JP2001131008A - 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative, agrochemical and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new 2,3-dihydrobenzofuran-2-carboxylic acid amide having decreased phytotoxicity and excellent effect and provide an agrochemical, especially a herbicide containing the derivative as an active component. SOLUTION: The objective dihydrobenzofuran-2-carboxylic acid amide derivative is expressed by general formula (I) (Z1 and Z2 are each independently H or a lower alkyl; X1 and X2 are each independently H, OH, a lower alkyl, a lower alkoxy, a halogen-substituted alkoxy, benzyloxy, a halogen, nitro, cyano, phenyl or a haloalkl; Y1 and Y2 are each independently H, a lower alkyl, a lower alkoxy or a halogen; Q1 and Q2 are each independently H or a lower alkyl; and X1, X2, Z1 and Z2 are not H at the same time). The agrochemical, especially herbicide contains the compound as an active component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative and an agricultural chemical, particularly a herbicide, containing the compound as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, various compounds such as aliphatic amide compounds and chloroacetanilide compounds have been known as amide compounds having herbicidal activity. However, there is no report on the fact that the 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to the present invention has little phytotoxicity to useful plants and has excellent herbicidal activity. On the other hand, conventionally-known amide compounds exhibiting herbicidal activity have not always been sufficiently satisfactory in terms of the amount of drug delivered and the selectivity.

[0003]

The problem to be solved by the present invention is to provide a novel 2,3-dihydro which has little phytotoxicity to important crops, especially rice, and has excellent herbicidal activity against various weeds. An object of the present invention is to provide a benzofuran-2-carboxylic acid amide derivative and an agricultural chemical, particularly a herbicide containing the amide derivative as an active ingredient.

[0004]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted extensive studies on the synthesis of a derivative having a 2,3-dihydrobenzofuran-2-carboxylic acid amide structure and the pharmacological activity thereof. A novel 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative having a structure completely different from that of known compounds is useful, having high herbicidal activity against pesticides, especially important weeds in paddy fields, and extremely high safety against rice. It has been found that the herbicide is used for paddy fields, and the present invention has been completed.

That is, the present invention provides: (1) The following general formula (I)

[0006]

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(Wherein, Z ₁ and Z ₂ each independently represent a hydrogen atom or a lower alkyl group, and X ₁ and X ₂ each independently represent a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom Represents an alkoxy group, a benzyloxy group, a halogen group, a nitro group, a cyano group, a phenyl group or a haloalkyl group, and Y ₁ and Y ₂ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. Q ₁ and Q ₂ each independently represent a hydrogen atom or a lower alkyl group provided that X ₁ , X ₂ , Z
Except when ₁ and Z ₂ are both hydrogen atoms. A) 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative represented by the formula:

(2) The 2,3- according to (1), wherein Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group.
A dihydrobenzofuran-2-carboxylic acid amide derivative, (3) the 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to (1), wherein Z ₁ and Z ₂ are each independently a hydrogen atom or a methyl group,

(4) X ₁ and X ₂ each independently represent a hydrogen atom, a hydroxyl group, a lower alkyl group, a methoxy group, a difluoromethoxy group, a halogen atom, a nitro group, a cyano group, a benzyloxy group, a phenyl group (provided that 2,3-dihydrobenzofuran-2 according to any one of (1) to (3), except that X ₁ and X ₂ are simultaneously a hydrogen atom.
-Carboxamide derivatives,

(5) The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of (1) to (3), wherein X ₁ is a halogen atom and X ₂ is a hydrogen atom. (6) 2,3-Dihydrobenzofuran-2 according to any one of (1) to (5), wherein Y ₁ and Y ₂ are each independently a hydrogen atom, a halogen atom, a methyl group or a methoxy group.
-Carboxamide derivatives,

(7) The 2,3-dihydrobenzofuran-2-carboxylic acid amide according to any one of (1) to (5), wherein Y ₁ and Y ₂ are each independently a hydrogen atom or a halogen atom. (8) The 2,3- derivative according to any one of (1) to (7), wherein Q ₁ and Q ₂ are each independently a methyl group or an ethyl group.
Dihydrobenzofuran-2-carboxylic acid amide derivative,

