JP2009114128A - Amide derivative of amino acid and herbicide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a herbicide exhibiting excellent herbicidal activities with a small amount of the herbicide, and having excellent selectivity. <P>SOLUTION: The amide derivative of an amino acid is represented by general formula (I) (wherein, X is a halogen, an alkyl or a haloalkyl; R<SP>1</SP>to R<SP>5</SP>are each selected from H, an alkyl, an alkoxy, an oxyalkyl, a cycloalkyl, a haloalkyl, a cyanoalkyl, an aminoalkyl, an alkenyl, a haloalkenyl, an alkynyl, a benzyl and a carboxyalkenyl). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel amino acid amide derivative and a herbicide containing the same 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, Various herbicides having various structures such as urea, acid amide, heterocyclic, phenol, diphenyl ether, and pyridinium have been proposed and put into practical use.

  So far, compounds described below are known as compounds belonging to amino acid amide derivatives.

［式（Ａ）中、Ｒ¹およびＲ^２はハロゲン原子または炭素数１〜４のアルキル基であり、Ｒ^３は炭素数１〜４のアルキル基である。］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）。 (1) General formula (A)

Wherein (A), R ¹ and ^{R 2} is a halogen atom or an alkyl group having 1 to 4 carbon atoms, ^{R 3} is an alkyl group having 1 to 4 carbon atoms. The phenoxy alkanoic acid amide derivative represented by this is described, and it is described that this derivative has herbicidal activity (see Patent Document 1).

［式（Ｂ）中、Ｒ¹およびＲ^２はハロゲン原子または炭素数１〜４のアルキル基であり、Ｒ^３は炭素数１〜４のアルキル基であり、Ｒ⁴およびＲ⁵は水素原子または炭素数１〜３のアルキル基である。］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）。 (2) General formula (B)

[In the formula (B), R ¹ and R ² are a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are hydrogen atoms or It is a C1-C3 alkyl group. The phenoxyalkanoic 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はハロゲン、（置換）低級アルキル、低級アシル、シアノ基等；ｎ＝０〜３；Ｒ^１、Ｒ^２はＨ、低級アルキル；Ｒ^３、Ｒ^４はＨ、低級アルキル、それらが結合している炭素原子と共に５〜７員炭素環を形成等；Ｒ５は、Ｈ、（置換）低級アルキル、（置換）低級アルケニル基等］で表わされる置換フェノキシカルボン酸アミド誘導体が記載され、この誘導体は殺菌活性を有することが記載されているが除草活性についての記載はない（特許文献３参照）。 (3) General formula (C)

[In the formula (C), X is halogen, (substituted) lower alkyl, lower acyl, cyano group, etc .; n = 0 to 3; R ¹ and R ² are H, lower alkyl; R ³ and R ⁴ are H, lower A substituted phenoxycarboxylic acid amide derivative represented by H, (substituted) lower alkyl, (substituted) lower alkenyl group, etc.]. Although it is described that this derivative has bactericidal activity, there is no description on herbicidal activity (see Patent Document 3).

In general, in the development of herbicides, it is required to develop herbicides that exhibit high herbicidal effects at low doses, have herbicidal activity against a wide variety of weeds, and are excellent in safety. However, when the amino acid amide derivatives as described above are used as herbicidal active ingredients, the herbicidal effect is insufficient at low doses, and even if they exhibit herbicidal activity, selective herbicidal use of crops and weeds Since it is inferior in activity, it has a large phytotoxicity to crops, so it cannot always be used satisfactorily as a herbicide.
US Pat. No. 3,953,507 US Pat. No. 4,051,184 JP-A-5-194344

  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 amino acid amide derivative and a herbicide containing the same that can be used for a wide variety of weeds.

  As a result of intensive investigations to solve the above problems, the present inventors have found that the compound according to the present invention has an excellent herbicidal effect at low doses against paddy rice and field crop weeds without causing phytotoxicity to crops. The present invention has been completed.

［一般式（Ｉ）において、Ｘは、ハロゲン原子、炭素数１〜６のアルキル基、または炭素数１〜６のハロゲン化アルキル基を示し、Ｒ^１は、水素原子、炭素数１〜６のアルキル基または炭素数１〜６のアルキル基で置換された炭素数１〜６のアルキルオキシ基を示し、Ｒ^２およびＲ^３は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、炭素数１〜６のヒドロキシアルキル基を示し、Ｒ⁴およびＲ⁵は、それぞれ独立に水素原子、炭素数１〜９のアルキル基、炭素数３〜６のシクロアルキル基、炭素数１〜６のヒドロキシアルキル基、炭素数１〜６のアルキル基で置換された炭素数１〜６のアルキルオキシ基、炭素数１〜６のオキシアルキル基、炭素数１〜６のハロゲン化アルキル基、炭素数１〜６のシアノアルキル基、炭素数１〜６の置換されていてもよいアミノアルキル基、炭素数３〜６のアルケニル基、炭素数３〜６のハロゲン化アルケニル基、炭素数３〜６のアルキニル基、置換されていてもよいベンジル基、炭素数２〜７のカルボキシルアルキル基、または炭素数３〜７のカルボキシルアルケニル基を示し、Ｒ⁴およびＲ⁵が-Ｃ_２Ｈ_４ＯＣ_２Ｈ_４-、-Ｃ_４Ｈ_８-の場合、Ｒ⁴およびＲ⁵のそれぞれが結合する炭素原子とともに５員環または６員環を形成してもよく、ｎは、０〜５の整数を示し、ｎが２以上のとき、それぞれのＸは同一でも相異なっていてもよい。］で表されるアミノ酸アミド誘導体に関するものである。 That is, the amino acid amide derivative according to the first invention of the present application is represented by the following general formula (I):

[In General Formula (I), X represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 6 carbon atoms, and R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 1 represents an alkyloxy group having 1 to 6 carbon atoms substituted with an alkyl group or an alkyl group having 1 to 6 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, carbon 1 to 6 represents a hydroxyalkyl group, and R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a hydroxy group having 1 to 6 carbon atoms. An alkyl group, an alkyloxy group having 1 to 6 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms, an oxyalkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms 6 cyanoalkyl groups, 1 to 6 carbon atoms An aminoalkyl group which may be substituted, an alkenyl group having 3 to 6 carbon atoms, a halogenated alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, an optionally substituted benzyl group, carbon A carboxyalkyl group having 2 to 7 carbon atoms, or a carboxyalkenyl group having 3 to 7 carbon atoms, wherein R ⁴ and R ⁵ are —C ₂ H ₄ OC ₂ H ₄ —, —C ₄ H ₈ —, R ⁴ And R ⁵ may form a 5-membered ring or a 6-membered ring together with the carbon atom to which each of R ⁵ is bonded, n represents an integer of 0 to 5, and when n is 2 or more, each X is the same or a phase May be different. ] It is related with the amino acid amide derivative represented by this.

