JPH05170739A - Benzooxadinylpyridone derivative, its production, herbicide containing the same as active ingredient and its intermediate - Google Patents

Abstract

(57) [Summary] (Modified) [Structure] A benzoxazinylpyridone derivative represented by the general formula shown. [In the formula, R represents an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group or an alkoxyalkyl group, and X represents a hydrogen atom, a halogen atom,
Represents a methyl group optionally substituted with a halogen atom or an ethyl group optionally substituted with a halogen atom,
Y represents a hydrogen atom or a methyl group. [Effect] The above compounds have excellent herbicidal activity against various weeds which are problematic in soil treatment of fields, foliage treatment and flooding treatment of paddy fields, and some of them have major crops and weeds. It is useful as an active ingredient of herbicides because of its excellent selectivity.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel benzoxazinylpyridone derivative, a process for producing the same, a herbicide containing the same as an active ingredient, and an intermediate thereof.

[0002]

BACKGROUND OF THE INVENTION There are many known compounds that can be used as active ingredients of herbicides, but they have insufficient herbicidal efficacy or poor selectivity between crops and weeds. It's hard to say that it's always satisfying. In addition, it is described in JP-A-62-70362 and JP-A-63-68566 that certain phenylpyridone derivatives can be used as an active ingredient of an insecticide.

[0003]

SUMMARY OF THE INVENTION The present inventors have made various studies in view of such circumstances, and as a result, the pyridone derivative having a benzoxazine ring has few drawbacks as described above.
The inventors have found that the compound has an excellent herbicidal effect and exhibits excellent selectivity between crops and weeds, and completed the present invention.

That is, the present invention has the general formula

[Chemical 6] [In the formula, R represents an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group or an alkoxyalkyl group, and X represents a hydrogen atom, a halogen atom,
Represents a methyl group optionally substituted with a halogen atom or an ethyl group optionally substituted with a halogen atom,
Y represents a hydrogen atom or a methyl group. ] The benzoxazinyl pyridone derivative (henceforth the compound of this invention) shown by these is provided.

In the compound represented by the above chemical formula 6, the substituent R is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group. Group, n-heptyl group, n-octyl group, 2-propenyl group, 1-methyl-
2-propenyl group, 2-butenyl group, 1-methyl-2-
Butenyl group, 3-methyl-2-butenyl group, 1,3-dimethyl-2-butenyl group, 2-methyl-2-propenyl group, 1,2-dimethyl-2-propenyl group, 1,2,3
-Trimethyl-2-butenyl group, 2,3-dimethyl-2
-Butenyl group, 2-methyl-2-butenyl group, 1,2-
Dimethyl-2-butenyl group, 2-propynyl group, 1-methyl-2-propynyl group, 2-butynyl group, 1-methyl-2-butynyl group, 2-pentynyl group, 1-methyl-2
-Pentynyl group, 3-butynyl group, 1-methyl-3-butynyl group, 1,2-dimethyl-3-butynyl group, methoxymethyl group, 1-methoxyethyl group, ethoxymethyl group, 1-ethoxyethyl group, n -A propoxymethyl group,
Isopropoxymethyl group, 1- (n-propoxy) ethyl group, n-butoxymethyl group, 1- (n-butoxy) ethyl group, methoxyethyl group, ethoxyethyl group, 1-methyl-2-methoxyethyl group, 1 -Methyl-2-ethoxyethyl group, n-propoxyethyl group, n-butoxyethyl group, 1-methyl-2- (n-butoxy) ethyl group,
2-fluoroethyl group, 2,2-difluoroethyl group,
2,2,2-trifluoroethyl group, 2-chloroethyl group, 3-chloro-2-propenyl group, 2-chloro-2-
Examples thereof include a propenyl group and a 2,3-dichloro-2-propenyl group. Examples of the substituent X include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group,
Examples thereof include a fluoromethyl group, difluoromethyl group, and fluoroethyl group, and examples of the substituent Y include a hydrogen atom and a methyl group.

