JPH05230045A - Oxirane derivative and herbicide containing the same as an active ingredient - Google Patents

Abstract

PURPOSE:To provide a novel compound useful as a herbicide because it shows excellent herbicidal activity against weeds in rice plant paddies and has high selectivity, particularly selectivity between rice plant and barnyard grasses. CONSTITUTION:A compound of formula I (X is halogen, haloalkyl of 1 to 4 carbon atoms; R<1> is H, 1 to 4 C alkyl, phenyl; R<2> is H, 1 to 6C alkyl; n is 0, 1), for example, 3-(1,1,1-trichloro-3,4-epoxybutan-3-yl)benzaldehyde-0-methyloxime. The compound of formula I is prepared by epoxidizing an alkenyl derivative of formula II with a peroxide such as peracetic acid in an inert solvent such as methylene chloride at 0 to 80 deg.C. It can effectively control weeds in rice plant paddies with such a reduced dose as the compound does not cause chemical damage to the rice plant.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel oxirane derivative and a herbicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Herbicides are extremely important agents for labor saving of weed control work and improvement of productivity of agricultural and horticultural crops. Therefore, research and development of herbicides have been actively conducted for many years, and a wide variety of agents are currently available. Has been put to practical use. But,
Even today, there is a demand for the development of a new drug having more excellent herbicidal properties, in particular, a drug capable of controlling only the target weeds at a low dose without causing phytotoxicity on cultivated crops.

Along with paddy rice, various weeds in paddy fields, such as annual grass weeds such as Nobie, annual cyperaceous weeds such as tabular clam, annual broad-leaved weeds such as eel, yellow cypress, urinary cucumber, hirshiro, hiramemodaka, firefly, matsubai, mizugaya, are available. It is known that perennial weeds such as kurogwai, Japanese sardines, and celery grow, and it is extremely important for rice cultivation that these weeds do not cause chemical damage to paddy rice, and that they are effectively weeded with a small amount of spraying because of environmental pollution. is important. In particular, since Nobie is a grass weed, a drug having herbicidal activity against Nobie is likely to cause phytotoxicity to paddy rice. Therefore, it has high herbicidal activity against Nobie and has an intergeneric selection between paddy and Nobie. The development of highly effective drugs has become an important issue.

Examples of the oxirane derivative having herbicidal activity include those described in Japanese Patent Publication No. 53-37409.

[Chemical 3] Compound represented by [generic name: tridifane (trid
iphane)] and the formulas described in JP-A-1-508736.

[Chemical 4] The compound represented by (Compound No. 1 in the publication) is known.

[0005]

However, the compound represented by the formula (I) described in JP-B-53-37409 has already been put to practical use as a herbicide for controlling weeds of grass family in the corn field. However, when it is used as a herbicide for paddy rice, its selectivity is poor, and it may cause phytotoxicity to paddy rice.

Further, the compound represented by the formula (II) described in JP-A-1-508736 has an excellent herbicidal effect on paddy field weeds such as Nobie, Tamagami-tsutsui, Mizuhaya-tsui, and annual broad-leaved weeds. Requires a relatively high dose and is not always satisfactory for practical use.

Therefore, an object of the present invention is to provide a novel compound having excellent herbicidal activity against paddy field weeds, capable of efficiently removing the paddy field weeds at a low dose, and capable of suppressing the phytotoxicity against paddy rice to an extremely low level. And to provide a herbicide containing the same as an active ingredient.

[0008]

[Means for Solving the Problems] The present inventors focused on the fact that the above-mentioned known oxirane derivatives have herbicidal activity against grasses, and have investigated other paddy weeds such as grasshopper annual weeds. As a result of extensive research on oxirane derivatives having excellent herbicidal activity and selectivity against oxirane derivatives, a novel oxirane derivative having a phenyl skeleton, in which an oxime or an alkyloxime is directly or indirectly bonded to the phenyl skeleton, It has excellent herbicidal activity against paddy field weeds such as, Nobie, Pleurotus cornucopsis, Cyperus cylindrica, and annual broad-leaved weeds, and also has high selectivity, especially intergeneric selectivity between paddy rice and Nobie, with low dosage The inventors have found that weeds can be removed efficiently and that they cause little phytotoxicity to paddy rice, and the present invention has been completed based on this finding.

That is, the present invention has the general formula

[Chemical 5] (In the formula, X represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R ² represents a hydrogen atom or 1 to 1 carbon atoms. 6 represents an alkyl group, and n represents 0 or 1.), and a herbicide containing the oxirane derivative as an active ingredient.

The oxirane derivative represented by the general formula (III) is a novel compound, and X, R ¹ , R ² and n in the formula will be specifically described as follows.

