JP2007182404A - Aryloxy-n-(alkoxyalkyl)alkanoic acid amide derivative and herbicide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new aryloxy-N-(alkoxyalkyl)alkanoic acid amide derivative exhibiting excellent herbicidal activities even with a little amount, having excellent selective herbicidal activities of crops and weeds, and usable for wide targets such as the weeds of paddy rice and field crop; and to provide a herbicide containing the derivative. <P>SOLUTION: The aryloxy-N-(alkoxyalkyl)alkanoic acid amide derivative is represented by general formula (I). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative and a herbicide containing it as a herbicidal 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, Herbicides having various structures such as urea, acid amide, heterocyclic, phenol, diphenyl ether, and pyridinium have been proposed or put into practical use.

［式（Ａ）中、Ｒ₁およびＲ₂は、独立にハロゲン原子またはＣ1〜Ｃ4アルキル基を示し、Ｒ₃はＣ1〜Ｃ4アルキル基を示し、Ｒ₄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、Ｒ₁およびＲ₂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、Ｒ₃はＣ1〜Ｃ4アルキル基を示し、Ｒ₄およびＲ₅は水素原子または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。）。
また、上記のアリールオキシアルカン酸アミド誘導体には、殺ダニ活性を示すものも知られている。
（３）一般式（Ｃ）

［式（Ｃ）中、Ｘは、フッ素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、Ｒ₁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Ｒ₃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Ｒ₃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。）。
オランダ特許第７２０７９７１号 ベルギー特許第８５０１５４号 米国特許第３９７１８５０号明細書 Among these, examples of the acid amide herbicide include aryloxyalkanoic acid amide derivatives, and the compounds described in the following publications have been known so far.
(1) General formula (A)

[In the formula (A), R ₁ and R ₂ independently 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 the 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, R ₄ and R ₅ represent a hydrogen atom or C1- A C3 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 2).
In addition, among the above aryloxyalkanoic acid amide derivatives, those showing acaricidal activity are also known.
(3) General formula (C)

[In formula (C), X represents a fluorine 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 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).
Dutch Patent No. 7207971 Belgian Patent No. 850154 US Pat. No. 3,971,850

  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.

  The present invention is intended to solve the above-described problems, and exhibits excellent herbicidal activity even at a low dose, is excellent in selective herbicidal activity between crops and weeds, and is also suitable for paddy rice and field crops. It is an object of the present invention to provide a novel aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative and a herbicide containing the same, which can be used for a wide range of subjects such as weeds.

［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、Ｒ_５およびＲ_６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_７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あるいはＲ_７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員環または６員環を形成していてもよく、ｎは、０ないし５の整数を示し、ｎが２以上のときはそれぞれのＸは、同一または相異なっていてもよい。］で表されることを特徴としている。 As a result of diligent studies to solve the above problems, the present inventors have found that the compound represented by the following general formula (I) does not cause phytotoxicity to crops and has a low dosage for paddy rice and field crop weeds. The present invention was completed by finding an excellent herbicidal effect. That is, the aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative according to the present invention has 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 , R ₅ and R ₆ each independently represent a hydrogen atom or a C1-C6 alkyl group, and R ₇ represents a hydrogen atom, a C1-C6 alkyl group Group, C3-C6 alkenyl group, C3-C6 alkynyl group, C1-C6 alkyloxy C1-C6 alkyl group, C1-C6 halogenated alkyl group or benzyl group, R ₁ or R ₇ is C1-C6 alkyloxy When showing a C1-C6 alkyl group, it is each independently the both ends of the oxygen atom in a C1-C6 alkyloxy C1-C6 alkyl group. Two bonded alkyl chains may be bonded 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 Sometimes each X may be the same or different. It is characterized by being represented.

  The herbicide according to the present invention is characterized by containing an aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative represented by the above general formula (I) as a herbicidal active ingredient.