Among the compounds of the present invention, preferred compounds
Is R is C₂~ C_FourAlkyl group, C₃~ C_FourAlkenyl
Base, C₃~ C_FourAlkynyl group, 2-fluoroethyl group
Or C ₁~ C₃Alkoxymethyl group, X is hydrogen source
Child, fluorine atom, chlorine atom, bromine atom, methyl group, full
Is an oromethyl group or a difluoromethyl group, and Y is water
The compound which is an elementary atom or a methyl group is mentioned.

Further preferred compounds are those in which R is n-
Propyl group, isopropyl group, sec-butyl group, C ₃
To C ₄ alkenyl group, C _{3 to} C ₄ alkynyl group, 2-fluoroethyl or methoxymethyl group, X is a fluorine atom, chlorine atom, bromine atom or methyl group, and Y
And a compound in which is a hydrogen atom or a methyl group.

Next, a method for producing the compound of the present invention will be described. The compound of the present invention has the general formula

[Chemical 7] [In the formula, X and Y have the same meanings as described above. ] The compound shown by these, and general formula RW [I] [In formula, W represents a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, or a methanesulfonyloxy group, and R has the same meaning as the above. Represents. ] It can manufacture by making it react with the compound shown by these.

This reaction is usually carried out in a solvent in the presence of a base, the reaction temperature range is 0 to 100 ° C., and the reaction time range is 0.5 to 10 hours. Of the compound of the general formula [I] with respect to 1 equivalent of the compound represented by the formula
The compound represented by is 1 to 2 equivalents, and the base is 1 to 2 equivalents.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and diethylene glycol dimethyl ether. Ethers, acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone, isophorone and cyclohexanone, alcohols such as methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol and glycerin, nitriles such as acetonitrile and isobutyronitrile, pyridine , Triethylamine, N, N-diethylaniline, tributylamine, N
-A tertiary amine such as methylmorpholine, formamide,
Examples thereof include acid amides such as N, N-dimethylformamide and acetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, liquid ammonia, water and the like, or a mixture thereof.

Examples of the base include organic bases such as pyridine, triethylamine and N, N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, sodium methoxide and sodium ethoxy. Examples thereof include alkali metal alkoxides such as Cd.

After completion of the reaction, the reaction solution is poured into water and the resulting crystals are filtered or subjected to usual post-treatments such as organic solvent extraction and concentration, and if necessary, chromatography, distillation,
The desired compound of the present invention can be obtained by purification by an operation such as recrystallization.

Tables 1 to 10 show some of the compounds of the present invention represented by Chemical formula 6 which can be produced according to the above production method.
In the table, R, X and Y are the substituents R and X of Chemical formula 6, respectively.
And Y.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5]

[0019]

[Table 6]

[0020]

[Table 7]

[0021]

[Table 8]

[0022]

[Table 9]

[0023]

[Table 10]

Some of the compounds of the present invention have optical isomers derived from asymmetric carbon, and these optical isomers are also included in the present invention.

Next, a method for producing the compound represented by Chemical formula 7, which is a starting material compound for the compound of the present invention, will be explained. The compound represented by Chemical formula 7 can be produced according to the following route.

[0026]

[Chemical 8] [In the formula, R'represents an alkyl group, and X and Y have the same meanings as described above. ]

(Production Method A) [II] + [III] → [IV] The compound [IV] can be produced by reacting the compound [II] with the compound [III]. This reaction is generally carried out without solvent or in a solvent in the presence of a base, the reaction temperature range is 0 to 100 ° C., and the reaction time range is
The reaction time is 0.5 to 24 hours, and the amount of the reagent used for the reaction is 1 to 1.1 equivalents of the compound [III] and 1 to 2 equivalents of the base with respect to 1 equivalent of the compound [II].