X is a halogen atom or a haloalkyl group having 1 to 4 carbon atoms. Examples of the halogen atom include chlorine, fluorine, iodine and bromine, and chlorine is particularly preferable. As the haloalkyl group having 1 to 4 carbon atoms,
Examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group having one or more of the above halogen atoms, and particularly preferred are a trifluoromethyl group and a monochloromethyl group.

R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group, and particularly preferable ones are a methyl group and an ethyl group.

R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and particularly preferable ones are:
A methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. In the following, a methyl group is Me,
The ethyl group may be abbreviated as Et, the n-propyl group as n-Pr, the i-propyl group as i-Pr, and the n-butyl group as n-Bu.

N is 0 or 1. When n is 0, it means that the oxime or alkyl oxime is directly bonded to the phenyl group, and when n is 1, it means that the oxime or alkyl oxime is bonded to the phenyl group via the oxymethylene group. ..

Typical examples of the oxirane derivative of the present invention represented by the general formula (III) include the following.

3- (1,1,1-trichloro-3,4-
Epoxybutan-3-yl) benzaldehyde O-methyloxime 3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) benzaldehyde O-ethyloxime 3- (1,1,1-trichloro- 3,4-epoxybutan-3-yl) benzaldehyde O-normal propyl oxime 3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) benzaldehyde O-normal butyl oxime 3- (1, 1,1-Trichloro-3,4-epoxybutan-3-yl) acetophenone O-methyloxime 3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) acetophenone O-ethyloxime 3 -(1,1,1-Trichloro-3,4-epoxybutan-3-yl) acetophenone O-isopropyl Oxime 3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) acetophenone O-normabutyl oxime [3- (1,1,1-trichloro-3,4-epoxybutane-3- Yl) phenyl] ethylketone O-methyloxime [3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenyl] ethylketone O-ethyloxime 3- (2,2-dichloro-1, 1,1-trifluoro-
4,5-epoxypentan-4-yl) acetophenone O-methyloxime 3- (1,2,2-trichloro-4,5-epoxypentan-4-yl) acetophenone O-methyloxime [3- (1,1 , 1-Trichloro-3,4-epoxybutan-3-yl) phenoxy] acetone oxime [3- (1,1,1-Trichloro-3,4-epoxybutan-3-yl) phenoxy] acetone O-methyloxime [3- (1,1,1-Trichloro-3,4-epoxybutan-3-yl) phenoxy] acetone O-ethyloxime α- [3- (1,1,1-trichloro-3,4-epoxybutane -3-yl) phenoxy] benzophenone O
-Methyloxime [3- (2,2-dichloro-1,1,1-trifluoro-4,5-epoxypentan-4-yl) phenoxy]
Acetone O-methyl oxime [3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenoxy] acetaldehyde O-
Methyl oxime [3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenoxy] acetaldehyde O-
Methyl oxime [3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenoxy] acetaldehyde O-
Ethyl oxime [3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenoxy] acetaldehyde O-
Ethyloxime 3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) benzaldehyde O-isopropyloxime Further, the compound of the present invention has optical isomers based on the quaternary carbon of the oxirane moiety. It exists and is usually obtained as a racemate, but each enantiomer can be obtained by a known method such as asymmetric synthesis. The compound of the present invention may be a racemate or each optical isomer alone, and each can be used as a herbicide.

The compounds of the present invention also have geometrical isomers in the oxime part. When it is obtained as a mixture of E form and Z form, it can be separated by a known method. The compound of the present invention may be a mixture of E isomers and Z isomers, or each geometrical isomer (E isomer or Z isomer) alone, and each can be used as a herbicide.

The oxirane derivative (III) of the present invention can be produced by epoxidizing an alkene derivative (IV) such as a butene derivative or a pentene derivative with a peroxide as shown by the following formula. ..

[0019]

[Chemical 6] (X, R ¹ , R ² and n in the formula have the same meanings as above.) The peroxide used in this reaction is not particularly limited, and is usually one used for epoxidation of an ethylenic double bond. For example, cumene hydroperoxide, t-butyl-hydroperoxide, cyclohexyl hydroperoxide, peracetic acid, α-hydroperoxyisobutyric acid, perbenzoic acid, perorganic carboxylic acid such as m-chloroperbenzoic acid, etc. are used. Of these, perorganocarboxylic acids, especially peracetic acid and m-chloroperbenzoic acid, are preferred. The reaction is usually carried out in an inert solvent, preferably at a temperature in the range 0-80 ° C. Examples of the inert solvent include methylene chloride, chloroform, carbon tetrachloride, dichloromethane,
Halogenated hydrocarbons such as 1,1,1-trichloroethane and o-dichlorobenzene are preferably used. Further, if desired, the reaction may be carried out by adding a buffering agent such as sodium acetate, sodium benzoate, disodium hydrogen phosphate, lithium carbonate to the reaction system. Regarding the use ratio of the alkene derivative (IV) and the peroxide,
It is desirable to use the peroxide in a ratio of 1 to 4 times the equivalent of the alkene derivative (IV). The reaction time varies depending on the reaction temperature and the type of peroxide used, and cannot be uniquely determined, but is usually about 1 to 50 hours.

