JP2008133207A - Oxazolinone derivative, method for producing the same and herbicide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new oxazolinone derivative (I) exhibiting excellent herbicidal activity at a low dose, having excellent selective herbicidal activity between crops and weeds, having high safety to crops, human and animals and widely usable for the weeds on a paddy rice field and a plowed land, and to provide a herbicide containing the derivative. <P>SOLUTION: The oxazolinone derivative is expressed by general formula (I) [X is a halogen atom, a 1-6C alkyl group or a 1-6C halogenated alkyl group; R is a hydrogen atom or a 1-6C alkyl group; n is an integer of 0-5; and when n is ≥2, each X may be the same or different]. The invention further provides a herbicide containing the derivative. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel oxazolinone derivative, a process for producing the same, and a herbicide containing it as a herbicidal active ingredient.

  Herbicides are mainly used to control weeds that grow on farmland and create an environment suitable for crop cultivation. So far, phenoxy, benzoic acid or phenylacetic acid, halogenated carboxylic acid, carbamate, 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 oxazolinone derivatives.
(1) General formula (A)

[In Formula (A), R is an alkyl group, a cycloalkyl group, a phenyl group, a halogen atom or a haloalkyl group-substituted phenyl group. ] The 5-thienyl oxazoline derivative represented by this is known, and this derivative is known to have herbicidal activity (see Patent Document 1). (2) General formula (B)

[In Formula (B), Y is a hydrogen atom or a chlorine atom, n is 1-2, Z is a hydrogen atom, a chlorine atom, a nitro group, a methoxy group, a methyl group or an acetyl group, Y and Z are not hydrogen atoms. ] Is known, and this derivative is known to have insecticidal activity (see Patent Document 2).
(3) General formula (C)

[In formula (C), R is a C1-C4 alkyl group, an unsubstituted phenyl group, or a phenyl group monosubstituted by a halogen atom, a C1-C4 alkyl group or an alkoxy group. ] Is known, and this derivative is known to have antiparasitic activity (see Patent Document 3).

In general, in the development of herbicides, it is required to develop herbicides that exhibit high herbicidal effects even at low dosages, have herbicidal activity against a wide variety of weeds, and are excellent in safety. However, when the oxazolinone derivative as described above is used as a herbicidal active ingredient, the herbicidal effect is insufficient at low doses, and even if it shows herbicidal activity, selective herbicidal activity of crops and weeds Therefore, the herbicide is not always satisfactory because it has a large phytotoxicity to crops.
Japanese Unexamined Patent Publication No. 57-035598 Japanese Examined Patent Publication No. 46-022140 British Patent No. 1250973

  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 to provide a novel oxazolinone derivative that can be used for a wide range of subjects such as weeds, a simple and efficient production method that is excellent in safety, and a herbicide containing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the following specific novel oxazolinone derivatives and herbicides containing the same do not harm crops, and weeds of rice and field crops. In contrast, the present inventors have found that an excellent herbicidal effect is exhibited at a low dose, and the present invention has been completed.

  That is, the oxazolinone derivative according to the present invention has the general formula (I)

[In the 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 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. N represents an integer of 0 to 5, and when n is 2 or more, the plurality of X may be the same or different from each other. It is characterized by being represented.

In addition, the herbicide according to the present invention is characterized by containing an oxazolinone derivative represented by the above general formula (I) as a herbicidal active ingredient.
The production method of the oxazolinone derivative (I) according to the present invention is characterized in that it includes the following steps (i) to (iv).