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like. Ethers, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone and other ketones, methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, 2-methoxyethanol, diethylene glycol, glycerin and other alcohols, ethyl formate , Ethyl acetate, butyl acetate, diethyl carbonate, etc. esters, acetonitrile, isobutyronitrile, etc. nitriles, pyridine, triethylamine , N, N-diethylaniline,
Tertiary amines such as tributylamine and N-methylmorpholine, formamide, N, N-dimethylformamide,
Examples thereof include acid amides such as acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, liquid ammonia, water and the like, or a mixture thereof.

Examples of the base include organic bases such as pyridine, triethylamine and N, N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, sodium methoxide and sodium ethoxy. Examples thereof include alkali metal alkoxides such as Cd.

After the completion of the reaction, the reaction solution is poured into water, and the resulting crystals are filtered or subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purification is carried out by operations such as chromatography and recrystallization. Thus, the compound [IV] can be obtained. The compound [III] is disclosed in JP-A-63-
It can be produced according to the production method described in 68566.

(Production Method B) [IV] → [V] The compound [V] can be produced by reducing the compound [IV]. This reaction is usually performed in a solvent in the presence of a reducing agent. Examples of the reducing agent include a metal such as iron and tin and a protonic acid, and in some cases, a combination of hydrogen and a metal such as platinum and palladium.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and diethylene glycol dimethyl ether. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone and cyclohexanone, fatty acids such as formic acid, acetic acid and oleic acid, methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, 2-methoxyethanol, diethylene glycol, Alcohols such as glycerin, ethyl formate, ethyl acetate, butyl acetate,
Esters such as diethyl carbonate, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N, N-diethylaniline, tributylamine,
Examples thereof include tertiary amines such as N-methylmorpholine, acid amides such as formamide, N, N-dimethylformamide and acetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, liquid ammonia, water and the like, or a mixture thereof.

After completion of the reaction, the insoluble matter is filtered off, then the usual post-treatments such as extraction with an organic solvent and concentration are carried out, and if necessary, purification is carried out by operations such as chromatography and recrystallization to give the compound [V ] Can be obtained.

(Production Method C) [V] → [VI] The compound [VI] can be produced by diazotizing the compound [V] to form a diazonium salt, and subsequently performing diazo decomposition without isolation.

The diazotization reaction is usually carried out in the presence of an acid such as sulfuric acid, the reaction temperature range is -10 to 10 ° C, and the reaction time range is 1 to 5 hours. The amount of sodium nitrite is 1-2 with respect to 1 equivalent of compound [V].
It is equivalent. The subsequent diazo decomposition reaction is usually
It is carried out in a solvent such as water in the presence or absence of an acid such as sulfuric acid. The reaction temperature range is 80 to 120 ° C., and the reaction time range is 0.5 to 2 hours.

After completion of the reaction, the reaction solution is subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purified by a procedure such as chromatography, recrystallization and the like to obtain the compound [VI].

(Production Method D) [VI] → [VII] The compound [VII] can be produced by nitrating the compound [VI]. This reaction is usually carried out without solvent or in a solvent, The reaction temperature range is -20 to 20.
The reaction time range is 0.5 to 2 hours, and the amount of the reagent to be used in the reaction is 1 equivalent of the compound [VI] to 1 nitric acid.
~ 1.1 equivalents.

Examples of the solvent include halogenated hydrocarbons such as chloroform, carbon tetrachloride and dichloroethane, water or a mixture thereof.

After completion of the reaction, the reaction solution is subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purified by a procedure such as chromatography, recrystallization and the like to obtain the compound [VII]. it can.