Further, the oxirane derivative (III) of the present invention
Can also be produced by reacting the carbonyl derivative (V) with hydroxylamine or O-alkylhydroxylamine in the presence of a base, as shown by the following formula.

[0021]

[Chemical 7] (X, R ¹ , R ² and n in the formula have the same meanings as above.) Examples of the O-alkylhydroxylamine used in this reaction include O-methylhydroxylamine and O-ethylhydroxylamine. You can The base is not particularly limited, for example sodium carbonate, sodium hydrogen carbonate, potassium carbonate,
Inorganic bases such as potassium hydrogen carbonate, triethylamine,
Amines such as pyridine can be used. This reaction is usually carried out in an inert solvent, preferably 15 to
It is carried out at temperatures in the range of 80 ° C. As the inert solvent, alcohols such as methanol and ethanol are preferably used. Regarding the usage ratio of the carbonyl derivative (V) and hydroxylamine or O-alkylhydroxylamine, hydroxylamine or O-alkylhydroxylamine is used in a ratio of 1 to 4 times the equivalent of the carbonyl derivative (V). desirable. The reaction time varies depending on the reaction temperature and the type of the base used and cannot be uniquely determined, but is usually about 1 to 20 hours.

The oxirane derivative produced by the above reaction can be recovered by a conventional method, but may be further purified by a known means such as column chromatography if necessary.

The alkene derivative (IV) can be produced by the following process using the propene derivative (VI) as a raw material.

[0024]

[Chemical 8] (In the formula, X, R ¹ , R ² and n have the same meanings as described above, and X ′ represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms.) That is, a catalyst such as cuprous chloride and piperidine Of propene derivative (VI) and polyhaloalkane (CC
The desired alkene derivative (IV) or polyhaloalkane derivative (VII) can be obtained by reacting 1 ₂ XX ') with a temperature of 0 ° C to the boiling point of the polyhaloalkane for about 1 to 20 hours. In this case, the alkene derivative (IV) may be directly led or the polyhaloalkane derivative (VII) may be led by appropriately selecting the reaction conditions. When a polyhaloalkane derivative (VII) is obtained, it is prepared by using, for example, o-dichlorobenzene, 1,2
Heating to a suitable temperature in the presence of a catalyst such as cuprous chloride or ferric chloride in a solvent such as dichloroethane can lead to the desired alkene derivative (IV).

The alkene derivative (IV) can also be produced by the following process using the propenecarbonyl derivative (VIII) as a raw material.

[0026]

[Chemical 9] (In the formula, X, R ¹ , R ² and n have the same meaning as described above, and X ′ represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms.) That is, the propene carbonyl derivative (VIII ) By polyhaloalkylation of
An alkene carbonyl derivative (IX) is obtained. Next, this alkene carbonyl derivative (IX) can be converted into the desired alkene derivative (IV) by oxime etherification by the above-mentioned method.

The propene derivative (VI) or the propene carbonyl derivative (VIII) is prepared from the following five processes (first to fifth processes) using readily available raw materials.
Can be manufactured by.

First, the first process will be described.

[0029]

[Chemical 10] (In the formula, X, R ¹ , R ² and n have the same meanings as described above, and X ′ represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms.) That is, 3-isopropenylphenol and α-halo The desired propene carbonyl derivative (VIII) can be obtained by reacting the carbonyl derivative in the presence of a base at a temperature usually in the range of 15 to 80 ° C. This reaction is usually a polar solvent such as acetone, dimethylformamide, dimethylsulfoxide,
It is carried out in a solvent such as N-methylpyrrolidone, and as the base, for example, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium hydroxide and the like are preferably used.

Next, a propene carbonyl derivative (VIII)
The desired propene derivative (VI) can be obtained by oxime etherification by the above-mentioned method. Alternatively, the propene carbonyl derivative (VIII) is reacted with hydroxylamine in the same manner as above to obtain an oxime derivative (X), which is then added to a solvent such as acetone, dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone. The desired propene derivative (VI) can also be obtained by reacting an alkyl halide in the presence of a base at a temperature usually in the range of 15 to 80 ° C. As the base in this reaction, for example, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium hydroxide and the like are preferable, and if desired, a catalyst such as sodium iodide or potassium iodide may be added to this reaction system. May be added to carry out the reaction.