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

In general formula (I), the C1-C6 alkyl group represented by X, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ or R ₇ is a straight chain having 1 to 6 carbon atoms. Or it means a branched 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, 3,3-dimethylbutyl group, 1,1-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 1-ethyl-2-methyl-propyl group, 1-methyl-1-ethylpropyl group, 1,2-dimethylbutyl group, Examples include 2-methyl-1-ethylpropyl group and 2,2-dimethylbutyl group.

In general formula (I), the C1-C6 halogenated alkyl group represented by X or R ₇ 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. Or it means a branched alkyl group. 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 general formula (I), the C3-C6 alkenyl group represented by R ₇ means a linear 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 general formula (I), the C3 to C6 alkynyl group represented by R ₇ 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 general 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 general formula (I), the C1-C6 alkyloxy C1-C6 alkyl group represented by R ₁ or R ₇ 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, it means an alkyloxyalkyl group in which two alkyl chains bonded to both ends of an oxygen atom are bonded to form a 5- or 6-membered ring including the oxygen atom. Examples of the alkyloxyalkyl group forming a 5- or 6-membered ring including an oxygen atom include a 2-tetrahydrofuryl group, a 2-tetrahydropyranyl group, and the like.

Specific examples of the aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivatives represented by the general formula (I) according to the present invention are illustrated in Tables 1-2.
In addition, the compound numbers in the following Tables 1-2 are referred also in the Example and test example which are mentioned later.

  The aryloxy-N- (alkoxyalkyl) 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 suitable for crops and livestock. It is highly safe and can be used as a novel herbicidal active ingredient that can be used for a wide range of subjects such as paddy rice and weed crops. According to the herbicide of the present invention containing the aryloxy-N- (alkoxyalkyl) 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 shows a herbicidal effect, it is possible to obtain a high-quality crop with high safety.

（上記した一般式（Ｉ）〜（VI）中のＸ、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇およびｎは、前記一般式（Ｉ）中と同様の意味を示す。）
アリールオキシ−Ｎ−（アルコキシアルキル）アルカン酸アミド誘導体（Ｉ）の製法について概説すると、まず、第一工程では、一般式（II）で示されるフェノール類（フェノール類（II））と、一般式（III）で示されるα−ブロモアルカン酸エステル類（α−ブロモアルカン酸エステル類（III））を、カリウムｔ−ブトキシドなどの塩基の存在下に反応させたのち、エステル部分を水酸化ナトリウムなどの塩基を用いて加水分解すると、一般式（IV）で示されるアリールオキシアルカン酸誘導体（アリールオキシアルカン酸誘導体（IV））が得られる。
第二工程では、ａ）として、第一工程で得られたアリールオキシアルカン酸誘導体（IV）を、一般式（Ｖ）で示されるアミノアルコール類（アミノアルコール類（Ｖ））と、Ｎ，Ｎ−ジイソプロピルエチルアミンなどの３級アミンの存在下、１Ｈ−ベンゾトリアゾール−１−イルオキシトリス（ジメチルアミノ）ホスホニウムヘキサフルオロホスファートなどの縮合剤を用いて反応させるか、あるいは、ｂ）としてアリールオキシアルカン酸誘導体（IV）をオキサリルクロリドなどの酸クロル化剤を用いて酸塩化物としたのち、水酸化ナトリウムなどの塩基の存在下にアミノアルコール類（Ｖ）と反応させると、一般式（VI）で示されるアリールオキシ−Ｎ−（ヒドロキシアルキル）アルカン酸アミド誘導体（アリールオキシ−Ｎ−（ヒドロキシアルキル）アルカン酸アミド誘導体（VI））が得られる。
第三工程では、第二工程で得られたアリールオキシ−Ｎ−（ヒドロキシアルキル）アルカン酸アミド誘導体（VI）の水酸基を、種々のアルキル化剤を用いてアルキル化することで、一般式（Ｉ）で示されるアリールオキシ−Ｎ−（アルコキシアルキル）アルカン酸アミド誘導体（アリールオキシ−Ｎ−（アルコキシアルキル）アルカン酸アミド誘導体（Ｉ））が得られる。 The aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative represented by the general formula (I) of the present invention can be produced by the following method.