(9) 2,3-dihydrobenzofuran-2- represented by the general formula (I) described in (1) to (8)
The 2,3-dihydrobenzofuran-2-carboxylic acid according to any one of (1) to (8), wherein the carboxylic acid amide derivative is a (-)-2,3-dihydrobenzofuran-2-carboxylic acid amide derivative. Acid amide derivatives,

(10) A pesticide containing as an active ingredient the 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of (1) to (9), (11) (1) to (9) 2) according to any one of 10);
A herbicide containing a 3-dihydrobenzofuran-2-carboxylic acid amide derivative as an active ingredient;

(12) General formula (II)

[0015]

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(Wherein, Z ₁ and Z ₂ each independently represent a hydrogen atom or a lower alkyl group, and X ₁ and X ₂ each independently represent a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom Represents a lower alkoxy group, a benzyloxy group, a halogen group, a nitro group, a cyano group, a phenyl group or a haloalkyl group substituted by Z ₁ ,
Except when Z ₂ , X ₁ and X ₂ are simultaneously a hydrogen atom. 2,3-dihydrobenzofuran-2- represented by
Carboxylic acid or a reactive derivative thereof, and the following general formula (II
I)

[0017]

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(In the formula, Y ₁ and Y ₂ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen group, and Q ₁ and Q ₂ each independently represent a hydrogen atom or a lower alkyl group. Wherein the amine is reacted directly or in the presence of a solvent (a).
General formula (I)

[0019]

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(Wherein Q ₁ , Q ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ ,
Z ₁ and Z ₂ have the same definitions as above. A method for producing a 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative represented by the formula:

(13) The method for producing a 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to (12), wherein Z ₁ and Z ₂ are each independently a hydrogen atom or a methyl group, (14) X ₁ or X ₂ is a halogen atom (12)
Or 2,3-dihydrobenzofuran according to (13).
A method for producing a 2-carboxylic acid amide derivative,

(15) The 2,3-dihydrobenzofuran-2-carboxylic acid amide according to any one of (12) to (14), wherein Y ₁ and Y ₂ are each independently a hydrogen atom or a halogen atom. A method for producing a derivative,

(16) The 2,3-dihydrobenzofuran-2-carboxylic acid amide according to any one of (12) to (15), wherein Q ₁ and Q ₂ are each independently a methyl group or an ethyl group. A method for producing a derivative,

(17) 2,3 represented by the general formula (II)
-Dihydrobenzofuran-2-carboxylic acid or a reactive derivative thereof is 2,3-dihydrobenzofuran-2-carboxylic acid optically resolved by an optically active substance or a reactive derivative thereof (12) to (16) A method for producing a 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of (16).

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative of the present invention is represented by the following general formula (I).

[0026]

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Here, Z ₁ and Z ₂ each independently represent a hydrogen atom or a lower alkyl group. The lower alkyl group may be a linear or chain lower alkyl group, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, ter
Those having 1 to 4 carbon atoms such as a t-butyl group are exemplified.
Preferred examples of Z ₁ and Z ₂ include hydrogen, a methyl group and an ethyl group, and more preferred are a hydrogen and a methyl group.

X ₁ and X ₂ are a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, a benzyloxy group, a halogen group, a nitro group, a cyano group, or a haloalkyl group. Represents

The lower alkyl group of X ₁ or X ₂ is a linear or chain lower alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Examples thereof include those having 1 to 4 carbon atoms such as a butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

As the lower alkoxy group for X ₁ or X ₂ ,
Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-
Those having 1 to 4 carbon atoms such as a butoxy group and a tert-butoxy group are exemplified.

The alkoxy group which may be substituted with a halogen atom for X ₁ or X ₂ is, as a halogen atom, 1 to 3
A fluorine atom which may be the same or different from each other,
Examples include a chlorine atom, a bromine atom or an iodine atom, and an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Examples include those having a number of 1 to 4, specifically, for example, chloromethoxy group, difluoromethoxy group, trifluoromethoxy group, difluorochloromethoxy group, pentafluoroethoxy group, 3,3,3-trifluoro-n -Propoxy group and the like.