(i) reacting a phenol (II) represented by the following formula (II) with an α-haloalkanoic acid ester (III) represented by the following formula (III) in the presence of a base, if necessary, in a solvent. To obtain a phenoxyalkanoic acid derivative (IV) by
(ii) Next, the obtained phenoxyalkanoic acid derivative (IV) is converted into a phenoxyalkanoic acid halide (V) using a halogenating agent, and then in the presence of a base, if necessary, in a solvent. A step of obtaining a phenoxyalkanoic acid amide derivative (VII) by reacting with aminobutyric acid esters (VI);
(iii) a step of hydrolyzing the phenoxyalkanoic acid amide derivative (VII) in the presence of a base, if necessary, in a solvent to obtain a phenoxyalkanoic acid amide derivative (VIII);
(iv) Next, the obtained phenoxyalkanoic acid amide derivative (VIII) is reacted with a condensing agent in the presence of a base, if necessary, in a solvent to obtain an oxazolinone derivative (I).

(In the above reaction formula, X, R and n are as defined in the general formula (I), R ₁ represents a lower alkyl having 1 to 6 carbon atoms, and Hal represents a halogen atom.)

  The oxazolinone 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, and also in paddy rice and field cropping. 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 oxazolinone derivative represented by the general formula (I) of the present invention as an active ingredient, it can be used in low doses against paddy rice and field crop weeds without causing any phytotoxicity to the crop. Because of its excellent herbicidal effect, it is possible to obtain a high-quality crop with high safety.

  According to the present invention, the oxazolinone derivative (I) can be produced simply and efficiently with excellent safety.

Hereinafter, the novel oxazolinone derivative according to the present invention, the production method thereof, and the herbicide containing this as an herbicidal active ingredient will be specifically described.
[New oxazolinone derivatives]
The novel oxazolinone derivative according to the present invention is represented by the general formula (I). (Hereinafter also referred to as oxazolinone derivative (I).)

[In the 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 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. N represents an integer of 0 to 5, and when n is 2 or more, the plurality of X may be the same or different from each other. ].

In the present invention, the oxazolinone derivative (I) has two H atoms bonded to the 4-position carbon atom of the oxazolinone ring substituted with a methyl group (CH 3) and the X-position at the 2-position.
-Substituted phenyloxy-R methyl group {Xn-Ph-O-CR-, Ph: phenyl group, X,
n and R are the same as those in (I) above. } Has a particularly large feature in that it is replaced with {}, and is considered to have a large role in herbicidal activity.

In the oxazolinone derivative represented by the general formula (I), specific examples of the substituents represented by X and R include the following.
As the “halogen atom”, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The “C 1-6 alkyl group” means a straight 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-ethyl Or the like can be mentioned Rupuropiru group.
The “halogenated alkyl group having 1 to 6 carbon atoms” is a linear or branched chain having 1 to 6 carbon atoms in which at least a part of hydrogen atoms in the alkyl group is 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.

In the oxazolinone derivative (I), Xn on the benzene ring is preferably 3,4-dimethyl, 3,5-dimethyl, 3-methyl-4chloro, 2,4-dichloro, 3,5-
Dichloro, 3,5-difluoro, 2,3,4,5,6-tetrafluoro, 3,5-bistrifluoromethyl.

  In the oxazolinone derivative (I), R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and i-propyl.

In a preferred embodiment of the present invention, when Xn and R are as described above, the effects of the present invention tend to appear remarkably.
Specific examples of the oxazolinone derivative (I) according to the present invention are shown in Table 1. However, the present invention is not limited to these specific examples.

  The compound numbers in Table 1 are also referred to in the following Table 2, Examples, Formulation Examples and Test Examples.

<Note 1>
In Table 1, for example, “position and number n of X” in compound number 1 is “3,5- (CH ₃ ) ₂ ”. This means that two substituents X: (CH ₃ ) are present at the 3,5 positions on the benzene ring.

For example, in Compound No. 9, “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 positions 3 and 5 on the benzene ring, and “4-Cl” Is X: Cl at position 4 on the benzene ring.
Means there is one.

Therefore, in Compound No. 9, “3,5- (CH ₃ ) ₂ -4-Cl” has CH _{3 in} the 3 and 5 positions on the benzene ring (2 in total), and 4 positions. This means that there is one Cl. The same applies to other compounds.