(X, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and n in the general formulas (I) to (VI) are the same as those in the general formula (I). Show meaning.)
The production process of the aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative (I) will be outlined. First, in the first step, the phenols represented by the general formula (II) (phenols (II)) and the general formula After reacting the α-bromoalkanoic acid ester represented by (III) (α-bromoalkanoic acid ester (III)) in the presence of a base such as potassium t-butoxide, the ester moiety is converted to sodium hydroxide or the like. Hydrolysis using a base of the above yields an aryloxyalkanoic acid derivative (aryloxyalkanoic acid derivative (IV)) represented by the 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 An acid derivative (IV) is converted into an acid chloride using an acid chlorinating agent such as oxalyl chloride and then reacted with an aminoalcohol (V) in the presence of a base such as sodium hydroxide. Aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivatives represented by formula (Aryloxy-N- (hydroxy) Alkyl) alkanoic acid amide derivatives (VI)) is obtained.
In the third step, the hydroxyl group of the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) obtained in the second step is alkylated using various alkylating agents to obtain a compound represented by the general formula (I An aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative (aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative (I)) is obtained.

(上記した一般式（Ｉ）〜（VI）中のＸ、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇およびｎは、前記一般式（Ｉ）中と同様の意味を示す。） Preferred examples of these steps will be described more specifically below.

(X, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and n in the general formulas (I) to (VI) are the same as those in the general formula (I). Show meaning.)

<First step>
In the first step, phenols (II) and α-bromoalkanoic acid esters (III) are first reacted in an organic solvent such as ethylene glycol dimethyl ether using a base such as potassium t-butoxide. The aryloxyalkanoic acid derivative (IV) can be obtained by hydrolyzing the ester moiety in a mixed solvent of an organic solvent such as ethanol and water using a base such as sodium hydroxide without any particular purification of the intermediate. Have gained.

  Examples of the organic solvent used when the phenol (II) and the α-bromoalkanoic acid ester (III) are reacted in the first step include, for example, tetrahydrofuran, acetonitrile, N, N-dimethyl in addition to ethylene glycol dimethyl ether. Examples include formamide and dimethyl sulfoxide. In addition to potassium t-butoxide, examples of the base include sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, and sodium hydride. Examples of the organic solvent used for hydrolyzing the ester moiety include, in addition to ethanol, methanol, n-propanol, isopropanol, t-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 bases such as α-bromoalkanoic acid esters (III) and potassium t-butoxide are each in an amount of 1 to 2 equivalents, preferably 1 to 1.5 equivalents, per mole of phenols (II). Used. 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 amino alcohol (V) are mixed in an organic solvent such as N, N-dimethylformamide, for example, Reaction with 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 An oxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) is obtained.

  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. Without any particular purification, it is reacted with an amino alcohol (V) in the presence of a base such as sodium hydroxide to obtain an aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI).

  In the second step a), the organic solvent used when the aryloxyalkanoic acid derivative (IV) and aminoalcohol (V) are reacted using a condensing agent is not limited to N, N-dimethylformamide. For example, N-methyl-2-pyrrolidone, tetrahydrofuran, dichloromethane, chloroform and the like can be mentioned. 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 equivalents, preferably 1 equivalent, per mole of the aryloxyalkanoic acid derivative (IV). A tertiary amine such as N, N-diisopropylethylamine is used in an amount of 1 to 8 equivalents, preferably 2 to 4 equivalents. A condensing agent such as 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate is used in an amount of 1 to 2 equivalents, preferably 1 to 1.2 equivalents. 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.