  Moreover, 2nd invention of this application is related with the herbicide which contains the amino acid amide derivative shown by the said general formula (I) as a herbicidal active ingredient.

    The amino acid amide derivative according to the present invention, when used as a herbicidal active ingredient, exhibits excellent herbicidal activity even at low dosages, and is excellent in selective herbicidal activity in various combinations of crops and weeds. It can be used for a wide range of objects such as weeds of things.

  In addition, according to the herbicide of the present invention containing the amino acid amide derivative represented by the general formula (I) of the present invention as an active ingredient, it has a low dosage for paddy rice and field crop weeds without causing phytotoxicity to the crop Because of its excellent herbicidal effect, it is possible to obtain crops with high safety and good quality.

  Hereinafter, the novel amino acid amide derivative according to the present invention, the production method thereof, and the herbicide containing this as an herbicidal active ingredient will be specifically described.

[Amino acid amide derivative of the present invention]
The amino acid amide derivative of the present invention is represented by the general formula (I). (Hereinafter also referred to as amino acid amide derivative (I))
In the present invention, the amino acid amide derivative (I) is characterized in that the amino acid amide-bonded to phenoxybutyric acid is further extended by the amide bond, and is considered to have a large role in herbicidal activity.
In the amino acid amide derivative represented by the general formula (I), specific examples of each substituent represented by X, R ¹ , R ² , R ³ , R ⁴ and R ⁵ include the following. However, it is not limited to the example shown here.

  Examples of the “halogen atom” represented by X include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom is preferable.

  The “alkyl group having 1 to 6 carbon atoms” represented by X means a linear or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, 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-methyl-2-ethylpropyl group, 2-methyl-1-ethylpropyl group and 2-methyl-2- Or the like can be mentioned Chirupuropiru group. Of these, a methyl group is preferable.

  The “C 1-6 halogenated alkyl group” represented by X is a linear or branched chain having 1 to 6 carbon atoms in which at least a part of the hydrogen atoms in the alkyl group are substituted with halogen atoms. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples thereof include trifluoromethyl group, chloromethyl group, bromomethyl group, dichloromethyl group, difluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 1,1-difluoro. Examples thereof include an ethyl group, a 2,2,2-trifluoroethyl group, a 3-chloropropyl group and a 3-iodopropyl group. Of these, a trifluoromethyl group is preferable.

The “alkyl group having 1 to 6 carbon atoms” represented by R ¹ means a linear or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, n-hexyl group, 4-methyl Pentyl 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 Groups, 1-ethyl-2-methyl-propyl group, 1-methyl-1-ethylpropyl group, 1-methyl-2-ethylpropyl group, 2-methyl-1-ethylpropyl group and 2-methyl-2 -An ethylpropyl group etc. can be mentioned. Of these, an ethyl group is preferable.

The “C1-C6 alkyloxy group substituted with a C1-C6 alkyl group” represented by R ¹ means that a part of the alkyl group is substituted with a hydroxyl group, having a C1-C6 In which the hydroxyl group of the linear or branched alkyl group is substituted with a linear or branched chain having 1 to 6 carbon atoms, and as the alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, n-hexyl group, 4-methyl Pentyl 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 Base 1-ethyl-2-methyl-propyl group, 1-methyl-1-ethylpropyl group, 1-methyl-2-ethylpropyl group, 2-methyl-1-ethylpropyl group and 2-methyl-2-ethylpropyl group Groups. Examples thereof include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, propoxymethyl group, isopropoxymethyl group and the like. Of these, a methoxymethyl group is preferred.

The “alkyl group having 1 to 6 carbon atoms” represented by R ² and R ³ means a linear or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, 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-methyl-2-ethylpropyl group, 2-methyl-1-ethylpropyl group and And 2-methyl-2-ethylpropyl group, and the like. Of these, a methyl group is preferable.

“Hydroxyalkyl group having 1 to 6 carbon atoms” represented by R ² and R ³ is a straight chain or branched chain having 1 to 6 carbon atoms in which a part of hydrogen atoms in the alkyl group is substituted with a hydroxyl group. A chain-like hydroxyalkyl group is meant. Examples thereof include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-hydroxy-2-methylpropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2 And -hydroxybutyl group.

The “alkyl group having 1 to 9 carbon atoms” represented by R ⁴ and R ⁵ means a linear or branched alkyl group having 1 to 9 carbon atoms, examples of which are described above. In addition, heptyl group, octyl group, nonyl group and the like including the group mentioned in the “C1-C6 alkyl group” can be exemplified.

The “cycloalkyl group having 3 to 6 carbon atoms” represented by R ⁴ and R ⁵ means a cyclic alkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and cyclopentyl. Group, cyclohexyl group and the like. Of these, a cyclohexyl group is preferred.

“Hydroxyalkyl group having 1 to 6 carbon atoms” represented by R ⁴ and R ⁵ is a straight chain or branched chain having 1 to 6 carbon atoms in which a part of hydrogen atoms in the alkyl group is substituted with a hydroxyl group. A chain-like hydroxyalkyl group is meant. Examples thereof include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-hydroxy-2-methylpropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2 And -hydroxybutyl group. Of these, a 2-hydroxyethyl group is preferable.