Examples of the halogen atom for X ₁ or X ₂ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The phenyl group represented by X ₁ or X ₂ represents a substituted or unsubstituted phenyl group, for example, a phenyl group, a phenyl group substituted by an alkyl group having 1 to 2 carbon atoms,
Examples include a phenyl group substituted with two halogen atoms, and preferably an unsubstituted phenyl group.

Examples of the haloalkyl group represented by X ₁ or X ₂ include, as a halogen atom, 1 to 3 fluorine atoms, chlorine atoms, bromine atoms or iodine atoms which may be the same or different from each other. , Ethyl group,
Examples thereof include those having 1 to 4 carbon atoms such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and specifically, for example, chloromethyl group, difluoromethyl Group, trifluoromethyl group,
Difluorochloromethyl group, pentafluoroethyl group,
3,3,3-trifluoro-n-propyl group and the like.

X ₁ or X ₂ is preferably a hydrogen atom,
Hydroxyl group, methyl group, isopropyl group, t-butyl group, methoxy group, difluoromethoxy group, halogen atom, nitro group, cyano group, benzyloxy group, phenyl group,
Particularly preferred is a halogen atom, and particularly preferred is a halogen atom at the 7-position.

Y ₁ and Y ₂ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen group. As the lower alkyl group for Y ₁ or Y ₂ ,
A linear or chain lower alkyl group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t
Examples thereof include those having 1 to 4 carbon atoms such as an ert-butyl group.

As the lower alkoxy group for Y ₁ or Y ₂ ,
Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-
Those having 1 to 4 carbon atoms such as a butoxy group and a tert-butoxy group are exemplified.

Examples of the halogen atom for Y ₁ or Y ₂ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Y ₁ or Y ₂ is preferably a hydrogen atom, a halogen atom, a methyl group or a methoxy group, particularly preferably a hydrogen atom or a halogen atom.

Q _{1 and} Q ₂ each independently represent a hydrogen atom or a lower alkyl group. The lower alkyl group for Q ₁ or Q ₂ is a linear or chain lower alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group. , A sec-butyl group, a tert-butyl group and the like having 1 to 4 carbon atoms. Preferably, Q ₁ or Q ₂ is a hydrogen atom or a methyl group.

However, the case where X ₁ , X ₂ , Z ₁ and Z ₂ are simultaneously hydrogen atoms is excluded.

Hereinafter, the compounds of the 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to the present invention will be specifically described. The symbols in the table have the following meanings. bz: benzyl, Pr: propyl, iPr: isopropyl, tBu: tert-butyl, Ph: phenyl. Further, the following (+) and (-) represent optically active substances,
They represent dextrorotatory and levorotatory, respectively.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to the present invention has the following reaction formula (1):

[0049]

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The following general formula (II):

[0051]

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2,3-dihydrobenzofuran-2-carboxylic acid or a reactive derivative thereof represented by
"2,3-dihydrobenzofuran-2-carboxylic acid derivative") and a compound represented by the general formula (III)

[0053]

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The reaction can be carried out directly or in the presence of the solvent (a) with the corresponding amine represented by the formula (1). X ₁ , X ₂ , Z ₁ and Z _{2 in the} general formula (II) and Q ₁ , Q ₂ , Y ₁ and Y ₂ in the general formula (III) are as defined above.

The reaction temperature in the reaction formula (1) is 0 to 1
The temperature can be appropriately set within the range of 00 ° C. or the boiling point of the solvent (a). The reaction time varies depending on the compound used, the type of the solvent, and the like, but is usually 1 to 24 hours. The reactive derivatives of 2,3-dihydrobenzofuran-2-carboxylic acid include corresponding acid anhydrides, acid halides, carboxylic esters, and the like.

As the solvent (a), water, halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), aromatics Hydrocarbons (toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.) And acid amides (dimethylformamide, dimethylacetamide, etc.), nitriles (acetonitrile, propionitrile, etc.), sulfoxides (dimethylsulfoxide, sulfolane, etc.). Preferred are halogenated hydrocarbons and aromatic hydrocarbons, and more preferred is dichloromethane.