  In b), the organic solvent used for the reaction in which the aryloxyalkanoic acid derivative (IV) is an acid chloride includes 1,2-dichloroethane, chloroform, benzene, toluene, xylene and the like 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 in reacting the obtained acid chloride 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. Bases used for reacting acid chlorides with amino alcohols (V) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine, tri-n-propylamine, N, N-diisopropylethylamine etc. are mentioned. In the reaction for converting the aryloxyalkanoic acid derivative (IV) to an acid chloride, the acid chlorinating agent such as oxalyl chloride is used in an amount of 1 to 2 equivalents, preferably 1-1. Used in an amount of 5 equivalents. 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 equivalents, preferably 1 equivalent, per mole of the acid chloride. 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 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 a reaction product of the above a) or b), can be used, for example, for extracting ethyl acetate, toluene, etc. into the reaction solution containing the derivative (VI) 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.

  As the amino alcohols (V), commercially available products can be used, or synthesized with reference to British Patent No. 1363068.

<Third step>
In the third step, the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) obtained in the second step is alkylated under acidic or basic conditions to produce aryloxy- N- (alkoxyalkyl) alkanoic acid amide derivative (I) is obtained. Under acidic conditions, aryloxy-N- (alkoxyalkyl) alkanoic acid is reacted with an alkylating agent such as 2,3-dihydrofuran in the presence of an acid catalyst such as hydrochloric acid in an organic solvent such as dichloromethane. An amide derivative (I) is obtained. For basic conditions, aryloxy-N- (alkoxyalkyl) alkanes can be obtained by alkylation in an organic solvent such as tetrahydrofuran, for example, using sodium hydride as the base and alkyl halide as the alkylating agent. The acid amide derivative (I) is obtained.

  Examples of the organic solvent used for alkylating the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) under acidic conditions in the third step include, for example, 1,2-dichloroethane, in addition to dichloromethane. Examples include chloroform, tetrahydrofuran, diethyl ether and the like. In addition to hydrochloric acid, examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, and the like. Examples of the alkyl agent include alkylating agents such as ethyl vinyl ether and 3,4-dihydro-2H-pyran in addition to 2,3-dihydrofuran. In the above reaction, the amount of the acid catalyst such as hydrochloric acid is 0.01 to 1 equivalent, preferably 0.05 to 0.5 equivalent, per mole of the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI). Used in The alkylating agent such as 2,3-dihydrofuran is used in an amount of 1 to 10 equivalents, preferably 2 to 5 equivalents. The reaction is usually performed at a temperature of -70 to 60 ° C, preferably 0 to 40 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 15 minutes to 6 hours.

  On the other hand, as the organic solvent used for alkylating the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) under basic conditions in the third step, other than tetrahydrofuran, for example, 1, 4 -Dioxane, diethyl ether, dichloromethane, 1,2-dichloroethane, chloroform, benzene, toluene, N, N-dimethylformamide and the like. Examples of the base include sodium hydride, triethylamine, N, N-diisopropylethylamine, potassium carbonate, and the like. Examples of the alkyl halide include alkylating agents such as methyl iodide, chloromethyl methyl ether, and propargyl bromide. In the above reaction, a base such as sodium hydride is used in an amount of 1 to 3 equivalents, preferably 1 to 2.5 equivalents per mole of aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI). . The alkylating agent such as methyl iodide is used in an amount of 1 to 4 equivalents, preferably 1 to 3 equivalents. 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- (alkoxyalkyl) alkanoic acid amide derivative (I), which is a reaction product of the above reaction, is prepared by adding, for example, an extraction solvent such as toluene and ethyl acetate, water, and the like to the reaction solution containing the derivative (I). Is added, and the mixture is separated, and the extract is washed with saturated brine, and then the solvent is distilled off. The obtained target product (aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative (I)) can be further purified by operations such as column chromatography or recrystallization, if necessary.

About this invention compound (I) obtained by said method, the manufacture example (3rd process) from aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative (VI) was shown in Examples 1-4 mentioned later. .
The production method (first step and second step) of the aryloxy-N- (hydroxyalkyl) alkanoic acid amide derivative (VI) is shown in Reference Production Example 1.