(Production Process E) [VII] → [VIII] The compound [VIII] includes the compound [VII] and the general formula WCH ₂ CO ₂ R ′ [IX] [wherein W and R ′ have the same meanings as described above]. Represent. ] It can manufacture by making it react with the compound shown by these. This reaction is usually carried out in the presence of a base in a solvent, the reaction temperature range is 0 to 100 ° C., the reaction time range is 0.5 to 10 hours, and the amount of reagents to be used in the reaction is Compound [IX] is 1 to 1 equivalent to Compound [VII].
2 equivalents, 1 to 2 equivalents of base.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, dichloroethane, chlorobenzene and dichlorobenzene. , Diethyl ether,
Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methanol, ethanol, isopropanol, t-
Butanol, octanol, cyclohexanol, 2-
Alcohols such as methoxyethanol, ethylene glycol and glycerin, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N, N-diethylaniline, Examples thereof include tertiary amines such as tributylamine and N-methylmorpholine, acid amides such as formamide, N, N-dimethylformamide and acetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, liquid ammonia, water and the like, or a mixture thereof. ..

Examples of the base include organic bases such as pyridine, triethylamine and N, N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, sodium methoxide and sodium ethoxy. Examples thereof include alkali metal alkoxides such as Cd. After completion of the reaction, the compound is obtained by pouring the reaction solution into water and collecting the resulting crystals by filtration, or by performing usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purification by operations such as chromatography and recrystallization. [VIII] can be obtained.

(Production Method F) [VIII] → Chemical Formula 7 The compound represented by the chemical formula 7 can be produced by reducing the compound [VIII] to cyclize. This reaction is usually performed in a solvent in the presence of a reducing agent, the reaction temperature range is 70 to 150 ° C., and the reaction time range is 10 minutes to 2
It's time.

Examples of the reducing agent include a combination of a metal such as iron and tin and a protonic acid, or a combination of a metal such as platinum and palladium and hydrogen.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane and ligroin, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated carbonization such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene. Hydrogens, ethers such as diisopropyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether, ketones such as methyl isobutyl ketone, isophorone and cyclohexanone, fatty acids such as formic acid, acetic acid and oleic acid, ethanol,
Alcohols such as isopropanol, t-butanol, octanol, cyclohexanol, 2-methoxyethanol, diethylene glycol and glycerin, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate, nitriles such as acetonitrile and isobutyronitrile. , Tertiary amines such as pyridine, triethylamine, N, N-diethylaniline, tributylamine and N-methylmorpholine, acid amides such as formamide, N, N-dimethylformamide and acetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, Examples include water and the like or a mixture thereof.

After completion of the reaction, the insoluble matter is filtered off, and then ordinary post-treatments such as extraction with an organic solvent and concentration are carried out, and if necessary, purification is carried out by operations such as chromatography and recrystallization to give compound 7 The compounds shown can be obtained.

The compounds of the present invention have excellent herbicidal activity. That is, the compound of the present invention, various weeds that are problematic in the foliar treatment and soil treatment of upland fields, for example, buckwheat vine, Sanaetade, purslane, chickweed, white azalea, Aogateto, Japanese radish, Noragarashi, Nazuna, Astragalus vulgaris, Ebisugusa, Ichibi, America. Sida, field pansy, yamgra, American morning glory, Malva morning glory, Convolvulus vulgaris, Anemone duckweed, photokenosa, white butterfly, morning glory, dogwood throat, red-billed corn, corn marigold, sunflower, etc. Barnyardgrass, green foxtail, stiltgrass, bluegrass, bluegrass, oat, oats, scorpion sorghum, oatgrass, horsetail, Rhododendron chinensis, grass weeds such as Aquinoe gnocologsa, weeding weeds such as Commelinae, cyperaceae weeds such as Kogomegayatsu, etc., which have herbicidal activity, and among the compounds of the present invention, corn, wheat, rice, soybean, It does not show any harmful effects on major crops such as cotton.

Further, some of the compounds of the present invention are various weeds which are problematic in the flooding treatment of paddy fields, for example,
It has herbicidal activity against grass weeds such as Taenia japonica, broad-leaved weeds such as Azena, scabbard, and Mizohabe, Cyperaceae weeds such as cypress, firefly, matsubai, konagi, urikawa, and is a problem for rice. It does not show such phytotoxicity.