On the other hand, 2,3-dihydrobenzofuran-2-carboxylic acid represented by the general formula (II) can be reacted with a suitable reaction aid (dicyclohexylcarbodiimide, water-soluble carbodiimide, carbonyldiimidazole, N-methyl-2-chloroform). Condensing agents such as pyridinium halogenides, phosphorus pentachloride,
Chlorinating agents such as phosphorus trichloride, phosphorus oxychloride, oxalyl chloride, thionyl chloride, triethylamine, pyridine, dimethylaniline, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc. An organic or inorganic base) can be used for the reactive derivatization.

The optically active form of the compound represented by the general formula (I) is exemplified by the following reaction formula (2):

[0059]

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As shown in the above formula, the racemic 2,3-dihydrobenzofuran-2-carboxylic acid represented by the general formula (II) is optically resolved using an optically active substance, and the obtained optically active 2 By reacting a 2,3-dihydrobenzofuran-2-carboxylic acid derivative (general formula (IV)) with an amine, a 2,3-dihydrobenzofuran-2-carboxylic acid represented by general formula (-)-(I) is obtained. Acid amide derivatives can be produced.

Where Q ₁ , Q ₂ , X ₁ , X ₂ , Y ₁ ,
Y ₂ , Z ₁ and Z ₂ are as defined above, and are the same as defined in the above general formula (I). The optically active substance used in the optical resolution is not particularly limited as long as it is a known and commonly used optical resolution agent. Specifically, for example, (S)-(−)-methylbenzylamine, (S) −
(-)-1- (1-octyl) -ethylamine, (-)
-Cis-N-benzyl-2- (hydroxymethyl) -cyclohexylamine and (l) -amphetamine or S
-Naphthylethylamine and the like, preferably (S)-(-)-methylbenzylamine.

The 2,3-dihydrobenzofuran-2-carboxylic acid represented by the general formula (II), which is an intermediate used for producing the 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to the present invention. The acid derivatives are listed in Table 7 below.
This will be specifically described in Table 9 below.

[0063]

[Table 7]

[0064]

[Table 8]

[0065]

[Table 9]

The 2,3-dihydrobenzofuran of the present invention
Pesticides, particularly herbicides, containing a 2-carboxylic acid amide derivative as an active ingredient exhibit excellent selectivity for rice, which is an important crop, as their action characteristics, while causing harmful weeds which are problematic in most paddy fields, For example, it shows an excellent herbicidal effect on grass weeds such as nobies, cyperaceae weeds such as stag beetle and scallop, annual broadleaf weeds such as oak, and perennial weeds such as urikawa, and has excellent selectivity.

In addition, the herbicide according to the present invention can be effectively used in various treatment methods such as flooded soil treatment, soil treatment and soil admixture, from before the emergence of weeds to the growing season after the emergence. .

When the compound of the present invention is actually used as a pesticide, it is possible to use the drug substance alone as a form of use. Agents, diluents, emulsifiers, spreading agents,
Auxiliaries such as thickeners can be mixed and formulated into dosage forms such as wettable powders, liquids, oils, powders, granules, sols (flowable), and used.

Examples of solid and liquid carriers include talc, clay, bentonite, kaolin, diatomaceous earth, montmorillonite, mica, vermiculite, gypsum, calcium carbonate, white carbon, wood powder, starch, alumina, silicate, and sugar polymer. , Waxes, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol, etc.), petroleum fractions (petroleum ether, kerosene, solvent naphtha, etc.), Aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene, etc.), ethers (isopropyl ether, tetrahydrofura) ), Ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetanilide, etc.), nitrile (E.g., acetonitrile, propionitrile, acrylonitrile), sulfoxides (e.g., dimethyl sulfoxide), and alcohol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether).