<Herbicide>
Next, the herbicide according to the present invention will be specifically described. The herbicide according to the present invention contains an aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative represented by the above general formula (I) as a herbicidal active ingredient. The aryloxy-N- (alkoxyalkyl) 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- (alkoxyalkyl) alkanoic acid amide derivative (I) having such characteristics as a herbicidal active ingredient exhibits an excellent herbicidal effect, and selection of weeds and crops. Therefore, when the herbicide of the present invention is used, a crop with excellent safety and 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- (alkoxyalkyl) alkanoic acid amide derivative (I) of the present invention exhibits excellent selective herbicidal activity between the above-mentioned weeds and crops, the derivative (I) is herbicidated. The herbicide contained as an active ingredient is effective as a selective herbicide between the 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.

  The herbicide of the present invention can be used in various dosage forms. When formulated, the active ingredient, that is, the herbicidally active ingredient aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative (I), A method such as mixing 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 can be employed. The preparation is usually in the form of a formulation used as an agrochemical, such as a granule, fine granule, wettable powder, wettable powder, emulsion, aqueous solvent, flowable tablet, tablet, powder, microcapsule or paste. Can be used.

  The herbicide of the present invention is mixed with other agricultural chemicals such as fungicides, insecticides, herbicides, acaricides, safeners, plant growth regulators, fertilizers, or soil conditioners. Or may be used in combination. In particular, when used in combination with other pesticides, the amount of herbicide used can be reduced to save labor, and the herbicide application target (herbicidal spectrum) can be reduced by the cooperative action of both agents. It can also 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.), ammonium sulfate, urea, polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, etc.), 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 into emulsions, wettable powders, flowables, etc., various surfactants are incorporated for the purposes of emulsification, dispersion, solubilization, wetting, foaming, lubrication, and spreading. Is done. 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- (alkoxyalkyl) alkanoic acid amide derivative (I) is contained in an amount of 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 liquids or emulsions, 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 powders and emulsions, a diluted chemical obtained by diluting in water or a suitable solvent may be sprayed in the range of about 0.3 g to 300 g per 10 are as the converted amount of the active ingredient. .

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-methoxymethoxy-2-methylpropan-2-yl) butanamide (Synthesis of Compound No. 2)
A 50 ml four-necked flask was equipped with a stirrer, a thermometer, and a Dimroth condenser to make a reaction vessel, in which 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl ) 0.60 g (1.88 mmol) of butanamide was added and dissolved in 10 ml of dichloromethane. Under ice-cooling, 0.32 g (2.44 mmol) of N, N-diisopropylethylamine and 0.20 g (2.44 mmol) of chloromethyl methyl ether were sequentially added to the reaction vessel, followed by stirring at room temperature for 1 hour. After completion of the reaction, a saturated aqueous ammonium chloride solution (20 ml) was added, and the mixture was extracted twice with ethyl acetate (50 ml). The obtained organic layer was washed with saturated brine (20 ml) and dried over anhydrous sodium sulfate. After filtering the desiccant, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (silica gel “Silica gel 60H” (trade name, manufactured by Merck & Co., Inc., developing solvent ethyl acetate: hexane 1: 5). Purification gave 0.58 g (85% yield) of 2- (3,5-dichlorophenoxy) -N- (1-methoxymethoxy-2-methylpropan-2-yl) butanamide as a colorless oil.
NMR data was as shown in Tables 3 to 5 below.

Synthesis of 2- (3,5-dichlorophenoxy) -N- (1-methoxy-2-methylpropan-2-yl) butanamide (Synthesis of Compound No. 3)
A 50 ml four-necked flask was equipped with a stirrer, a thermometer, and a Dimroth condenser to make a reaction vessel, in which 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl ) 0.80 g (2.50 mmol) of butanamide was added and dissolved in 20 ml of tetrahydrofuran. Under ice-cooling, 0.25 g (6.25 mmol) of sodium hydride (purity 60%) and 1.05 g (7.50 mmol) of methyl iodide were sequentially added to the reaction vessel, and the mixture was brought to room temperature for 30 minutes at the same temperature. And stirred for 2 hours. After completion of the reaction, water (20 ml) was added and extracted twice with ethyl acetate (50 ml). The obtained organic layer was washed with saturated brine (20 ml) and dried over anhydrous sodium sulfate. After the desiccant was filtered, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (silica gel “Silica gel 60H” (trade name, manufactured by Merck & Co., Ltd., developing solvent ethyl acetate: toluene 1:40). Purification gave 0.58 g (70% yield) of 2- (3,5-dichlorophenoxy) -N- (1-methoxy-2-methylpropan-2-yl) butanamide as a colorless oil.
NMR data was as shown in Tables 3 to 5 below.