The “C1-C6 alkyloxy group substituted with a C1-C6 alkyl group” represented by R ⁴ and R ⁵ is a compound in which a part of the alkyl group is substituted with a hydroxyl group. It means that the hydroxyl group of a linear or branched alkyl group having 1 to 6 is substituted with a linear or branched chain having 1 to 6 carbon atoms. As the alkyl group, a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, 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-Echi Butyl, 1-ethyl-2-methyl-propyl, 1-methyl-1-ethylpropyl, 1-methyl-2-ethylpropyl, 2-methyl-1-ethylpropyl and 2-methyl-2- An ethylpropyl group is mentioned. Examples thereof include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, propoxymethyl group, isopropoxymethyl group and the like. Of these, a methoxyethyl group is preferred.

The “oxyalkyl group having 1 to 6 carbon atoms” represented by R ⁴ and R ⁵ means that an oxygen atom is substituted with a linear or branched alkyl group having 1 to 6 carbon atoms. And examples thereof include methyloxy group, ethyloxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, s-butyloxy group, tert-butyloxy group, n-pentyloxy group, And neopentyloxy group. Of these, a methyloxy group and an isopropyloxy group are preferable.

The “halogenated alkyl group having 1 to 6 carbon atoms” represented by R ⁴ and R ⁵ is a straight chain having 1 to 6 carbon atoms in which at least a part of hydrogen atoms in the alkyl group is substituted with a halogen atom. Or a halogenated alkyl group in the form of a branched chain, and the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples thereof include trifluoromethyl group, chloromethyl group, bromomethyl group, dichloromethyl group, difluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 1,1-difluoro. Examples thereof include an ethyl group, 2,2,2-trifluoroethyl group, 3-chloropropyl group, 2-chloropropyl group, 3-bromopropyl group, 2-bromopropyl group, and 3-iodopropyl group. Of these, a 2-chloroethyl group is preferable.

The “C 1-6 cyanoalkyl group” represented by R ⁴ and R ⁵ is a straight chain having 1-6 carbon atoms, wherein a part of hydrogen atoms in the alkyl group are substituted with a cyano group, or It means a branched cyanoalkyl group. Examples thereof include cyanomethyl group, cyanoethyl group, cyanopropyl group, cyanobutyl group and the like.

The “optionally substituted aminoalkyl group having 1 to 6 carbon atoms” represented by R ⁴ and R ⁵ means that a part of hydrogen atoms in the alkyl group is substituted with an amino group and has 1 to 1 carbon atoms. 6 linear or branched aminoalkyl groups. The amino group may be mono- or disubstituted with a lower alkyl group. Examples thereof include 2-methylaminoethyl group, 2-dimethylaminoethyl group, 3-methylaminopropyl group, 3-dimethylaminoethyl group, 2-methylaminopropyl group, 2-dimethylaminoethyl group and the like. Can do. Of these, a 2-dimethylaminoethyl group is preferable.

The “alkenyl group having 3 to 6 carbon atoms” represented by R ⁴ and R ⁵ means an alkyl group having an unsaturated bond having 3 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, An isobutenyl group can be exemplified.

The “halogenated alkenyl group having 3 to 6 carbon atoms” represented by R ⁴ and R ⁵ means an alkyl group having an unsaturated bond having 3 to 6 carbon atoms in which at least one portion is substituted with halogen, Examples thereof include a chloroallyl group, a bromoallyl group, and a fluoroallyl group.

The “C3-C6 alkynyl group” represented by R ⁴ and R ⁵ means an alkyl group having a triple bond having 3 to 6 carbon atoms. Examples thereof include a propargyl group and a 2-butynyl group. , 2-pentyne group, 2-hexyne group and the like.

The “optionally substituted benzyl group” represented by R ⁴ and R ⁵ means a group in which the benzene cyclic hydrogen of the benzyl group is unsubstituted and substituted with 1 to 5 by an appropriate substituent. Examples thereof include a benzyl group, a 4-chlorobenzyl group, a 4-fluorobenzyl group, and a 3,5-dichlorobenzyl group.

The “carboxyl alkyl group having 2 to 7 carbon atoms” represented by R ⁴ and R ⁵ means a group in which the alkyl group described above is substituted with a carboxyl group, and examples thereof include a carboxymethyl group. Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, (biscarboxy) methyl group, (bismethoxycarbonyl) methyl group, (bisethoxycarbonyl) methyl group, and the like.

The “carboxyl alkenyl group having 3 to 7 carbon atoms” represented by R ⁴ and R ⁵ means a group in which the above-described alkenyl group is substituted with a carboxyl group. A vinyl group, 2-carboxyl propenyl group, 2-methoxycarbonylvinyl group, 2-ethoxycarbonylvinyl group, 2-methoxycarbonylpropenyl group, 2-ethoxycarbonylpropenyl group, etc. can be mentioned.

Specific examples of the amino acid amide derivative (I) according to the present invention are shown in Table 1-1 to Table 1-6. However, the present invention is not limited to these specific examples.
In addition, the compound numbers in Table 1-1 to Table 1-6 are also referred to in the following Table 2, Examples, Formulation Examples, and Test Examples.

<Note 1>
In Table 1-1 to Table 1-6, for example, “position and number n of X” in compound number 1 is “3,5-Cl ₂ ”. This means that there are two substituents X: chlorine atoms (Cl) at positions 3, 5 on the benzene ring.
For example, in Compound No. 118, “X position and number n” is “3,5- (CH ₃ ) ₂ -4-Cl”. Here, “3,5- (CH ₃ ) ₂ ” means that _two substituents X: CH ₃ are present at the 3,5 positions on the benzene ring, and “4-Cl” It means that there is one X: chlorine atom (Cl) at the 4-position on the benzene ring.
Accordingly, the Compound No. 118, _{"3,5- (CH 3) 2 -4-} Cl " refers to a 3,5 position on the benzene ring, CH ₃ is present a total of two, is Cl to the position of the 4 It means that there is one. Of course, other compounds have the same meaning.

[Method for producing amino acid amide derivative of the present invention]
The amino acid amide derivative (I) of the present invention can be produced, for example, by combining the following first step with any one of the second step a), the second step b) or the second step c).