Next, the second process will be described.

[0032]

[Chemical 11] (Wherein R ¹ and R ² have the same meanings as described above, and X ′
Represents a halogen atom. ) That is, first, in 3-cyanobenzophenone in an ether such as diethyl ether, diisopropyl ether, or tetrahydrofuran,
A phosphorus ylide such as triphenylphosphine methylene ylide is usually reacted at room temperature to obtain 3-isopropenylbenzonitrile (XI).

Next, 3-isopropenylbenzonitrile (XI) was mixed with diethyl ether, diisopropyl ether, and
Ether such as tetrahydrofuran or benzene,
In an aromatic solvent such as toluene, a Grignard reagent such as methylmagnesium halide or ethylmagnesium halide or an alkyllithium such as methyllithium or ethyllithium is usually reacted at a temperature in the range of -50 to 110 ° C to obtain a desired propene carbonyl derivative ( VIII)
Can be obtained.

Next, the desired propene derivative (VI) is obtained by the two-step reaction of the oxime etherification of the propene carbonyl derivative (VIII) by the above method or the oxime formation and O-alkylation by the same method as above. be able to.

Next, the third process will be described.

[0036]

[Chemical 12] (Wherein R ¹ and R ² have the same meanings as described above, and X ′
Represents a halogen atom. ) That is, first, the cyanocarbonyl derivative (XII) is oxime-etherified by the above method, or oxime-ized by the same method as described above, O-
The two-step reaction of alkylation gives the cyanooxime ether derivative (XIII).

Next, a cyanooxime ether derivative (XI
II) is reacted with an ether such as diethyl ether, diisopropyl ether or tetrahydrofuran or an aromatic solvent such as benzene or toluene with a Grignard reagent such as methyl magnesium halide or methyl lithium at a temperature usually in the range of -50 to 110 ° C. The desired propene derivative (VI) can be obtained by obtaining the ether acetophenone derivative (XIV) and then subjecting this to the Wittig reaction in the same manner as above. Alternatively, the oxime ether acetophenone derivative (XIV) is reacted with a Grignard reagent of methylmagnesium halide or methyllithium in the same manner as above to obtain a carbinol derivative (XV), which is then preferably t-butylcarbinol or the like. In the presence of the polymerization inhibitor and the inorganic salt such as potassium sulfate, usually 100 to 1
The desired propene derivative (VI) can also be obtained by heating at a temperature in the range of 50 ° C. and dehydration.

Next, the fourth process will be described.

[0039]

[Chemical 13] (In the formula, X, R ¹ , R ² and n have the same meanings as described above, X ′ represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, and X ″ represents a halogen atom.) That is, first, cyanocarbonyl Derivative (XII) and ethylene glycol,
The acetal derivative (XVI) is obtained by reacting with a diol such as 1,3-propanediol in the presence of an acid by heating to a temperature usually in the range of 80 to 150 ° C. while removing water. This reaction is usually carried out in an aromatic solvent such as benzene or toluene. The acid is not particularly limited, and for example, p-toluenesulfonic acid, oxalic acid, adipic acid, sulfuric acid, acetic acid and the like are preferably used.

Next, the isopropenyl acetal derivative (XVII) is obtained from the acetal derivative (XVI) by the Grignard reaction and the Wittig reaction according to the above-mentioned method, which is then hydrolyzed in the presence of an acid to give the desired propene carbonyl. The derivative (VIII) can be obtained. This reaction is usually performed in an inert solvent such as acetone, diethyl ether or tetrahydrofuran. The acid is not particularly limited, and sulfuric acid, hydrochloric acid, etc. are preferably used.

Next, the desired propene derivative (VI) can be obtained from the propene carbonyl derivative (VIII) by the same method as in the third process.

Further, an isopropenyl acetal derivative (X
Olefin carbonyl derivatives (IX) can also be obtained by the above polyhaloalkylation of VII).

Next, the fifth process will be described.

[0044]

[Chemical 14] (Wherein R ¹ and R ² have the same meanings as described above, and X ′
Represents a halogen atom. ) That is, first, 3-cyanobenzoic acid ethyl ester is reacted with a Grignard reagent of methylmagnesium halide in the same manner as above to obtain a carbinol derivative (XVIII), which is then dehydrated by the same method as described above. The desired propene carbonyl derivative (VIII) can be obtained. Next, the desired propene derivative (VI) can be obtained from the propene carbonyl derivative (VIII) by the same method as in the third process.