  The oxazolinone 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 in combinations of weeds and crops shown below. As shown, it is useful as a novel herbicidal active ingredient that can be used for a wide range of subjects such as paddy rice and field weeds.

  Moreover, according to the herbicide according to the present invention containing the oxazolinone 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 exhibits a herbicidal effect, it is possible to obtain a high-quality crop with high safety. The herbicide of the present invention is effective, for example, for weeds or broadleaf weeds.

  In other words, the oxazolinone derivative of the present invention is, for example, in the case where rice in the genus Cropaceae, barnyard grass, weeping konagi, etc. grows in the field, that is, the type of crop and weed is Species. Even if it is the same kind, there is almost no phytotoxicity to crop rice, and it shows a selective herbicidal effect only on weeds. In addition, when rice and broad-leaved weeds grow in the field, crops such as soybeans (broad-leaved crops) and wheat (crop genus crops), weeds cultivated weeds (eg, Japanese mosquito, nobier, enokorogusa) and broad-leaved leaves The same effect can be obtained when weeds (eg Inuta) grow.

For example, Aspen weeping (Alopecurus), oat (Avena)
, Bromus, Cyperus, Digitaria, Echinochloa, Eleocharis, Eleusine, Monochoria
, Prickly millet (Panicum), sparrow tree (Paspalum), prickly pear (Phleum),
Examples include Poa, Pod, Sagittaria, Scirpus, Setaria, and Johnson Grass (Sorghum).

Examples of broad-leaved weeds include Abutilon, Amaranthus, Ambrosia, Bidens, Chenopodium, and Galium.
, Ipomoea, Lindernia, 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, for example, peanut (Arachis),
Examples include sugar beet, rape (Brassica), soybean (Glycine), cotton (Gossypium), tomato (Lycopersicon) and the like.

In addition, the application effect of the herbicide of this invention is not limited to the weeds and crops illustrated above.
The oxazolinone derivative (I) according to the present invention can be produced, for example, by the following production method A.
[Production method A]

In the above reaction formula, X, R and n are as defined in the general formula (I), R ₁ represents the same lower alkyl as described above, and Hal represents a halogen atom.
In the production method A, the phenoxyalkanoic acid derivative (IV) is 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, the α-haloalkanoic acid ester (III) is used in an amount of 1 to 3 mol, preferably 1 to 1.2 mol, with respect to 1 mol of phenol (II). 4
It is used in an amount of mol, preferably 2 to 2.5 mol.

  This 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 this reaction, for example, the phenoxyalkanoic acid derivative (IV) is acidified by, for example, distilling off the solvent from the reaction solution containing the derivative (IV), adding water, and then adding hydrochloric acid, sulfuric acid, or the like. And extracted with an extraction solvent such as diethyl ether, toluene, ethyl acetate, and then washed with water and saturated brine, and the solvent is distilled off.

Next, the obtained phenoxyalkanoic acid derivative (IV) is converted into a phenoxyalkanoic acid halide (V) using a halogenating agent, and then reacted with 2-aminobutyric acid esters (VI) in the presence of a base. Thus, 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 organic solvents such as dichloromethane, 1,2-dichloroethane, chloroform, benzene, toluene and xylene. Examples of the halogenating agent include oxalyl chloride, thionyl chloride, phosphorus trichloride, phosphorus pentachloride and the like.

In this reaction, the halogenating agent is generally 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.

Solvents used when the obtained phenoxyalkanoic acid halide (V) is reacted with 2-aminobutyric acid esters (VI) include dichloromethane, 1,2-dichloroethane, chloroform, tetrahydrofuran, benzene, toluene, xylene and the like. In some cases, the organic solvent can be used as a mixed solvent of these organic solvents and 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 amount of 2-aminobutyric acid esters (VI) used is phenoxyalkanoic acid halide (V).
It is 1-2 mol normally with respect to 1 mol, Preferably it is 1-1.1 mol. The base is usually used in an amount of 1 to 2 mol, preferably 1 to 1.1 mol. 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) is extracted, for example, by adding water and an organic solvent to the reaction solution containing the derivative (VII), and further washed with water and saturated saline. Obtained by distilling off.