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant or other auxiliaries for formulation to prepare an emulsion, a wettable powder, a suspension,
Formulated in granules, wettable granules, etc. These formulations contain the compound of the present invention as an active ingredient in a weight ratio of 0.03 to 80%, preferably 0.05 to 70%.

As solid carriers, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powder,
Examples thereof include fine powders or granules of urea, ammonium sulfate, synthetic hydrous silicon oxide and the like, and liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve, acetone, cyclohexanone. , Ketones such as isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wet extension, etc. include alkyl sulfate ester salts, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates. Anionic surfactants such as ester salts, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Is mentioned.

Other auxiliaries for formulation include lignin sulfonate, alginate, polyvinyl alcohol,
Examples include gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like.

The compound of the present invention is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of weeds. Soil treatment includes soil surface treatment and soil admixture treatment, and foliage treatment includes treatment from above the plant,
There are local treatments that treat only weeds so that they do not adhere to crops.

Further, it is expected that the herbicidal effect is enhanced by using it in combination with other herbicides. Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like. The compound of the present invention can be used as an active ingredient of a herbicide for paddy fields, upland fields, orchards, meadows, lawns, forests, non-agricultural fields, and the like.

When the compound of the present invention is used as an active ingredient of a herbicide, the treatment amount varies depending on weather conditions, formulation form, treatment time, method, place, target weed, target crop, etc., but is usually 0.05 per 1 are. g to 80 g, preferably
0.15 g to 40 g, and emulsions, wettable powders, suspending agents, etc., usually have a predetermined amount of water of 1 liter to 10 liters per are (adding auxiliary agents such as spreading agents if necessary). Is diluted and treated, and granules and the like are usually treated without being diluted. Examples of the spreading agent include polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, and paraffin in addition to the above-mentioned surfactant.

The compound of the present invention can also be used as an active ingredient of defoliants such as cotton and potato, and harvesting aids such as desiccants.

[0057]

INDUSTRIAL APPLICABILITY The compound of the present invention has an excellent herbicidal activity against various weeds which are problematic in the soil treatment and foliage treatment of upland fields, and the flooding treatment of paddy fields, and some of them are major crops. Since it shows excellent selectivity between the weeds and the weeds, it can be used for various purposes as an active ingredient of a herbicide.

[0058]

EXAMPLES The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown.

Production Example 1 (Production of Compound (3) of the Present Invention) 1- (7-Fluoro-3-oxo-3,4-dihydro-
2H-1,4-benzooxyzan-6-yl) -4-trifluoromethyl-2-pyridone (492 mg) was dissolved in dimethylformamide (2.0 ml), and propargyl bromide 3 was added thereto.
57 mg and 414 mg of potassium carbonate were added, and 20-40
Heated at ° C for 2 hours. After the reaction is completed, the reaction solution is poured into water,
It was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuum. The residue was washed with diethyl ether to give the desired compound 4 as white crystals.
44 mg was obtained. ¹ H-NMR δ (ppm) [CDCl ₃ , 60 MHz] 2.45 (q, J = 2 Hz, 1 H), 4.65 (d, J = 2 H
z, 2H), 4.70 (s, 2H), 6.45 (d, J = 6H
z, 1H), 6.78 (bs, 1H), 7.05 (d, J = 11H)
z, 1H), 7.32 (d, J = 7Hz, 1H), 7.72
(D, J = 7Hz, 1H)

Next, a compound 6 produced according to this production method is used.
Table 11 shows some of the compounds of the present invention represented by.

[0061]

[Table 11]

Next, production examples of starting compounds for the compounds of the present invention will be shown.

Production Example 2 (Production of Compound [IV]) 9.2 g of sodium hydride was suspended in 100 ml of N, N-dimethylformamide, and 2-hydroxy-4-trifluoromethylpyridine ( Compound [III])
A solution of 53 g dissolved in 100 ml of N, N-dimethylformamide was added. After bringing the mixture to room temperature, 3,4-
51 g of difluoronitrobenzene (compound [II]) was added dropwise and heated at 80 to 90 ° C. for 11 hours. After the reaction,
The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate and concentrated. The residue was washed with diethyl ether to obtain 45 g of the objective compound as yellow crystals.