第二工程

First step

Second step

In the above reaction scheme, X, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are as defined in the general formula (I), R represents a lower alkyl, and Hal represents a halogen atom. Indicates.

  In the above reaction formula, first, in the first step, the phenoxyalkanoic acid derivative (IV) can be produced by reacting the phenol (II) with the α-haloalkanoic acid ester (III) in the presence of a base. . Examples of the base used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. This reaction is preferably performed in the presence of a solvent, and examples of the solvent used include alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, and tert-butanol. In the above reaction, with respect to 1 mol of phenol (II), α-haloalkanoic acid ester (III) is 1 to 3 mol, preferably 1 to 1.2 mol, and the base is 2 to 4 mol. Preferably 2-2.5 mol is used. The reaction is usually performed at a temperature of 0 to 120 ° C, preferably 10 to 90 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours. After completion of the reaction, the phenoxyalkanoic acid derivative (IV) is obtained by, for example, distilling off the solvent of the reaction solution containing the derivative (IV), adding water, and then acidifying with hydrochloric acid, sulfuric acid, etc., diethyl ether, After extraction with an extraction solvent such as toluene or ethyl acetate, the extract is washed with water and saturated brine, and the solvent is distilled off.

  Next, the resulting phenoxyalkanoic acid derivative (IV) is converted into a phenoxyalkanoic acid halide (V) using a halogenating agent, and then reacted with an amino acid ester (VI) in the presence of a base, A phenoxyalkanoic acid amide derivative (VII) can be produced. This halogenation reaction is preferably carried out in a solvent, and examples of the solvent used include dichloromethane, 1,2-dichloroethane, chloroform, benzene, toluene, xylene and the like, and examples of the halogenating agent include oxalyl chloride, thionyl chloride, Examples include phosphorus trichloride and phosphorus pentachloride. The halogenating agent is used in an amount of 1 to 2 mol, preferably 1 to 1.5 mol, per 1 mol of the phenoxyalkanoic acid derivative (IV). This reaction is usually performed at a temperature of 0 to 100 ° C, preferably 20 to 80 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours. Examples of the solvent used when the obtained phenoxyalkanoic acid halide (V) is reacted with the amino acid ester (VI) include dichloromethane, 1,2-dichloroethane, chloroform, tetrahydrofuran, benzene, toluene, xylene and the like. In some cases, it can also be used as a mixed solvent with water. Examples of the base used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine, tri n-propylamine, N, N-diisopropylethylamine and the like. The usage-amount of amino acid ester (VI) is 1-2 mol with respect to 1 mol of phenoxyalkanoic acid halide (V), Preferably it is 1-1.1 mol, A base is 1-2 mol, Preferably it is 1 ~ 1.1 mol is used. This reaction is usually performed at a temperature of 0 to 80 ° C, preferably 0 to 40 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours. After completion of the reaction, the phenoxyalkanoic acid amide derivative (VII) can be obtained, for example, by adding water and an organic solvent to a reaction solution containing the derivative, followed by washing with water and saturated brine, and distilling off the solvent. It is done. If necessary, the obtained target product can be further purified by operations such as column chromatography or recrystallization.

  Subsequently, hydrolysis of the phenoxyalkanoic acid amide derivative (VII) of the above reaction formula to the phenoxyalkanoic acid amide derivative (VIII) proceeds more easily in the presence of a base. Examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. This hydrolysis reaction is preferably carried out in the presence of a solvent, and examples of the solvent used include water and alcohols such as methanol, ethanol and isopropanol. In some cases, a mixed solvent with water is used. Can also be used. When the ester moiety is hydrolyzed, 1 to 2 mol, preferably 1 to 1.5 mol, of a base such as sodium hydroxide is used with respect to 1 mol of the phenoxyalkanoic acid amide derivative (VII). 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. After completion of the reaction, the phenoxyalkanoic acid amide derivative (VIII) is made acidic by adding hydrochloric acid, sulfuric acid, etc. after adding water to the reaction solution containing the derivative (VIII), for example, diethyl ether, toluene, ethyl acetate, etc. After extraction with a solvent for extraction, it is obtained by washing with water and saturated saline and distilling off the solvent.

  In the second step a), the phenoxyalkanoic acid amide derivative (VIII) obtained in the first step is converted to a phenoxyalkanoic acid halide (IX) using a halogenating agent, and then an amine (X ) To produce the amino acid amide derivative (I). This halogenation reaction is preferably carried out in a solvent, and examples of the solvent used include dichloromethane, 1,2-dichloroethane, chloroform, benzene, toluene, xylene and the like, and examples of the halogenating agent include oxalyl chloride, thionyl chloride, Examples include phosphorus trichloride and phosphorus pentachloride. The halogenating agent is used in an amount of 1 to 2 mol, preferably 1 to 1.5 mol, per 1 mol of the phenoxyalkanoic acid amide derivative (VIII). This reaction is usually performed at a temperature of 0 to 100 ° C, preferably 20 to 80 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours. Examples of the solvent used when the obtained phenoxyalkanoic acid halide (IX) and amines (X) are reacted include dichloromethane, 1,2-dichloroethane, chloroform, tetrahydrofuran, benzene, toluene, xylene, and the like. In some cases, it can be used as a mixed solvent with water. Examples of the base used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine, tri n-propylamine, N, N-diisopropylethylamine and the like. The usage-amount of amine (X) is 1-2 mol with respect to 1 mol of phenoxyalkanoic acid halide (IX), Preferably it is 1-1.1 mol, A base is 1-2 mol, Preferably it is 1-. 1.1 moles are used. This reaction is usually performed at a temperature of 0 to 80 ° C, preferably 0 to 40 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours. After completion of the reaction, the amino acid amide derivative (I) can be obtained, for example, by adding water and an organic solvent to a reaction solution containing the derivative, followed by washing with water and saturated brine, and distilling off the solvent. If necessary, the obtained target product can be further purified by operations such as column chromatography or recrystallization.