If necessary, the obtained target product can be further purified by operations such as column chromatography or recrystallization.
The phenoxyalkanoic acid amide derivative (VII) is easily hydrolyzed in the presence of a base to give a phenoxyalkanoic acid amide derivative (VIII).

  Examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. This hydrolysis reaction is preferably performed in the presence of a solvent, and examples of the solvent used include water and alcohols such as methanol, ethanol and isopropanol. When the ester moiety is hydrolyzed, the base such as sodium hydroxide is usually used in an amount of 1 to 2 mol, preferably 1 to 1.5 mol, relative to 1 mol of the phenoxyalkanoic acid amide derivative (VII). Used. 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 obtained by adding water to a reaction solution containing the derivative (VIII) and then acidifying with hydrochloric acid, sulfuric acid, etc., and adding 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.

Next, the obtained phenoxyalkanoic acid amide derivative (VIII) is reacted with a condensing agent in the presence of a base (intramolecular dehydration condensation and cyclization reaction) to produce the oxazolinone derivative (I) of the present invention. it can.

  This cyclization reaction is preferably carried out in a solvent, and examples of the solvent used include dichloromethane, 1,2-dichloroethane, chloroform, acetonitrile, dimethylformamide and the like.

  Examples of the condensing agent include 1,3-dicyclohexylcarbodiimide, 1-ethyl-3- (3'-dimethylaminopropyl) carbodiimide, 2-methyl-6-nitrobenzoic acid 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 to be used is usually 1 to 2 mol, preferably 1 to 1.1 mol, and the base is usually 1 to 4 mol, preferably 2 to 1 mol with respect to 1 mol of the phenoxyalkanoic acid amide derivative (VIII). Used in an amount of 3 moles. 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 (I) of the present invention can be extracted, for example, by adding water and an organic solvent to the reaction solution containing the derivative, followed by further washing with water and saturated saline, and distilling off the solvent. Is obtained. The obtained object (I) can be further purified by operations such as column chromatography or recrystallization, if necessary.

Next, a general formulation method for the oxazolinone derivative (I) according to the present invention will be described in detail.
[Herbicides containing oxazolinone derivatives and their production (formulation)]
The herbicide of the present invention can be used in various dosage forms. When formulated, the active ingredient, that is, the oxazolinone derivative represented by the general formula (I), which is a herbicidal active ingredient, is used as a carrier or diluent. Depending on the method, it is possible to employ a method such as mixing with at least one of an additive (eg, a surfactant) and an auxiliary agent by a known method.

  The herbicides obtained in this way are in the form of preparations usually used as agricultural chemicals, such as granules, fine granules, wettable powders, wettable granules, emulsions, aqueous solvents, flowables, tablets, powders, microcapsules. It can be used in the form of an agent or paste.

  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. Such carriers are not limited to specific ones, and specific examples include the following solid carriers or liquid carriers.

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, in addition to these various components, various adjuvants and additives such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, sodium alginate, gelatin, tragacanth rubber, etc. Etc. can be used.

  The herbicide of the present invention contains the oxazolinone derivative represented by the general formula (I) in a range of usually 0.001 to 95% by weight, preferably 0.01 to 75% by weight, regardless of the dosage form. It 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. .