The carbonyl derivative (V) is obtained by converting the propene carbonyl derivative (VIII) or ethyl 3-isopropenylphenoxyacetate (3-isopropenylphenol and ethyl promoacetate into the first of the first process).
Can be produced by the same method as the step), and can be produced by the following sixth process.

[0046]

[Chemical 15] (X, R ¹ and n in the formula have the same meanings as described above,
X'represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms. ) That is, first, the propene carbonyl derivative
(VIII) or ethyl 3-isopropenylphenoxyacetate is reduced in an ether such as diethyl ether, diisopropyl ether or tetrahydrofuran with lithium aluminum hydride or the like at a temperature usually in the range of 0 to 80 ° C. to give an alcohol derivative ( XIX). Alternatively, the alcohol derivative (XI is usually reduced by reducing with sodium borohydride in an alcohol such as methanol, ethanol or isopropanol at a temperature usually in the range of 0 to 80 ° C.
X) can also be obtained.

Next, the epoxy alcohol derivative (IIX) is obtained by the two-step reaction of the polyhaloalkylation and oxidation of the alcohol derivative (XIX) by the above method.

Next, the epoxy alcohol derivative (IIX) is added in an inert solvent such as methylene chloride or pyridine,
The desired carbonyl derivative (V) can be obtained by oxidation with a chromic acid compound such as a chromium trioxide-pyridine complex at a temperature usually in the range of 0 to 30 ° C. Alternatively, the desired carbonyl derivative (V) can be obtained by oxidizing the epoxy alcohol derivative (IIX) with dimethyl sulfoxide, oxalyl chloride or the like.

The oxirane derivative of the present invention is an annual weed such as Nobie, which is a paddy weed: Annual weeds of Cyperaceae, such as P. persicae: Annual broad-leaved weeds, such as Scutellaria japonica, and Weeds: excellent weeding against perennial weeds such as Cyperus japonicus. In addition to having activity, it has high selectivity, and can control these weeds effectively with a dosage of about 100 g per 10 ares, and the dosage may bring about any phytotoxicity to paddy rice. Absent.

The herbicide of the present invention contains the above-mentioned oxirane derivative, that is, the novel oxirane derivative of the present invention represented by the general formula (III), as an active ingredient. It can be used by mixing it with a liquid carrier or a solid carrier such as a fine powder of a mineral substance, and formulating it into a form such as a wettable powder, an emulsion, a powder or a granule. A surfactant may be added in order to impart emulsifying property, dispersibility, spreadability and the like during formulation.

When the herbicide of the present invention is used in the form of a wettable powder, it is usually used in a proportion of 10 to 55% by weight of the oxirane derivative of the present invention, 40 to 88% by weight of a solid carrier and 2 to 5% by weight of a surfactant. The composition may be blended to prepare a composition, which may be used. When used in the form of an emulsion, it is usually prepared by mixing 20 to 50% by weight of the oxirane derivative of the present invention, 35 to 75% by weight of a solvent, and 5 to 15% by weight of a surfactant.

On the other hand, when it is used in the form of powder, it is usually 1 to 16% by weight of the oxirane derivative of the present invention, and the solid carrier 80
˜97% by weight and 2 to 5% by weight of the surfactant may be mixed and prepared. When used in the form of granules, the oxirane derivative of the present invention may be prepared by blending it in a proportion of 0.5 to 16% by weight, a solid carrier 80 to 97% by weight, and a surfactant 2 to 5% by weight. .. Here, a fine powder of a mineral substance is used as the solid carrier, and examples of the fine powder of a mineral substance include diatomaceous earth, oxides such as slaked lime, phosphates such as apatite, sulfates such as gypsum, talc and pyro. Examples thereof include silicates such as ferrite, clay, kaolin, bentonite, acid clay, white carbon, quartz powder, and silica stone powder.

An organic solvent is used as the solvent,
Specifically, aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated hydrocarbons such as o-chlorotoluene, trichloromethane and trichloroethylene, alcohols such as cyclohexanol, amyl alcohol and ethylene glycol, isophorone, cyclohexanone and cyclohexenyl. There may be mentioned ketones such as cyclohexanone, butyl cellosolve, ethers such as dimethyl ether and methyl ethyl ether, esters such as isopropyl acetate, benzyl acetate and methyl phthalate, amides such as dimethylformamide, or a mixture thereof.

Further, as the surfactant, any of anionic type, nonionic type, cationic type and zwitterionic type (amino acid, betaine, etc.) can be used.

The herbicide of the present invention may contain other herbicidal active ingredients, if necessary, in addition to the oxirane derivative represented by the general formula (III) as an active ingredient. As such other herbicidal active ingredients, conventionally known herbicides, for example, phenoxy type, diphenyl ether type, triazine type, urea type, carbamate type, thiol carbamate type, acid anilide type, pyrazole type, phosphoric acid type, sulfonylurea type , Oxadiazone-based compounds, and the like, which can be appropriately selected and used from these herbicides.

