diluted drug solution was sprayed on the plants at a rate of 100 liters per 10 ares. When the application amount of the active ingredient was converted, it corresponded to 120 g or 30 g per 10 ares. The test was carried out in a two-ream system per chemical solution concentration group, and the herbicidal rate (%) was obtained from the formula (Equation 1) 21 days after the drug treatment. The results are shown in Table 7.

<Test Example 5> Tick-killing test against spider mite Ten adult female spider mites were released on each of the seedlings grown in plastic cups. One day after the release, the kidney seedlings were placed on a turntable, and a sufficient amount of an emulsion diluted solution (containing an active compound equivalent to 200 ppm) prepared according to the preparation example was sprayed with a spray gun. After the treatment, it was placed in a constant temperature room at 25 ° C. (16 hours illumination), the number of female adults parasitized 8 days after the treatment was examined, and the control value (%) was calculated by the following formula 2.
This test was carried out in two consecutive systems, and the results are shown in Table 8.
Moreover, in this test, no phytotoxicity was observed on the kidney seedlings.

（米国特許第４１１７１６６号明細書に記載） The comparative compound (G) is a known compound shown below and was tested according to the compound of the present invention.

(Described in US Pat. No. 4,117,166)

Claims (3)

Aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivatives represented by general formula (I).

[Wherein, X represents a halogen atom, a C1-C6 alkyl group or a C1-C6 halogenated alkyl group, and R ₁ represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group or a C1-C6 alkyl group. Represents an oxy C1-C6 alkyl group, R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a C1-C6 alkyl group, and R ₆ represents a hydrogen atom, a C1-C6 alkyl group, C3 -C6 alkenyl group, C3-C6 alkynyl group, C1-C6 alkyloxy C1-C6 alkyl group, C1-C6 halogenated alkyl group or benzyl group, one or both of R ₁ and R ₆ are C1-C6 alkyloxy When representing a C1-C6 alkyl group, each independently represents an oxygen atom in the C1-C6 alkyloxy C1-C6 alkyl group. Two alkyl chains that are bonded to both ends of each other may be bonded to form a 5-membered or 6-membered ring including this oxygen atom, n is an integer of 0 to 5, and n is 2 In these cases, each X may be the same or different. ]   A herbicide comprising an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the general formula (I) according to claim 1 as a herbicidal active ingredient.   An acaricide which comprises an aryloxy-N- (oxyiminoalkyl) alkanoic acid amide derivative represented by the general formula (I) according to claim 1 as an acaricide active ingredient.