Synthesis of 2- (3,5-dichlorophenoxy) -N- (2-methyl-1-propargyloxypropan-2-yl) butanamide (Synthesis of Compound No. 4)
A 50 ml four-necked flask was equipped with a stirrer, a thermometer, and a Dimroth condenser to make a reaction vessel, in which 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl ) 0.80 g (2.50 mmol) of butyramide was added and dissolved in 20 ml of tetrahydrofuran. Under ice-cooling, 0.25 g (6.25 mmol) of sodium hydride (purity 60%) and 0.89 g (7.50 mmol) of propargyl bromide were sequentially added to the reaction vessel, and the same temperature was maintained for 30 minutes at room temperature. Stir for 2 hours. After completion of the reaction, a saturated aqueous ammonium chloride solution (20 ml) was added, and the mixture was extracted twice with ethyl acetate (50 ml). The obtained organic layer was washed with saturated brine (20 ml) and dried over anhydrous sodium sulfate. After the desiccant was filtered, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (silica gel “Silica gel 60H” (trade name, manufactured by Merck & Co., Ltd., developing solvent ethyl acetate: toluene 1:40). Purification gave 0.75 g (84% yield) of 2- (3,5-dichlorophenoxy) -N- (2-methyl-1-propargyloxypropan-2-yl) butanamide as a colorless oil.
NMR data was as shown in Tables 3 to 5 below.

Synthesis of 2- (3,5-dichlorophenoxy) -N- [2-methyl-1- (2-tetrahydrofuryloxy) propan-2-yl] butanamide (Synthesis of Compound No. 6)
A 100 ml four-necked flask was equipped with a stirrer, thermometer, and Dimroth condenser to make a reaction vessel, in which 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl ) 1.0 g (3.12 mmol) of butanamide was added and dissolved in 10 ml of dichloromethane. In this reaction vessel, 1.1 g (15.6 mmol) of 2,3-dihydrofuran and 40 mg (0.156 mmol) of pyridinium p-toluenesulfonate were sequentially added and stirred at room temperature for 30 minutes. After completion of the reaction, saturated aqueous sodium hydrogen carbonate solution (20 ml) was added, and the mixture was extracted twice with ethyl acetate (50 ml). The obtained organic layer was washed with saturated brine (20 ml) and dried over anhydrous sodium sulfate. After filtering the desiccant, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (silica gel “Silica gel 60H” (trade name, manufactured by Merck & Co., Inc., developing solvent ethyl acetate: hexane 1: 5). Purified and 1.2 g (99% yield) of 2- (3,5-dichlorophenoxy) -N- [2-methyl-1- (2-tetrahydrofuryloxy) propan-2-yl] butanamide as a colorless oil. Got.
NMR data was as shown in Tables 3 to 5 below.