Table 12 shows some of the compounds [IV] produced according to the above Production Examples.

[0065]

[Table 12]

Production Example 3 Production of Compound [V] 40 g of iron powder, 450 ml of acetic acid and 50 ml of water were mixed and the mixture was heated to 80 ° C.
Vigorously stirred with 1- (2-fluoro-4-
A solution of 43 g of nitrophenyl) -4-trifluoromethyl-2-pyridone (compound [IV]) dissolved in 100 ml of ethyl acetate was added dropwise, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the reaction solution was filtered through Celite, the filtrate was poured into water and extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate and concentrated to obtain 38 g of the objective compound as yellow crystals.

Table 13 shows some of the compounds [V] produced according to the above Production Examples.

[0068]

[Table 13]

Production Example 4 Production of Compound [VI] 1- (4-amino-2-fluorophenyl) -4-trifluoromethyl-2-pyridone (Compound [V]) 21
g, 98% sulfuric acid 24 g, and water 200 ml were mixed, and the mixture was heated and stirred at 80 ° C. for 1 hour, then the mixture was ice-cooled, and sodium nitrite 5.9 g was dissolved in water 60 ml to prepare a mixture of 5 to 10
The mixture was added dropwise at 0 ° C. and then stirred at the same temperature for 1 hour. Next, the reaction solution was filtered through Celite, and the filtrate was added dropwise to 300 ml of a saturated aqueous sodium sulfate solution heated and stirred at 100 ° C., and then 1
The mixture was heated and stirred at 00 ° C for 10 minutes. After the reaction was completed, the reaction solution was extracted with ether, dried over anhydrous magnesium sulfate, and concentrated. The residue was washed with chloroform to obtain 8 g of the objective compound as yellow crystals.

Table 14 shows some of the compounds [VI] produced according to the above Production Examples.

[0071]

[Table 14]

Production Example 5 Production of Compound [VII] To 25 ml of fuming nitric acid was added -5 g of 6.9 g of 1- (2-fluoro-4-hydroxyphenyl) -4-trifluoromethyl-2-pyridone (Compound [VI]). Add slowly at ~ 0 ° C,
Then, the temperature was gradually raised to room temperature. After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 6.5 g of the objective compound as yellow crystals.

Table 15 shows some of the compounds [VII] produced according to the above Production Examples.

[0074]

[Table 15]

Production Example 6 Production of Compound [VIII] 0.64 g of sodium hydride was suspended in 10 ml of N, N-dimethylformamide, and 1- (2-fluoro-4-hydroxy-5-nitrophenyl) was suspended in this suspension. ) -4-Trifluoromethyl-2-pyridone (Compound [VII]) 4.9 g
Was dissolved in 20 ml of N, N-dimethylformamide, and the mixture was stirred at room temperature for 30 minutes. Next, 4 g of bromoacetic acid methyl ester was added dropwise to this mixed solution, and then 50 ° C.
Heated for 3 hours. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract solution was washed with water, dried over anhydrous magnesium sulfate and concentrated. The residue was washed with ether to obtain 4.9 g of the target compound as yellow crystals.

Table 16 shows some of the compounds [VIII] produced according to the above Production Examples.

[0077]

[Table 16]

Production Example 7 Production of the compound represented by Chemical formula 1 1- (2-Fluoro-4-methoxycarbonylmethoxy-5-nitrophenyl) -4-trifluoromethyl-2
-Pyridone (Compound [VIII]) 4.5 g was added to ethyl acetate 60
dissolved in a mixed solution of 20 ml of acetic acid and 4 ml of iron powder and 4 g of acetic acid.
0 ml and 10 ml of water were added dropwise with vigorous stirring at 80 ° C. After completion of the reaction, the reaction solution was filtered through Celite, the filtrate was poured into water and extracted with ethyl acetate. The extract was washed with water and saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate,
Concentrated. The residue was washed with ether to obtain 3.1 g of the target compound as white crystals.