Furthermore, the herbicide of the present invention can be mixed with insecticides, fungicides, plant growth regulators, fertilizers, etc., if necessary.

[0057]

EXAMPLES Next, the present invention will be described in more detail with reference to production examples and test examples, but the present invention is not limited to these examples.

Production Example 1 Step 1 [Compound (VI) → Compound (IV)] 1.20 g (6.8 mmol) of 3-isopropenylbenzaldehyde O-methyloxime was dissolved in 30 ml of bromotrichloromethane to prepare a first chloride. Copper (0.01 g) and piperidine (1.2 ml, 12.1 mmol) were sequentially added, and the mixture was heated at 80 ° C. for 2 hours. Next, 5% by weight hydrochloric acid was added, and the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 50) to give 3- (1,
1,1-Trichloro-3-buten-3-yl) benzaldehyde O-methyloxime 1.08 g (yield 54
%) Was obtained.

Step 2 [Compound (IV) → Compound (II
I)] 3- (1,1,1-Trichloro-3-buten-3-yl) benzaldehyde O-methyloxime 1.08 g
(3.7 mmol) was dissolved in 15 ml of methylene chloride, 0.01 g of disodium hydrogen phosphate and 1.3 g (5.3 mmol) of 70% m-chloroperbenzoic acid were sequentially added, and the mixture was stirred at room temperature for 24 hours. .. Next, the methylene chloride layer was washed with a saturated sodium carbonate aqueous solution and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 30), and 3-
(1,1,1-trichloro-3,4-epoxybutane-
3-yl) benzaldehyde O-methyl oxime (Compound No. 1) was obtained. Yield 0.51g, yield 45%
Met. The analytical values of this product are shown in Table 3.

Production Examples 2 to 10 [Compound (VI) → Compound (IV) → Compound (III)] [Table 1 and Table 2] instead of 3-isopropenylbenzaldehyde O-methyloxime used in Production Example 1. The same operation as in Production Example 1 was carried out except that the various 3-isopropenylaryl O-alkyl oximes shown below were used, and the corresponding oxirane derivatives (Compound Nos. 2 to 10) are shown in Tables 1 and 2, respectively. Got at a rate.
These analytical values are shown in Tables 3 and 4.

Production Example 11 Step 1 [Compound (VI) → Compound (VII) → Compound (IV)] 0.75 g (4.0 mmol) of 3-isopropenylacetophenone O-methyloxime was added to 1,1,1- Dissolved in 15 ml of trichloro-2,2,2-trifluoroethane, 0.01 g of cuprous chloride and 0.8 ml of piperidine (8.
(1 mmol) was sequentially added, and the mixture was heated under reflux for 1 hour.
Next, 5% by weight hydrochloric acid was added, and the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. Chloroform was evaporated under reduced pressure to give the intermediate 3- (2,2,4-trichloro-1,1,1
-Trifluoropentan-4-yl) acetophenone
O-methyl oxime was obtained. This intermediate was dissolved in 20 ml of 1,2-dichloroethane to give 0.5 g of anhydrous ferric chloride.
(3.1 mmol) was added, and the mixture was heated under reflux for 7 hours. Next, water was added and the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 50) to give 3- (2,2-dichloro-1,1,1-trifluoro-4-penten-4-yl) acetophenone. O
0.80 g (59% yield) of methyl oxime was obtained.

Step 2 [Compound (IV) → Compound (II
I)] 3- (2,2-dichloro-1,1,1-trifluoro-
4-Penten-4-yl) acetophenone O-methyloxime 0.80 g (2.4 mmol) was dissolved in 15 ml of methylene chloride, and 0.01 g of disodium hydrogen phosphate was added.
1.0 g (4.1 mmol) of 70% m-chloroperbenzoic acid was sequentially added, and the mixture was stirred at room temperature for 30 hours. Next, the methylene chloride layer was washed with a saturated sodium carbonate aqueous solution and dried over anhydrous sodium sulfate. The crude product was subjected to column chromatography (silica gel, ethyl acetate: hexane = 1: 1).
30) and then 3- (2,2-dichloro-1,1,1)
-Trifluoro-4,5-epoxypentan-4-yl) acetophenone O-methyl oxime (Compound No.
11) 0.60 g (yield 72%) was obtained. Table 5 shows the analytical values of this product.