  In the second step b), the phenoxyalkanoic acid amide derivative (VIII) obtained in the first step is reacted with a condensing agent in the presence of a base (dehydration condensation and cyclization reaction in the molecule), whereby an oxazolinone derivative ( This is a step for producing an amino acid amide derivative (I) by reacting with amines (X) in the presence of an acid catalyst after conversion to XI). This cyclization reaction is preferably performed in a solvent, and examples of the solvent used include dichloromethane, 1,2-dichloroethane, chloroform, acetonitrile, dimethylformamide, and the like, and 1,3-dicyclohexylcarbodiimide, Examples thereof include 1-ethyl-3- (3′-dimethylaminopropyl) carbodiimide, 2-methyl-6-nitrobenzoic anhydride and the like. Examples of the base used include pyridine, triethylamine, tri-n-propylamine, N, N-diisopropylethylamine, 4-dimethylaminopyridine and the like. The amount of the condensing agent used is 1 to 2 mol, preferably 1 to 1.1 mol, and the base is 1 to 4 mol, preferably 2 to 3 mol, per 1 mol of the phenoxyalkanoic acid amide derivative (VIII). Used. This reaction is usually performed at a temperature of 0 to 80 ° C, preferably 0 to 40 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours. After completion of the reaction, the oxazolinone derivative (XI) can be obtained, for example, by adding water and an organic solvent to the reaction solution containing the derivative, followed by washing with water and saturated brine, and distilling off the solvent. If necessary, the obtained target product can be further purified by operations such as column chromatography or recrystallization. Examples of the solvent used when the obtained oxazolinone derivative (XI) and amines (X) are reacted include dichloromethane, 1,2-dichloroethane, chloroform, tetrahydrofuran, benzene, toluene, xylene and the like. Examples of the acid catalyst used include borane trifluoride / diethyl ether complex, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, and the like. The amount of the amine (X) used is 1 to 5 mol, preferably 1 to 2 mol, and the acid catalyst is 0.1 to 0.5 mol, preferably 0, per 1 mol of the oxazolinone derivative (XI). .2 to 0.5 mol is used. This reaction is usually performed at a temperature of 0 to 100 ° C, preferably 0 to 40 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours. After completion of the reaction, the amino acid amide derivative (I) can be obtained, for example, by adding water and an organic solvent to a reaction solution containing the derivative, followed by washing with water and saturated brine, and distilling off the solvent. If necessary, the obtained target product can be further purified by operations such as column chromatography or recrystallization.

  In the second step c), the phenoxyalkanoic acid amide derivative (VIII) obtained in the first step is reacted with an acid chloride (XII) in the presence of a base to form a mixed acid anhydride derivative (XIII). After the conversion, the amino acid amide derivative (I) is produced by reacting with an amine (X). The amidation reaction via the mixed acid anhydride is preferably carried out in a solvent, and examples of the solvent used include benzene, toluene, xylene, and the base used includes pyridine, triethylamine, tri-n-propyl. Amine, N, N-diisopropylethylamine, 4-dimethylaminopyridine and the like can be mentioned. The amount of the acid chloride (XII) used is 1 to 2 mol, preferably 1 to 1.1 mol, and the base is 1 to 4 mol, preferably 1 mol, per 1 mol of the phenoxyalkanoic acid amide derivative (VIII). 2-3 moles are used. This reaction is usually performed at a temperature of 0 to 80 ° C, preferably 0 to 40 ° C. The time required for adjusting the mixed acid anhydride derivative (XIII) varies depending on the reaction substrate and the reaction temperature, but is usually completed in 1 to 6 hours. After completion of the preparation, the amino acid amide derivative (I) can be produced by adding amines (X) to the system. The amount of amines (X) to be added is 1 to 5 mol, preferably 1 to 2 mol, per 1 mol of phenoxyalkanoic acid amide derivative (VIII). This reaction is usually performed at a temperature of 0 to 150 ° C, preferably 40 to 120 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 1 to 6 hours. After completion of the reaction, the amino acid amide derivative (I) can be obtained, for example, by adding water and an organic solvent to a reaction solution containing the derivative, followed by washing with water and saturated brine, and distilling off the solvent. If necessary, the obtained target product can be further purified by operations such as column chromatography or recrystallization.

[Herbicide of the present invention]
The amino acid amide derivative (I) of the present invention exhibits excellent herbicidal activity at a low dose, as shown in Test Examples described later, and also exhibits excellent selective herbicidal activity between weeds and crops shown below. Therefore, it is useful as a novel herbicidal active ingredient that can be used for a wide variety of weeds in paddy rice cultivation and field cultivation.

  In addition, according to the herbicide of the present invention containing the amino acid amide derivative (I) as an active ingredient (medicinal ingredient), 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 safe and high quality crop. 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.

  The application of the herbicide of the present invention is not limited to the weeds and crops exemplified above.

[Formulation of the herbicide of the present invention]
Next, a general formulation method for the amino acid amide derivative (I) according to the present invention will be described in detail.
The herbicide of the present invention can be used in various dosage forms, and when formulated, the active ingredient, that is, the herbicidally active ingredient, the amino acid amide derivative represented by the general formula (I) is used as a carrier or diluent, If necessary, it is possible to employ a method such as mixing with at least one of additives (eg surfactants) and adjuvants by a known method, and the herbicide thus obtained is usually a pesticide. For example, granules, fine granules, wettable powders, granular wettable powders, emulsions, aqueous solvents, flowables, tablets, powders, microcapsules, pastes and the like.

  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 (soybeans) Flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, etc.), alumina, silicate, sugar polymer, ammonium sulfate, urea, 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) ), Sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline ( Petroleum ether, solvent naphtha, etc.) 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, polysulphates, and the like. Anionic surfactants such as oxyethylene alkylalkyl sulfates and aryl sulfonates, cationic surfactants such as alkylamines (laurylamine, stearyltrimethylammonium chloride, etc.) and polyoxyethylene alkylamines, carboxylic acids (betaine) Type) and amphoteric surfactants such as sulfate ester salts, but are not limited to these examples.