Table 17 shows some of the compounds represented by Chemical formula 7 produced according to the above Production Examples.

[0080]

[Table 17]

Formulation examples are shown below. The compounds of the present invention are shown by the compound numbers in Table 11. Parts are parts by weight. Formulation Example 1 Compounds (1) to (11) of the present invention, 50 parts each, 3 parts calcium ligninsulfonate, 2 parts sodium lauryl sulfate and 45 parts synthetic silicon oxide hydroxide are thoroughly pulverized and mixed to obtain wettable powders. Formulation Example 2 5 parts each of the compounds (1) to (11) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate, 25 parts of xylene and 50 parts of cyclohexanone are mixed well to form an emulsion. obtain.

Formulation Example 3 2 parts each of the compounds (1) to (11) of the present invention, 1 part synthetic silicon oxide hydroxide, 2 parts calcium lignin sulfonate, 30 parts bentonite and 65 parts kaolin clay were thoroughly pulverized and mixed, and water was added. After adding and kneading well, it is granulated and dried to obtain granules. Formulation Example 4 Compounds of the present invention (1) to (11), 25 parts each, polyoxyethylene sorbitan monooleate 3 parts, CMC 3 parts,
69 parts of water is mixed and wet-milled until the particle size becomes 5 microns or less to obtain a suspension agent.

Next, it is shown in Test Examples that the compound of the present invention is useful as an active ingredient of a herbicide. The compounds of the present invention are shown by the compound numbers in Table 11, and the compounds used for comparison and control are shown by the compound symbols in Table 18.

[0084]

[Table 18]

In the evaluation of herbicidal efficacy and phytotoxicity, "0" was assigned to the test plants (weeds and crops) at the time of the survey, which showed no or almost no difference in their emergence and growth conditions from those of the untreated plants. , "5" means that the test plant is completely killed or the emergence or growth of the plant is completely suppressed, and is divided into 6 stages of 0 to 5, and is shown as 0, 1, 2, 3, 4, 5.

Test Example 1 Field soil surface treatment test Field soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, seeds were sown, and soil was covered. Formulation example 2
The test compound was made into an emulsion according to, and a predetermined amount thereof was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After the treatment, it was grown in a greenhouse for 20 days, and the herbicidal effect was investigated. The results are shown in Table 19.

[0087]

[Table 19]

Test Example 2 Field soil surface treatment test Field soil was filled in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and sows and Malaga morning glory were sown and covered with soil. The test compound was made into an emulsion according to Formulation Example 2, and the predetermined amount thereof was diluted with 10 liters of water per are.
The soil surface was treated with a small sprayer. After the treatment, it was grown in a greenhouse for 20 days, and the herbicidal effect was investigated. The results are shown in Table 20.

[0089]

[Table 20]

Test Example 3 Field and foliage treatment test Field soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and Malaba morning glory, Japanese radish and velvetleaf were sown and grown in a greenhouse for 10 days. Then, formulation example 2
The test compound was made into an emulsion in accordance with the procedure described in 1., and a predetermined amount thereof was diluted with water containing 10 liters of spreading agent per are, and the leaves were treated from above the plant with a small sprayer. After processing 20
The plants were cultivated in a greenhouse for one day and the herbicidal efficacy was investigated. The results are shown in Table 21.

[0091]

[Table 21]

Test Example 4 Field and foliage treatment test Field soil was filled in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of oats and oats were sown.
Raised for 0 days. Then, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount thereof was diluted with water containing 10 liters of spreading agent per are, and the leaves were treated from above the plants with a small sprayer. After the treatment, it was grown in a greenhouse for 20 days, and the herbicidal effect was investigated. The results are shown in Table 22.