Next, although an Example is given and the manufacture example of the oxazolinone derivative (I) based on this invention is demonstrated concretely, this invention is not limited to these Examples at all.
[Example]
Preparation of 2- {1- [3,5-bis (trifluoromethyl) phenoxy] propyl} -4,4-dimethyl-1,3-oxazol-5 (4H) -one (Compound No. 21)
A 2-({2- [3,5-bis (trimethyl) compound synthesized in the Reference Production Example described below was synthesized in a 100 ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer capable of measuring from −50 to 50 ° C. Fluoromethyl) phenoxy] butanoyl} amino) -2-methylpropionic acid 2.00 g (
5.0 mmol) and 1.18 g (15 mmol) of pyridine were dissolved in 30 ml of dichloromethane and cooled on ice.

  To this was added 1.44 g (7.5 mmol) of 1-ethyl-3- (3′-dimethylaminopropyl) carbodiimide and a catalytic amount of 4-dimethylaminopyridine, and the mixture was stirred at room temperature for 1 hour.

After completion of the reaction, the dichloromethane layer was washed successively with 30 ml of saturated aqueous ammonium chloride solution, 30 ml of 1N aqueous hydrochloric acid solution, 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The crude product thus obtained was purified by chromatography using silica gel (“Wakogel B-10”, manufactured by Wako Pure Chemical Industries, Ltd.) {developing solvent hexane: ethyl acetate = 8: 1 (volume ratio)}. 1.82 g of the title 2- {1- [3,5-bis (trifluoromethyl) phenoxy] propyl} -4,4-dimethyl-1,3-oxazol-5 (4H) -one (oil, Yield 95%) was obtained.

In addition, Table 2 shows ¹ H-NMR spectrum data of the compound of the present invention.
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]
Preparation of 2-({2- [3,5-bis (trifluoromethyl) phenoxy] butanoyl} amino) -2-methylpropionic acid Equipped with a stirrer, reflux condenser and thermometer capable of measuring from 0 to 100 ° C. In a 300 ml four-necked flask, 23.0 g (0.10 mol) of 3,5-bis (trifluoromethyl) phenol was dissolved in 150 ml of methanol, and 21.7 g (0.12 mol) of methyl 2-bromobutyrate was dissolved at room temperature. After adding at (20 degreeC), 9.60 g (0.24 mol) of sodium hydroxide was then added, and it heated and refluxed 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 obtained reaction mixture was extracted 3 times with 150 ml of ethyl acetate, and the organic layer was washed with 100 ml of saturated brine and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give oily 2- [ 28.4 g of a crude product of 3,5-bis (trifluoromethyl) phenoxy] butyric acid was obtained.

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., the above 2- [3,5-bis (trifluoromethyl) phenoxy] butyric acid was 28.4 g of the crude product was dissolved in 250 ml of dichloromethane, and 13.9 g (0.11 mol) of oxalyl chloride and a catalytic amount of N, N-dimethylformamide were successively added under ice cooling, followed by stirring at room temperature for 1 hour.

After completion of the reaction, dichloromethane was distilled off at room temperature under reduced pressure to give oily 2- [3,5
-Bis (trifluoromethyl) phenoxy] butyric acid chloride 30.1 g was obtained as a crude product.

  Subsequently, 16.9 g (0.11 mol) of 2-aminoisobutyric acid methyl ester hydrochloride and triethylamine 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. 11.1 g (0.11 mol) was dissolved in a mixed solvent of 150 ml of dichloromethane and 20 ml of water, and this solution was cooled to 3 ° C. and stirred vigorously while the 2- [3,5-bis (tri Fluoromethyl) phenoxy] butyric chloride 30.1 g of a crude product dissolved in 50 ml of dichloromethane was added dropwise.

After completion of dropping, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was washed with 150 ml of ice water. The organic layer was further washed with 150 ml of saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting crude product was chromatographed using silica gel (Wakogel B-10) ( Developing solvent hexane: ethyl acetate 3: 1 (volume ratio)), solid 2-({2- [3,5-bis (trifluoromethyl) phenoxy] butanoyl} amino) -2-methylpropionate 30.7 g of ester (yield 8
2%).