  In addition to these, various auxiliary agents such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, sodium alginate, gelatin, tragacanth rubber, and the like can be used. The herbicide of the present invention contains the oxazolinone derivative represented by the general formula (I) in a range of 0.001 to 95% by weight, preferably 0.01 to 75% by weight, regardless of the dosage form. Is desirable. 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.

  The herbicide formulation of the present invention obtained by the above method is, for example, in the case of granules and flowables, directly on the soil surface, in the soil or in water, as an equivalent amount of active ingredient from 0.3 g to 10 g What is necessary is just to spray by the quantity of the range of about 300g. 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 The present invention will be specifically described below with reference to examples (synthesis of compounds), formulation examples, and test examples, but the present invention is not limited to these ranges.

Preparation of 2- (4-chloro-3,5-dimethylphenoxy) -N- [2-{(2-methoxyethyl) amino} -1,1-dimethyl-2-oxoethyl] butanamide (second step a method) (Compound No. 136)
2-[{2- (4-Chloro-3,5] synthesized in the reference production example described below in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring from −50 to 50 ° C. -Dimethylphenoxy) butanoyl} amino] -2-methylpropionic acid 10.0 g (30.5 mmol) was dissolved in 100 ml of dichloromethane and ice-cooled. Oxalyl chloride (5.04 g, 39.7 mmol) and a catalytic amount of N, N-dimethylformamide (1 ml) were added, and the mixture was stirred at room temperature (20 ° C.) for 1 hour. After completion of the reaction, the solvent of the reaction mixture was distilled off under reduced pressure. In a 300 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer capable of measuring from −50 to 50 ° C., 50 ml of a solution in 5.73 g (76.3 mmol) of dichloromethane cooled with ice was obtained. The crude product was dissolved in 100 ml of dichloromethane and added dropwise. Then, it stirred at room temperature (20 degreeC) for 1 hour. 100 ml of saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted twice with 200 ml of ethyl acetate. The obtained organic layer was washed sequentially with 1N hydrochloric acid aqueous solution (100 ml), saturated sodium hydrogen carbonate aqueous solution (100 ml) and saturated brine (100 ml), dried over anhydrous sodium sulfate, and the crude product obtained by distilling off the solvent under reduced pressure. Was purified by chromatography using silica gel (Wakogel B-10, manufactured by Wako Pure Chemical Industries, Ltd.) {developing solvent hexane: ethyl acetate 1: 2 (volume ratio)} to give the title 2- (4-chloro-3 , 5-dimethylphenoxy) -N- [2-{(2-methoxyethyl) amino} -1,1-dimethyl-2-oxoethyl] butanamide (11.5 g, white powder, 98% yield).

Preparation of 2- (4-chloro-3,5-dimethylphenoxy) -N- {1,1-dimethyl-2-oxo-2- (prop-2-yn-1-ylamino) ethyl} butanamide (second step Method b) (Compound No. 127)
2-[{2- (4-Chloro-3,5] synthesized in the reference production example described below in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring from −50 to 50 ° C. -Dimethylphenoxy) butanoyl} amino] -2-methylpropionic acid 10.0 g (30.5 mmol) and pyridine 7.96 g (101 mmol) were dissolved in 100 ml of dichloromethane and cooled on ice. 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 8.78 g (45.8 mmol) and a catalytic amount of 4-dimethylaminopyridine (500 mg) were added, and the mixture was stirred at room temperature (20 ° C.) for 1 hour. After completion of the reaction, the dichloromethane layer was washed successively with 100 ml of water, 100 ml of 1N aqueous hydrochloric acid solution, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting crude product was purified by chromatography {developing solvent hexane: ethyl acetate 8: 1 (volume ratio)} using silica gel (Wakogel B-10, manufactured by Wako Pure Chemical Industries, Ltd.), and 2- {1- There was obtained 8.98 g (oil, yield 95%) of (4-chloro-3,5-dimethylphenoxy) propyl} -4,4-dimethyl-1,3-oxazol-5 (4H) -one. Ice-cooled 2- {1- (4-chloro-3,5-dimethylphenoxy) propyl} in a 300 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer capable of measuring from −50 to 50 ° C.} 3.19 g (58.0 mmol) of propargylamine was added dropwise to 100 ml of a dichloromethane solution of 8.98 g (29.0 mmol) of -4,4-dimethyl-1,3-oxazol-5 (4H) -one, and a catalytic amount of borane. Trifluoride-diethyl ether complex (500 mg) was added and stirred at 0 ° C. for 1 hour. After completion of the reaction, the dichloromethane layer was washed twice with 100 ml of saturated aqueous sodium hydrogen carbonate solution and then with 100 ml of saturated brine, dried over anhydrous sodium sulfate, and then the crude product obtained by distilling off the solvent under reduced pressure. Was purified by chromatography using silica gel (Wakogel B-10, manufactured by Wako Pure Chemical Industries, Ltd.) {developing solvent hexane: ethyl acetate 1: 1 (volume ratio)} to give 2- (4-chloro-3,5 -Dimethylphenoxy) -N- {1,1-dimethyl-2-oxo-2- (prop-2-yn-1-ylamino) ethyl} butanamide (9.31 g, white powder, yield 88%) was obtained.

Preparation of 2- (4-chloro-3,5-dimethylphenoxy) -N- [2-{(3-chloropropyl) amino} -1,1-dimethyl-2-oxoethyl] butanamide (second step c) (Compound No. 131)
2-[{2- (4-Chloro-3,5-) synthesized in a reference production example described later in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring from 0 to 200 ° C. 10.0 g (30.5 mmol) of dimethylphenoxy) butanoyl} amino] -2-methylpropionic acid and 9.24 g (91.5 mmol) of triethylamine were dissolved in 100 ml of toluene and cooled with ice. Pivalic acid chloride (4.05 g, 33.6 mmol) was added dropwise, and the mixture was stirred at room temperature (20 ° C.) for 1 hour. Next, after adding 5.95 g (45.8 mmol) of 3-chloropropylamine hydrochloride to the reaction mixture, the mixture was heated to reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, 100 ml of saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted twice with 200 ml of ethyl acetate. The obtained organic layer was washed sequentially with 1N hydrochloric acid aqueous solution (100 ml), saturated sodium hydrogen carbonate aqueous solution (100 ml) and saturated brine (100 ml), dried over anhydrous sodium sulfate, and the crude product obtained by distilling off the solvent under reduced pressure. Was purified by chromatography using silica gel (Wakogel B-10, manufactured by Wako Pure Chemical Industries, Ltd.) {developing solvent hexane: ethyl acetate 7: 1 → 3: 1 (volume ratio)} to give the title 2- (4 -Chloro-3,5-dimethylphenoxy) -N- [2-{(3-chloropropyl) amino} -1,1-dimethyl-2-oxoethyl] butanamide (9.84 g, white powder, yield 80%) Obtained.