Production Example 12 [Compound (VI) → Compound
(VII) → Compound (IV) → Compound (III)] 1,1,1-trichloro-2,2,2-trifluoroethane used in Production Example 11 was replaced with 1,1,1.
The same operation as in Production Example 11 was carried out except that 1,2-tetrachloroethane was used, and Compound No. 12-three
(1,2,2-Trichloro-4,5-epoxypentan-4-yl) acetophenone O-methyloxime (yield of step 1 64%, step 2 71%) was obtained. Table 5 shows the analytical values of this product.

Production Example 13 Step 1 [Compound (VIII) → Compound (IX) → Compound (IV)] 2.85 g (1 of 3-isopropenylphenoxyacetone)
5.0 mmol) was dissolved in 40 ml of bromotrichloromethane, 0.02 g of cuprous chloride and 2.2 ml of piperidine (2
2.2 mmol) were added sequentially and then heated at 80 ° C. for 45 minutes. Next, 5% by weight hydrochloric acid was added, and the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. Chloroform was distilled off under reduced pressure to give the intermediate 3- (1,1,1-trichloro-3).
-Buten-3-yl) phenoxyacetone was obtained. This intermediate was dissolved in 50 ml of ethanol, 2.09 g (30.0 mmol) of hydroxylamine hydrochloride and 4.77 g (45.0 mmol) of anhydrous sodium carbonate dissolved in 20 ml of water were added, and the mixture was stirred at room temperature for 2 hours. did. Next, water was added and the mixture was extracted with diethyl ether and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 5) to give 3-
3.05 g (yield 63%) of (1,1,1-trichloro-3-buten-3-yl) phenoxyacetone oxime was obtained.

Step 2 [Compound (IV) → Compound (II
I)] 3- (1,1,1-Trichloro-3-buten-3-yl) phenoxyacetone oxime (1.50 g, 4.7 mmol) was dissolved in methylene chloride (30 ml), and disodium hydrogenphosphate (0.02 g) was added. , 70% m-chloroperbenzoic acid (1.5 g, 6.1 mmol) were sequentially added, and the mixture was stirred at room temperature for 36 hours.

Next, the methylene chloride layer was washed with a saturated aqueous sodium carbonate solution and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 4) to give 3- (1,1,1)
1-trichloro-3,4-epoxybutan-3-yl)
Phenoxyacetone oxime (Compound No. 13) was obtained. The yield was 0.63 g (yield 40%). Table 5 shows the analytical values of this product.

Production Examples 14 and 15 [Compound (VIII)]
→ Compound (IX) → Compound (IV) → Compound (III)] Production except that O-methylhydroxylamine hydrochloride and O-ethylhydroxylamine hydrochloride were used instead of the hydroxylamine hydrochloride used in Production Example 13, respectively. The same operation as in Example 13 was performed, and the compound No. 3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenoxyacetone O-methyl oxime corresponding to 14,15 (yield of step 1 7
4%, yield of step 2 48%), 3- (1,1,1-
Trichloro-3,4-epoxybutan-3-yl) phenoxyacetone O-ethyloxime (yield of step 1 62%, step 2 45%) was obtained. Table 5 shows these analysis values.

Production Example 16 [Compound (VIII) → Compound (IX) → Compound (IV) → Compound (III)] In place of 3-isopropenylphenoxyacetone used in Production Example 13, 3-isopropenylphenoxyacetophenone. Was used, and O-methylhydroxylamine hydrochloride was used in place of hydroxylamine hydrochloride, the same operation as in Production Example 13 was performed, and Compound No. 3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenoxyacetophenone O-methyloxime (65% yield of step 1, 58% yield of step 2) corresponding to 16 was obtained. Obtained. Table 5 shows the analytical values of this product.

Production Example 17 [Compound (VIII) → Compound (IX) → Compound (IV) → Compound (III)] 3-isopropenylacetophenone used in Production Example 11 was replaced with 3-isopropenylacetophenone. The same operation as in Production Example 11 was carried out except that propenylphenoxyacetone was used, and the intermediate 3- (2,2-
Dichloro-1,1,1-trifluoro-4-pentene-
4-yl) phenoxyacetone was obtained. Next, in Production Example 13, 3- (2,2-dichloro-1,1,1-trifluoro-4-penten-4-yl) phenoxyacetone was used instead of 3-isopropenylphenoxyacetone. , And O-methylhydroxylamine hydrochloride instead of hydroxylamine hydrochloride were used, the same operation as in Preparation Example 13 was performed to give compound N
o. 3- (2,2-dichloro-1,1, corresponding to 17
1-Trifluoro-4,5-epoxypentan-4-yl) phenoxyacetone O-methyloxime (total yield 31%) was obtained. Table 6 shows the analytical values of this product.