Next, the obtained 2-({2- [3,5-bis (trifluoromethyl)] was obtained 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.
Phenoxy] butanoyl} amino) -2-methylpropionic acid methyl ester (30.7 g) was dissolved in 100 ml of methanol, and a solution of 6.00 g (0.15 mol) of sodium hydroxide in 20 ml of water was added at 10 ° C. Stir for 2 hours.

  After completion of the reaction, methanol was distilled off from the reaction mixture under reduced pressure, 200 ml of ice water was added to adjust the pH to 2 with a 1N aqueous hydrochloric acid solution, the aqueous layer was extracted three times with 250 ml of ethyl acetate, and the organic layer was washed with 100 ml of saturated brine. And then dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give solid 2-({2- [3,5-bis (trifluoromethyl) phenoxy] butanoyl} amino) -2- 28.2 g (yield 95%) of methylpropionic acid was obtained.

Next, the method of formulating the oxazolinone 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 the present invention is not limited only to these Formulation Examples 1 to 6, and it goes without saying that it can be formulated by mixing with other various additives at an arbitrary ratio. .

The compound numbers are the same as those shown in Table 1, and “parts” in the following examples are all parts by weight.
[Formulation Example 1 (Granule)]
Compound No. 15 parts of water was added to 1 part of 1 compound, 1 part of calcium lignin sulfonate, 1 part of lauryl sulfate, 30 parts of bentonite and 67 parts of talc, kneaded with a kneader, and granulated with an extrusion granulator. This was dried with a fluid dryer to obtain granules containing 1% of a herbicidal active ingredient (Compound No. 1).

[Formulation Example 2 (Flowable)]
Compound No. 21 compound 20.0 parts, sulfosuccinic acid di-2-ethylhexyl ester sodium salt 2.0 parts, polyoxyethylene nonylphenyl ether 2.0 parts, propylene glycol 5.0 parts, antifoaming agent 0.5 parts and water 70.5 parts was uniformly mixed and pulverized with a wet ball mill to obtain a flowable agent containing 20% of a herbicidal active ingredient (Compound No. 21).

[Formulation Example 3 (Dry flowable agent)]
Compound No. No. 26 compound, 75 parts, isoban no. 1 [anionic surfactant: manufactured by Kuraray Isoprene Chemical Co., Ltd., trade name] 10 parts, Vanillex N [anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd., trade name] 5 parts, white carbon 5 parts, 5 parts of clay was uniformly mixed and pulverized to obtain a dry flowable (granular hydration) agent containing 75% of a herbicidal active ingredient (Compound No. 26).

[Formulation example 4 (wettable powder)]
Compound No. 18 compounds of 15 parts, 15 parts of white carbon, 3 parts of calcium lignin sulfonate, 2 parts of polyoxyethylene nonylphenyl ether, 5 parts of diatomaceous earth, and 60 parts of clay were mixed uniformly by a pulverizing mixer to obtain a herbicidal active ingredient ( A wettable powder containing 15% of Compound No. 18) was obtained.

[Formulation Example 5 (emulsion)]
Compound No. 36 parts of Compound 36, Solpol 700H [Emulsifier, trade name, manufactured by Toho Chemical Co., Ltd.] and 60 parts of xylene were mixed to obtain an emulsion containing 20% of a herbicidal active ingredient (Compound No. 36).

[Formulation Example 6 (powder)]
Compound No. 30 parts of compound, 0.5 part 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. 30). A powder containing 0.5% was obtained.

In addition, all the oxazolinone 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 oxazolinone 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 development and phytotoxicity test for transplanted paddy rice Paddy soil is filled in a 1 / 5,000 are wide Wagner pot, water is added and chemical fertilizer (N: P: K = 17: 17: 17) was mixed, and scribing was performed.

  Thereafter, 30 seeds of Tainubier, broad-leaved weeds (Azena, Kogi), and firefly seeds were sown at a depth of 0 to 1 cm. Immediately after sowing, a two-leaf stage rice was transplanted. Immediately after transplanting rice, the water depth was kept at about 3 cm. Subsequent management was performed in a glass greenhouse. One day after 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 continuous systems 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 Table 3 below.
The compound numbers in Table 3 are the same as those shown in Table 1 above.