Next, ¹ H-NMR spectral data of the amino acid amide derivative of the present invention (compound represented by the general formula (1)) are shown in Tables 2-1 to 2-8.
The ¹ H-NMR spectrum data of each compound was measured with a JNM-LA300 type nuclear magnetic resonance apparatus manufactured by JEOL Datum Co., Ltd. using tetramethylsilane (TMS) as a standard substance and deuterated chloroform (CDCl ₃ ) as a solvent. It was measured.

[Reference production example (first step)]
Preparation of 2-[{2- (4-chloro-3,5-dimethylphenoxy) butanoyl} amino] -2-methylpropionic acid 500 ml equipped with stirrer, reflux condenser and thermometer capable of measuring from 0 to 100 ° C. In a four-necked flask, 78.3 g (0.50 mol) of 4-chloro-3,5-dimethylphenol was dissolved in 150 ml of methanol, and 109 g (0.60 mol) of methyl 2-bromobutyrate was added at room temperature. Next, 48.0 g (1.2 mol) of sodium hydroxide was added, and the mixture was heated to reflux for 3 hours. After completion of the reaction, the solvent was distilled off, 100 ml of water was added to the reaction mixture, and the mixture was acidified with hydrochloric acid. The reaction mixture was extracted with 200 ml of ethyl acetate three times, and the organic layer was washed with 200 ml of saturated brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to remove solid 2- (4-chloro 110 g of a crude product of (3,5-dimethylphenoxy) butyric acid was obtained. The obtained crude product was washed with hexane to obtain 107 g of 2- (4-chloro-3,5-dimethylphenoxy) butyric acid (white powder, yield 88%).

  Next, in a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring from 0 to 100 ° C., 30.0 g of 2- (4-chloro-3,5-dimethylphenoxy) butyric acid (0 .12 mol) was dissolved in 200 ml of dichloromethane, and 17.8 g (0.14 mol) of oxalyl chloride and a catalytic amount of N, N-dimethylformamide (1 ml) were successively added under ice cooling, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 32.1 g of oily 2- (4-chloro-3,5-dimethylphenoxy) butyric acid chloride as a crude product.

  Subsequently, in a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring up to −50 to 50 ° C., 21.5 g (0.14 mol) of 2-aminoisobutyric acid methyl ester hydrochloride and triethylamine 26 .3 g (0.26 mol) was dissolved in a mixed solvent of 150 ml of dichloromethane and 30 ml of water, and this solution was cooled to 3 ° C. and stirred vigorously while obtaining 2- (4-chloro-3,5- A solution of a crude product of 32.1 g of (dimethylphenoxy) butyric chloride in 100 ml of dichloromethane was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 45 minutes. After completion of the reaction, the reaction mixture was washed successively with 150 ml of ice-cold water and 150 ml of saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give solid 2-[{2- (4- 37.7 g of a crude product of chloro-3,5-dimethylphenoxy) butanoyl} amino] -2-methylpropionic acid methyl ester was obtained. The obtained crude product was washed with hexane, and 36.5 g of 2-[{2- (4-chloro-3,5-dimethylphenoxy) butanoyl} amino] -2-methylpropionic acid methyl ester (white powder, Rate 89%).

  Next, in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring from 0 to 100 ° C., the obtained 2-[{2- (4-chloro-3,5-dimethylphenoxy] was obtained. ) Butanoyl} amino] -2-methylpropionic acid methyl ester 36.5 g (0.11 mol) dissolved in 100 ml of methanol, sodium hydroxide 8.80 g (0.22 mol) dissolved in 20 ml of water at room temperature (20 ° C.) The solution was added and stirred at room temperature for 1 hour. After completion of the reaction, methanol was distilled off from the reaction mixture under reduced pressure, 100 ml of ice-cold water was added to adjust the pH to 2 with a 1N hydrochloric acid aqueous solution, the aqueous layer was extracted three times with 250 ml of ethyl acetate, and the organic layer was saturated with brine. After washing with 100 ml and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain solid 2-[{2- (4-chloro-3,5-dimethylphenoxy) butanoyl} amino] -2- A compositional organism of methylpropionic acid was obtained. The obtained crude product was washed with hexane, and 24.3 g of 2-[{2- (4-chloro-3,5-dimethylphenoxy) butanoyl} amino] -2-methylpropionic acid (white powder, yield 95) %).

  Next, the method of formulating the amino acid amide derivative (I) of the present invention as a herbicide will be specifically described by the following Formulation Examples 1 to 6. However, the herbicide of this invention is not limited only to these formulation examples 1-6, and it cannot be overemphasized that it can mix with other various additives in arbitrary ratios, and can be formulated.

  The compound numbers are those shown in Tables 1-1 to 1-6, and in the following examples, “parts” are all parts by weight.

[Formulation Example 1] (Granule)
No. 15 parts of water was added to 1 part of 136 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. 136).

[Formulation Example 2] (Flowable agent)
No. 20.0 parts of 127 compound, 2.0 parts of di-2-ethylhexyl sulfosuccinic acid sodium salt, 2.0 parts of polyoxyethylene nonylphenyl ether, 5.0 parts of propylene glycol, 0.5 part of antifoaming agent 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. 127).