Examples of the auxiliary include nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.),
Anionic surfactants (alkylbenzene sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, aryl sulfonate, etc.), and cationic surfactants (alkylamines, polyoxyethylene alkylamines, quaternary) Ammonium salts, etc.), amphoteric surfactants (alkylaminoethylglycine, alkyldimethylbetaine, etc.), polyvinyl alcohol, hydroxypropylcellulose, carboxymethylcellulose, gum arabic, tragacanth gum, xanthan gum, polyvinyl acetate, gelatin, casein, sodium alginate, etc. Is mentioned.

The content of the active ingredient compound in the pesticide according to the present invention, particularly in the herbicide, varies depending on the form of preparation.
Usually 0.01 to 20% by weight for powders and 1 to 5 for wettable powders
0% by weight, 0.01 to 10% by weight for granules, 0.1 to 50% by weight for emulsions, 0.1 to 50% by weight for flowables, 1 to 50% by weight for dry flowables,
Preferably, 0.1 to 3% by weight for powder and 1 to 1 for wettable powder.
0 to 40% by weight, 0.1 to 5% by weight for granules, 1 to 30% by weight for emulsions, 1 to 30% by weight for flowables, and 10 to 40% by weight for dry flowables.

The content of the adjuvant is from 0 to 80% by weight, and the content of the carrier is an amount obtained by subtracting the contents of the active ingredient compound and the adjuvant from 100% by weight.

The application amount of the herbicide of the present invention varies depending on the occurrence of weeds, the environment, the form of preparation used, and the like.
0.002 per hectare of compound active ingredient
It is desirable to select from a range of 2 kg, preferably from 0.025 to 0.6 kg.

The herbicide containing the compound of the present invention may be mixed with one or more other herbicides, or a pesticide such as a fungicide, an insecticide, a plant growth regulator, a fertilizer, a soil conditioner and the like. It can be used, and a mixed preparation with these can be used.

[0075]

EXAMPLES Next, the present invention will be described in detail with reference to Production Examples, Preparation Examples and Test Examples as examples, but the present invention is not limited to these examples. Example 1 Preparation of Compound No. 1 Oxalyl was added to a catalytic amount of N, N-dimethylformamide and 0.5 ml of 4,6-dichloro-2,3-dihydrobenzofuran-2-carboxylic acid in 4 ml of dichloromethane at room temperature. 0.26 ml of chloride was added dropwise and stirred for 2 hours. After the solvent was distilled off under reduced pressure, it was added to 5 ml of a dichloromethane solution of 0.42 g of α, α-dimethylbenzylamine and 0.7 g of triethylamine at room temperature. After completion of the reaction, the reaction solution was washed with 1N-hydrochloric acid and dried over anhydrous magnesium sulfate.
After concentration under reduced pressure by an evaporator, purification by silica gel chromatography (developing solvent: dichloromethane) gives N- (α, α-dimethylbenzyl) -4,6 of the present invention.
0.77 g of -dichloro-2,3-dihydrobenzofuran-2-carboxylic acid amide (Compound No. 1) was obtained.

Example 2 Preparation of Compound No. 87-B (optically active substance) A catalytic amount of N, N-dimethylformamide and (-)-7-methyl-2,3-dihydrobenzofuran-2-carboxylic acid 0 Oxalyl chloride (0.33 ml) was added dropwise to 0.62 g of a dichloromethane solution (4 ml) at room temperature, followed by stirring for 2 hours.
After evaporating the solvent under reduced pressure, 0.52 g of α, α-dimethyl-4-fluorobenzylamine and 0.7% of triethylamine
5 g of a 7 g dichloromethane solution was added at room temperature. After completion of the reaction, the reaction solution was washed with hydrochloric acid and dried over anhydrous magnesium sulfate. After concentration under reduced pressure by an evaporator, the residue was purified by silica gel chromatography (developing solvent: dichloromethane) to obtain Compound No. 87-B0.96 of the present invention.
g was obtained.

[Α] ²⁵ D = −86.3 ° (c = 0.2
4, methanol) Next, Examples 2 to 87- obtained in the same manner as in Example 1
Tables 10 to 26 show the physical property values of the compounds according to the present invention for A, 87-C to 100-C. The compound numbers are shown in Tables 1 to
It corresponds to the compound number in Table 6.