[Reference Production Example 1]
Synthesis of 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butanamide 1) Synthesis of 2- (3,5-dichlorophenoxy) butyric acid The flask was equipped with a stirrer, a thermometer, and a Dimroth condenser to make a reaction vessel, to which 5 g (0.031 mol) of 3,5-dichlorophenol was added and dissolved in 50 ml of 1,2-dimethoxyethane. In this reaction vessel, 4.8 g (0.043 mol) of potassium t-butoxide was added at room temperature, followed by stirring at room temperature for 10 minutes. Next, 8.4 g (0.043 mol) of ethyl 2-bromoacetate was added at room temperature, and the mixture was stirred at 60 ° C. for 2 hours. After completion of the reaction, 50 ml of a saturated aqueous ammonium chloride solution was added to the reaction mixture, followed by extraction twice 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 to obtain an oily crude product of ethyl 2- (3,5-dichlorophenoxy) butyrate. This crude product was dissolved in 50 ml of methanol, 10 ml of an aqueous 2.6 g (0.046 mol) potassium hydroxide solution 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 adjusted to pH 1 using 1 mol / l aqueous hydrochloric acid solution, and extracted from it three times with 100 ml of ethyl acetate, and the resulting organic layer was washed with 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) butanamide A reaction vessel equipped with a stirrer, thermometer and Dimroth condenser in a 50 ml four-necked flask In this, 2.5 g (0.01 mol) of 2- (3,5-dichlorophenoxy) butyric acid was added and dissolved in 30 ml of dichloromethane. Under ice-cooling, 1.9 g (0.015 mol) of oxalyl chloride and a catalytic amount of N, N-dimethylformamide were sequentially added to the reaction vessel, followed by stirring at room temperature for 1 hour. After completion of the reaction, dichloromethane was distilled off under reduced pressure to obtain oily 2- (3,5-dichlorophenoxy) butyryl chloride as a crude product. Next, a 50 ml four-necked flask was equipped with a stirrer, thermometer, and Dimroth condenser to prepare a reaction vessel, into which 3.6 g (0.04 mol) of 2-amino-2-methyl-1-propanol was added, and dichloromethane was added. Dissolved in 20 ml. Under ice cooling, 1.2 g (0.03 mol) of sodium hydroxide was dissolved in 10 ml of water and added to the reaction vessel. To this solution, a solution of 2- (3,5-dichlorophenoxy) butyryl chloride obtained previously in 10 ml of dichloromethane was added dropwise with vigorous stirring. After completion of dropping, the mixture was vigorously stirred at the same temperature for 30 minutes. After completion of the reaction, the organic layer was separated and washed with saturated brine. Dichloromethane was distilled off from the organic layer under reduced pressure, and the resulting mixture was purified by column chromatography using silica gel (silica gel “Silica gel 60H” (trade name, manufactured by Merck), developing solvent toluene: acetone 8: 1. ), 3.1 g (97% yield) of oily 2- (3,5-dichlorophenoxy) -N- (1-hydroxy-2-methylpropan-2-yl) butanamide.

Tables 3 to 5 show ¹ H-NMR data of the compounds of the present invention represented by the general formula (I).

Production of Herbicide Further, the method for formulating the aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative (I) of the present invention as a herbicide will be specifically described by Examples 5 to 10 below. However, the herbicide of this invention is not limited only to these Examples 5-10, and it cannot be overemphasized that it can mix with other various additives in arbitrary ratios, and can be formulated.
In addition, a compound number is shown to the said Table 1-2, and "part" shall show a weight part altogether in the following examples.

(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).

(Wettable powder)
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 uniformly mixed by a pulverizer and mixed to obtain a herbicidal active ingredient ( A wettable powder containing 15% of Compound No. 19) was 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).

(Powder)
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.

  All of the aryloxy-N- (alkoxyalkyl) 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 5 to 10 above. Can be formulated.

  Next, Test Examples 1 to 4 are shown to illustrate the herbicidal effect of the aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative (I) of the present invention.

なお表６〜表９中の化合物番号は、前記表１〜表２に示したものと同様のものである。
また、比較薬剤として、下記式で示される比較化合物（Ｄ）および比較化合物（Ｅ）を含む水和剤を実施例８に準じて調製し、同様に試験を実施した。その結果を表９に示す。比較薬剤として用いた比較化合物（Ｄ）および比較化合物（Ｅ）は、それぞれ次式(Ｄ)および(Ｅ)で示される化合物である。これらの比較化合物は、後出の試験例２〜試験例４においても同様に比較薬剤として用いられる。

<Test Example 1> Herbicidal effect test by paddy rice soil treatment and phytotoxicity test for transplanted paddy rice Paddy soil is filled in a 1 / 5,000 are wide Wagner pot, water is added, and 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 the rice transplantation, the wettable powder prepared according to Example 8 was diluted with the compounds shown in Tables 6 to 9 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 systems per chemical solution concentration group, and the herbicidal rate (%) was determined by the following formula 1 21 days after drug treatment. The results are shown in Tables 6 to 9 below.