[0093]

[Table 22]

Test Example 5 Paddy field flooding treatment test Paddy field soil was packed in a cylindrical plastic pot with a diameter of 8 cm and a depth of 12 cm, and seeds of Taenia japonica and broad-leaved weeds (Azena, Kishigusa, Mizochabe) were mixed to a depth of 1 to 2 cm. Complicated. After flooding to make paddy fields, rice at the two-leaf stage was transplanted and grown in a greenhouse. Six days later (the initial stage of the development of each weed), the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 5 ml of water and treated on the water surface. After the treatment, the plants were grown in a greenhouse for 20 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 23.

[0095]

[Table 23]

Test Example 6 Upland soil treatment test A vat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with upland soil, and cotton, velvetleaf, physalis sycamore, sycamore sorghum and Achinoe kurokosa were sown and covered with a thickness of 1 to 2 cm. .. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the compound was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 24.

[0097]

[Table 24]

Test Example 7 Upland Soil Treatment Test Field up soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, and seeds of wheat, barley, sunflower edodes, red-footed squirrel, field pansy, Nostocanthus chinensis, grasshopper and oats were sown. The soil was covered to a thickness of 2 cm. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the compound was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After the treatment, it was grown in a greenhouse for 27 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 25.

[0099]

[Table 25]

Test Example 8 Field foliage treatment test Field soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, and soybean, corn, rice, velvetleaf, Amaranthus edulis, and Physalis communis were sown and grown for 18 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 10 liters of water equivalent to 1 are containing a spreading agent, and uniformly sprayed from above the plant body over the entire foliage with a small sprayer. Processed. At this time, the growth status of weeds and crops varies depending on the grass species, but is in the 1 to 4 leaf stage, and the plant height is 2 to 20 cm.
Met. 20 days after the treatment, herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 26. The test was conducted in a greenhouse throughout the entire period.

[0101]

[Table 26]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display area C07D 265: 00) (72) Inventor Shoji Sakaki 4-2-1, Takashi Takarazuka, Hyogo Sumitomo Gaku Kogyo Co., Ltd. (72) Inventor Ryo Sato 42-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (72) Inventor Eiki Nagano 4-2-1 Takashi, Takarazuka-shi, Sumitomo Gaku Kogyo Co., Ltd.

Claims (6)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R represents an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group or an alkoxyalkyl group, and X represents a hydrogen atom, a halogen atom,
Represents a methyl group optionally substituted with a halogen atom or an ethyl group optionally substituted with a halogen atom,
Y represents a hydrogen atom or a methyl group. ] The benzoxazinyl pyridone derivative shown by these. 2. A general formula: ## STR2 ## [In the formula, X represents a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom or an ethyl group optionally substituted with a halogen atom, and Y represents a hydrogen atom or a methyl group. ] The compound shown by these, and general formula RW [In formula, R represents an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group, or an alkoxyalkyl group, W is a chlorine atom, a bromine atom, an iodine atom. , P-toluenesulfonyloxy group or methanesulfonyloxy group. ] The compound shown by these is made to react, The manufacturing method of the benzoxazinyl pyridone derivative of Claim 1 characterized by the above-mentioned. 3. A herbicide containing the benzoxazinylpyridone derivative according to claim 1 as an active ingredient. 4. A general formula: ## STR3 ## [In the formula, X represents a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom or an ethyl group optionally substituted with a halogen atom, and Y represents a hydrogen atom or a methyl group. ] The compound shown by these. 5. A general formula: ## STR4 ## [In the formula, X represents a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom or an ethyl group optionally substituted with a halogen atom, and Y represents a hydrogen atom or a methyl group. ] The compound shown by these. 6. A general formula: ## STR5 ## [Wherein, X represents a hydrogen atom, a halogen atom, a methyl group optionally substituted by a halogen atom or an ethyl group optionally substituted by a halogen atom, Y represents a hydrogen atom or a methyl group, and R ' Represents an alkyl group. ]
The compound represented by.