[Formulation Example 3] (Dry flowable agent)
No. No. 153, 75 parts, Isoban No. 153. 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 a herbicidal active ingredient (Compound No. 153).

[Formulation Example 4] (Wetting agent)
No. 15 parts of 154 compound, 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 pulverizing mixer to obtain a herbicidal active ingredient ( Compound No. 154) A wettable powder containing 15% is obtained.

[Formulation Example 5] (Emulsion)
No. 68 parts of Compound 68, Solpol 700H [Emulsifier: Toho Chemical Co., Ltd., trade name] 20 parts and 60 parts of xylene were mixed to obtain an emulsion containing 20% of a herbicidal active ingredient (Compound No. 68).

[Formulation Example 6] (Dust)
No. 67 parts of compound No. 67, 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. 67). A powder containing 0.5% was obtained.

  In addition, all the amino acid amide derivatives represented by the general formula (I) can be formulated into various dosage forms according to the formulation examples shown in the above Formulation Examples 1 to 6.

  Next, in order to illustrate the herbicidal effect of the amino acid amide derivative (I) of the present invention, Test Examples 1 to 4 are shown below.

[Test Example 1] Herbicidal effect test by pre-treatment of paddy rice generation and phytotoxicity test for transplanted rice paddy paddy soil filled in a 1 / 5,000 are Wagner pot, water added, and chemical fertilizer (N: P: K) = 17:17:17) and mixed. Thereafter, 30 seeds of Nobies, broad-leaved weeds (Azena, Konagi) 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 paddy rice transplantation, a wettable powder prepared according to Formulation Example 4 was diluted with water using the compounds shown in Table 3 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 concentration group, and the herbicidal rate (%) was determined by the following formula (1) 21 days after the drug treatment.

The results are shown in Tables 3-1 to 3-3 below.
The compound numbers in the table are the same as those shown in Tables 1-1 to 1-6.

The comparative compounds in Table 3 indicate the following compounds. This comparative compound is a compound described in JP-A-5-194344 of Patent Document 3. This comparative compound is also used in Test Examples 2, 3, and 4.

[Test Example 2] Herbicidal effect test by paddy rice growing season treatment 1 / 5,000 are wide Wagner pot filled with paddy soil, water added and chemical fertilizer (N: P: K = 17: 17: 17) ) Was mixed, and scavenging was performed. Thereafter, 30 seeds of Nobies, broad-leaved weeds (Azena, Konagi) 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 Formulation Example 4 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. The test was carried out in a two-reaction system per chemical solution concentration group, and the herbicidal rate (%) was determined according to the formula (1) 21 days after the drug treatment. The results are shown in Tables 4-1 to 4-3.
The compound numbers in the table are the same as those shown in Tables 1-1 to 1-6.

[Test Example 3] Herbicidal effect test and phytotoxicity test by upland field treatment 1) Herbicidal effect test on upland field weeds: field soil (alluvial loam soil) is packed in an unglazed pot with a size of 1 / 5,000 are and a surface layer of 1 cm 50 soils of each of the weeds of soil, barnyard grass, green crocodile, shiroza, Inuta, Inubibi and Hakobe were uniformly mixed, and the surface layer was lightly pressed. One day after sowing, an emulsion prepared according to Formulation Example 5 was diluted with water using the compounds shown in Table 5 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 Tables 5-1 to 5-3.

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. One day after sowing, an emulsion prepared according to Formulation Example 5 was diluted with water using the compounds shown in Table 5 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-reaction system per chemical solution concentration group, and the herbicidal rate (%) was determined according to the formula (1) 21 days after the drug treatment. The results are shown in Table 5.
The compound numbers in the table are the same as those shown in Tables 1-1 to 1-6.

[Test example 4] Herbicidal effect test and phytotoxicity test by field crop foliage treatment 1) Herbicidal effect test on field weeds: Field soil (alluvial loam soil) is packed in an unglazed pot of 1 / 5,000 are and the surface layer is 1 cm The soil and 50 weed seeds each of which were seeds of Japanese barnyard grass, Enocorosa, Shiroza, Inuta, Inubibi and Hakobe were uniformly mixed, and the surface layer was lightly pressed. Seven days after sowing, an emulsion prepared according to Formulation Example 5 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 Tables 6-1 to 6-3 below.

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, an emulsion prepared according to Formulation Example 5 was diluted with water using the compounds shown in Table 6 below, and the water-diluted drug solution was sprayed onto the plant body 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-reaction system per chemical solution concentration group, and the herbicidal rate (%) was determined according to the formula (1) 21 days after the drug treatment. The results are shown in Table 6 below.
The compound numbers in the table are the same as those shown in Tables 1-1 to 1-6.

Claims (2)

Formula (I)

[In General Formula (I), X represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group having 1 to 6 carbon atoms, and R ¹ represents a hydrogen atom, an alkyl having 1 to 6 carbon atoms. A C 1-6 alkyloxy group substituted with a group or a C 1-6 alkyl group, wherein R ² and R ³ are each independently a hydrogen atom, a C 1-6 alkyl group or a carbon number 1 to 6 hydroxyalkyl groups, each of R ⁴ and R ⁵ independently represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a hydroxyalkyl having 1 to 6 carbon atoms Group, an alkyloxy group having 1 to 6 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms, an oxyalkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms A cyanoalkyl group having 1 to 1 carbon atoms An optionally substituted aminoalkyl group having 3 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, an optionally substituted benzyl group, A carboxyalkyl group having 2 to 7 carbon atoms, or a carboxyalkenyl group having 3 to 7 carbon atoms, wherein R ⁴ and R ⁵ are —C ₂ H ₄ OC ₂ H ₄ —, —C ₄ H ₈ —, R ⁴ and R ⁵ may form a 5-membered or 6-membered ring together with the carbon atom to which each of R ⁴ and R ⁵ is bonded, and n represents an integer of 0 to 5, and when n is 2 or more, each X may be the same It may be different. ] The amino acid amide derivative represented by this.   A herbicide comprising the amino acid amide derivative represented by the general formula (I) according to claim 1 as a herbicidal active ingredient.