The compound numbers in Tables 6 to 9 are the same as those shown in Tables 1 and 2.
Moreover, the wettable powder containing the comparative compound (D) and the comparative compound (E) which are shown by a following formula as a comparative chemical | medical agent was prepared according to Example 8, and the test was implemented similarly. The results are shown in Table 9. The comparative compound (D) and the comparative compound (E) used as the comparative agent are compounds represented by the following formulas (D) and (E), respectively. These comparative compounds are also used as comparative agents in Test Examples 2 to 4 described later.

<Test Example 2> Herbicidal effect test by paddy rice growing season treatment 1 / 5,000 are wide Wagner pot is filled with paddy 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 8 using the compounds shown in Tables 10 to 13 below was diluted with water, 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 determined according to the above-mentioned formula 1 21 days after the drug treatment. The results are shown in Tables 10 to 13.

<Test Example 3> Herbicidal effect test and phytotoxicity test by upland field 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. One day after sowing, the emulsion prepared according to Example 9 was diluted with water using the compounds shown in Tables 14 to 17 below, and the water diluted chemical solution was sprayed on the soil surface at a rate of 100 liters per 10 ares. did. 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 Tables 14-17.

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 9 was diluted with water using the compounds shown in Tables 14 to 17 below, and the water diluted chemical solution was sprayed on the soil surface at a rate of 100 liters per 10 ares. did. 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 determined according to the above-mentioned formula 1 21 days after the drug treatment. The results are shown in Tables 14-17.

<Test Example 4> Herbicidal effect test and phytotoxicity test by field foliage treatment 1) Herbicidal effect test for field crop weeds: Field soil (alluvial loam) is packed in a 1/5000 are large unglazed pot, and 1 cm surface soil 50 weed seeds of Japanese barnyard beetle, Enokorogusa, Shiroza, and Inuta were mixed uniformly, and the surface layer was lightly pressed. Seven days after sowing, the emulsion prepared according to Example 9 was diluted with water using the compounds shown in Table 18 to Table 21 below, and the water diluted chemical solution was sprayed on the soil surface at a rate of 100 liters per 10 ares. did. 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 18 to Table 21.

  2) Chemical damage test on crops: 1 / 10,000 ares of unglazed pot filled with field soil (alluvial loam) and seeded seeds of each crop (5 soybeans, 10 wheats) in separate pots Then, the surface layer was lightly pressed. Seven days after sowing, using the compounds shown in Table 18 to Table 21 below, the emulsion prepared according to Example 9 was diluted with water, and the water-diluted drug solution was sprayed onto the plant body at a rate of 100 liters per 10 ares. did. 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 determined according to the above-mentioned formula 1 21 days after drug treatment. The results are shown in Tables 18-21.

Claims (2)

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 , R ₅ and R ₆ each independently represent a hydrogen atom or a C1-C6 alkyl group, and R ₇ represents a hydrogen atom, a C1-C6 alkyl group Group, C3-C6 alkenyl group, C3-C6 alkynyl group, C1-C6 alkyloxy C1-C6 alkyl group, C1-C6 halogenated alkyl group or benzyl group, R ₁ or R ₇ is C1-C6 alkyloxy When showing a C1-C6 alkyl group, it is each independently the both ends of the oxygen atom in a C1-C6 alkyloxy C1-C6 alkyl group. Two bonded alkyl chains may be bonded 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 Sometimes each X may be the same or different. ] The aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative represented by this. A herbicide comprising the aryloxy-N- (alkoxyalkyl) alkanoic acid amide derivative represented by the general formula (I) according to claim 1 as a herbicidal active ingredient.