<Test Example 2>
Weeding effect test by paddy rice growing season treatment Fill paddy soil in 1 / 5,000 are wide Wagner pot, add water and mix with fertilizer (N: P: K = 17: 17: 17), I wrote for him.

Thereafter, 30 seeds of Tainubier, broad-leaved weeds (Azena, Kogi), and firefly seeds were sown at a depth of 0 to 1 cm. Immediately after sowing, the water was submerged and the water depth was kept at about 3 cm.
Subsequent management was performed in a glass greenhouse. Seven days after sowing, the wettable powder prepared according to 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 Table 4.
The compound numbers in the table are the same as those shown in Table 1.

<Test Example 3>
Herbicidal effect test and phytotoxicity test by field soil treatment 1) Herbicidal effect test on field weeds:
A field pot (alluvial loam) is packed in an unglazed pot with a size of 1 / 5,000 are, and 50 cm each of 1 cm of surface soil and 50 kinds of weed seeds of hinokiba, Enokorogusa, Shiroza and Inuta are mixed together. Pressed lightly. 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 drug treatment.

The results are shown in Table 5.
2) Chemical damage test for crops:
Cultivate field soil (alluvial loam) in an unglazed pot with a size of 1 / 10,000 are, seeded each crop (5 soybeans, 10 wheat) in separate pots, and lightly pressed the surface layer . 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 Table 1.

<Test Example 4>
Herbicidal effect test and phytotoxicity test by field foliage treatment 1) Herbicidal effect test on field weeds:
A field pot (alluvial loam) is packed in an unglazed pot with a size of 1 / 5,000 are, and 50 cm each of 1 cm of surface soil and 50 kinds of weed seeds of hinokiba, Enokorogusa, Shiroza and Inuta are mixed together. Pressed lightly. 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 drug treatment.

The results are shown in Table 6 below.
2) Chemical damage test for crops:
Cultivate field soil (alluvial loam) in an unglazed pot with a size of 1 / 10,000 are, seeded each crop (5 soybeans, 10 wheat) in separate pots, and lightly pressed the surface layer . 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 Table 1.

Claims (3)

Formula (I)

[In the 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 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. N represents an integer of 0 to 5, and when n is 2 or more, the plurality of X may be the same or different from each other. ] The oxazolinone derivative represented by this.   A herbicide comprising the oxazolinone derivative represented by formula (I) according to claim 1 as a herbicidal active ingredient. The method for producing an oxazolinone derivative according to claim 1, comprising the following steps (i) to (iv):
(i) reacting a phenol (II) represented by the following formula (II) with an α-haloalkanoic acid ester (III) represented by the following formula (III) in the presence of a base, if necessary, in a solvent. To obtain a phenoxyalkanoic acid derivative (IV) by
(ii) Next, the obtained phenoxyalkanoic acid derivative (IV) is converted into a phenoxyalkanoic acid halide (V) using a halogenating agent, and then in the presence of a base, if necessary, in a solvent. A step of obtaining a phenoxyalkanoic acid amide derivative (VII) by reacting with aminobutyric acid esters (VI);
(iii) a step of hydrolyzing the phenoxyalkanoic acid amide derivative (VII) in the presence of a base, if necessary, in a solvent to obtain a phenoxyalkanoic acid amide derivative (VIII);
(iv) Next, the obtained phenoxyalkanoic acid amide derivative (VIII) is reacted with a condensing agent in the presence of a base, if necessary, in a solvent to obtain an oxazolinone derivative (I).

(In the above reaction formula, X, R and n are as defined in the general formula (I), R ₁ represents a lower alkyl having 1 to 6 carbon atoms, and Hal represents a halogen atom.)