[0078]

[Table 10]

[0079]

[Table 11]

[0080]

[Table 12]

[0081]

[Table 13]

[0082]

[Table 14]

[0083]

[Table 15]

[0084]

[Table 16]

[0085]

[Table 17]

[0086]

[Table 18]

[0087]

[Table 19]

[0088]

[Table 20]

[0089]

[Table 21]

[0090]

[Table 22]

[0091]

[Table 23]

[0092]

[Table 24]

[0093]

[Table 25]

[0094]

[Table 26]

Next, Formulation Examples and Test Examples will be given. The numbers in the Formulation Examples are percentages by weight.

[0096]

[Table 27]

The above was mixed and pulverized to obtain a wettable powder.

[0098]

[Table 28]

The above was uniformly dissolved to form an emulsion.

[0100]

[Table 29]

The above components were uniformly mixed and pulverized, kneaded by adding water, and then granulated and dried to obtain granules. (Test Example 1) Flooding soil treatment Two days before chemical treatment, pot (area 60 cm ² , depth 6 cm)
Was filled with field soil, and seeds of nobies, dog squirrels, puppies, and oysters were sown on the soil surface, and then the rice at the two leaf stage was transplanted into a flooded state. The medicinal solution prepared to a predetermined concentration was treated in a pot, and after 20 days, the herbicidal effect and the chemical damage to the crop were determined. The results are shown in Tables 31 to 34. The herbicidal effect and phytotoxicity were in accordance with the following criteria.

[0102]

[Table 30]

The compound numbers in the following Tables 31 to 34 correspond to the compound numbers shown in Tables 1 to 6, and the plant names are abbreviated as follows. Transplanted rice = R, nobie = E, dogfly = Sc, corn = M,
Tamayatsuri = Cy.

[0104]

[Table 31]

[0105]

[Table 32]

[0106]

[Table 33]

[0107]

[Table 34]

Test Example 2 Comparative test of herbicidal activity of racemic compound and optically active compound Comparative test of herbicidal effect of racemic compound and optically active compound shown in the Examples using the same method as in Test Example 1 (dose applied: 30
g / 10a). Table 35 shows the results. still,
The compound numbers in Table 35 below correspond to the compounds with the compound numbers described in Tables 1 to 6, and the plant names are abbreviated as follows. Transplanted rice = R, nobie = E, dogfly = Sc, oak = M, cyperus = Cy. The results are shown in Table 35. As is clear from Table 35, the activity of the (-)-form is more improved than that of the racemic form, and the activity of the other optically active form (+)-form is not recognized. In the -dihydrobenzofuran-2-carboxylic acid amide derivative, the (-)-optically active compound was found to be important.

[0109]

[Table 35]

Test Example 3 Test of herbicidal activity of target compound 1- (α, α-dimethylbenzyl)-
3- (p-tolyl) urea (indicated by "A" in the table below)
And (RS) -1-bromo-N- (α, α-dimethylbenzyl) -2,2-dimethylpropamide (indicated by “B” in the table below) to conduct a herbicidal activity test. The test method was performed in the same manner as in Test Example 1, and the applied drug amount was 30, 60 respectively.
g / 10a.

[Table 36]

[0111]

Industrial Applicability The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to the present invention exhibits selectivity for rice, which is an important crop, as an agrochemical, especially as a herbicide, and is excellent against various weeds. It has herbicidal activity.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tetsu Ohno 1-34-5-207, Miyakomachi, Chuo-ku, Chiba-shi, Chiba (72) Inventor Mika Takahashi 1-27-1-B318, Osakidai, Sakura-shi, Chiba ( 72) Inventor Toru Asada 4-18-6 Chuodai, Shisui-machi, Inba-gun, Chiba F-term (reference) 4H011 AB01 AB02 BA01 BB08 BC01 BC07 BC18 BC19 BC20 DA02 DA15 DA16 DD01 DG05 DH03

Claims (17)

[Claims] 1. A compound represented by the following general formula (I): (Wherein, Z ₁ and Z ₂ each independently represent a hydrogen atom or a lower alkyl group, and X ₁ and X ₂ each independently represent a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, or a halogen atom. Represents an alkoxy group, a benzyloxy group, a halogen group, a nitro group, a cyano group, a phenyl group or a haloalkyl group, and Y ₁ and Y ₂ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen group. , Q ₁ and Q ₂ each independently represent a hydrogen atom or a lower alkyl group, provided that X ₁ , X ₂ , Z ₁ and Z ₂ are simultaneously a hydrogen atom. −
Dihydrobenzofuran-2-carboxylic acid amide derivative. 2. The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to claim 1, wherein Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group. 3. The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to claim 1, wherein Z ₁ and Z ₂ are each independently a hydrogen atom or a methyl group. 4. X ₁ and X ₂ each independently represent a hydrogen atom, a hydroxyl group, a lower alkyl group, a methoxy group, a difluoromethoxy group, a halogen atom, a nitro group, a cyano group, a benzyloxy group, a phenyl group (however, 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of claims 1 to 3 is a.) except when ₁ and X ₂ are not hydrogen atoms at the same time. 5. The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to claim 1, wherein X ₁ is a halogen atom and X ₂ is a hydrogen atom. 6. The method according to claim _1, wherein Y ₁ and Y ₂ are each independently a hydrogen atom, a halogen atom, a methyl group or a methoxy group.
6. The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of 5. 7. The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to claim 1, wherein Y ₁ and Y ₂ are each independently a hydrogen atom or a halogen atom. 8. The compound according to claim _1, wherein Q ₁ and Q ₂ are each independently a methyl group or an ethyl group.
3-dihydrobenzofuran-2-carboxylic acid amide derivative. 9. The 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative represented by the general formula (I) according to claim 1, wherein the derivative is (-)-2,3-dihydrobenzofuran-2-carboxylic acid. The 2,3-dihydrobenzofuran-2 according to any one of claims 1 to 8, which is an acid amide derivative.
-Carboxamide derivatives. 10. An agricultural chemical comprising the 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of claims 1 to 9 as an active ingredient. 11. A herbicide comprising the 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of claims 1 to 10 as an active ingredient. 12. A compound of the general formula (II) (Wherein, Z ₁ and Z ₂ each independently represent a hydrogen atom or a lower alkyl group, and X ₁ and X ₂ each independently represent a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, or a halogen atom. Lower alkoxy group, benzyloxy group,
Represents a halogen group, a nitro group, a cyano group, a phenyl group or a haloalkyl group. However, the case where Z ₁ , Z ₂ , X ₁ and X ₂ are simultaneously a hydrogen atom is excluded. 2, 3)
-Dihydrobenzofuran-2-carboxylic acid or a reactive derivative thereof, and a compound represented by the following general formula (III): (Wherein, Y ₁ and Y ₂ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen group, and Q ₁ and Q ₂ each independently represent a hydrogen atom or a lower alkyl group. Wherein the amine represented by the general formula (I) is reacted directly or in the presence of the solvent (a). (Wherein Q ₁ , Q ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ and Z ₂ have the same definition as above). A method for producing a carboxylic acid amide derivative. 13. The method for producing a 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to claim 12, wherein Z ₁ and Z ₂ are each independently a hydrogen atom or a methyl group. 14. The method for producing a 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to claim 12, wherein X ₁ or X ₂ is a halogen atom. 15. The production of a 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of claims 12 to 14, wherein Y ₁ and Y ₂ are each independently a hydrogen atom or a halogen atom. Method. 16. The production of a 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of claims 12 to 15, wherein Q ₁ and Q ₂ are each independently a methyl group or an ethyl group. Method. 17. A 2,3-dihydrobenzofuran-2-carboxylic acid obtained by optically resolving a 2,3-dihydrobenzofuran-2-carboxylic acid represented by the general formula (II) or a reactive derivative thereof by an optically active substance Or the reactive derivative thereof. The method for producing a 2,3-dihydrobenzofuran-2-carboxylic acid amide derivative according to any one of claims 12 to 16, wherein the derivative is a reactive derivative thereof.