Production Examples 18 and 19 [Compound (V) → Compound (III)] 3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenoxyacetaldehyde 1.50 g
(4.8 mmol) was dissolved in 50 ml of ethanol, and 1.61 g (19.3 mmol) of O-methylhydroxylamine hydrochloride and 1.53 g (14.4 mmol) of anhydrous sodium carbonate dissolved in 20 ml of water were added. , Stirred at room temperature for 4 hours. Then add water and extract with diethyl ether,
It was dried over anhydrous sodium sulfate. Column chromatography of the crude product (silica gel, ethyl acetate: hexane =
1:15) and compound No. 3- (1,1,1-trichloro-3-buten-3-yl) phenoxyacetaldehyde O-methyl ether corresponding to 18,19, 0.42 g of Z isomer (yield 27%), 0.79 g of E isomer
(Yield 50%) was obtained. Table 6 shows these analytical values.

Production Examples 20 and 21 [Compound (V) → Compound (III)] Production Examples except that O-ethylhydroxylamine hydrochloride was used instead of O-methylhydroxylamine hydrochloride in Production Example 18. Perform the same operation as 18.
Compound No. 3- (1,1,1-trichloro-3-buten-3-yl) phenoxyacetaldehyde O-ethyl ether corresponding to 20,21, Z-form (yield 30%),
Form E (yield 45%) was obtained. Table 6 shows these analytical values.

Production Example 22 [Compound (VI) → Compound (IV) → Compound (III)] 3-isopropenylbenzaldehyde used in Production Example 1 Instead of O-methyloxime, 3-isopropenyl shown in Table 2 was used. The same operation as in Preparation Example 1 was carried out except that an aryl O-alkyl oxime was used,
The oxirane derivative (Compound No. 22) was obtained in the yields shown in Table 2. Table 6 shows these analytical values. Production Example 23 [Production Example of Starting Compound (VIII) of Production Examples 13 to 15 by the above-mentioned first process] 2.00 g (10.0 mmol) of 67% toluene solution of 3-isopropenylphenol and chloroacetone 2 ．
0 ml (25.1 mmol) was dissolved in 20 ml acetone,
Anhydrous potassium carbonate (2.00 g, 14.5 mmol) was added, and the mixture was heated under reflux for 8 hours. Next, acetone was distilled off under reduced pressure, followed by extraction with diethyl ether. The organic layer was washed successively with a 5% aqueous sodium hydroxide solution and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to give 3-isopropenylphenoxyacetone (1.85 g, yield 97%).
Got

Production Example 24 [Production Example of Starting Compound (VI) of Production Example 9 by the Second Process Above] Step 1 [3-cyanoacetophenone → compound (X
I)] Methyltriphenylphosphonium bromide 6.4 g
(17.9 mmol) was dissolved in 40 ml of tetrahydrofuran and a solution of n-butyllithium in n-hexane (1.55 mol / 1) 16.0 ml (24.8 mmol).
Was added dropwise at room temperature, and the mixture was stirred at room temperature for 10 minutes. Next, 2.0 g (13.8 mmol) of 3-cyanoacetophenone dissolved in 20 ml of tetrahydrofuran was added dropwise to this solution at room temperature, and the mixture was stirred at room temperature for 15 hours. Next, a saturated ammonium chloride aqueous solution was added, the mixture was extracted with diethyl ether, washed with saturated saline, and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 40), and 3-
1.62 g of isopropenyl benzonitrile (yield 82
%) Was obtained.

Step 2 [Compound (XI) → Compound (VI
II)] To 3 ml of a diethyl ether solution of 0.67 g (27.6 mmol) of magnesium, 5 ml of a diethyl ether solution of 2.3 ml (30.8 mmol) of ethyl bromide was added dropwise so that the diethyl ether was slowly refluxed at room temperature. Stirred for 10 minutes. Next, a solution of 1.62 g (11.3 mmol) of 3-isopropenylbenzonitrile dissolved in 20 ml of benzene was added dropwise to this solution at room temperature, and the mixture was heated under reflux for 2 hours. Next, a saturated aqueous solution of ammonium chloride was added at 0 ° C., extracted with diethyl ether, washed with saturated saline,
It was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure,
(3-isopropenylphenyl) ethyl ketone 1.93
g (yield 98%) was obtained. Step 3 [Compound (VIII) → Compound (VI)] (3-isopropenylphenyl) ethyl ketone 1.93
g (11.1 mmol) was dissolved in 20 ml of ethanol,
1.20 g of O-methylhydroxylamine hydrochloride (14.
4 mmol), 1.8 ml of pyridine (22.3 mmol)
Were sequentially added, and the mixture was heated under reflux for 2 hours. Next, water was added and the mixture was extracted with diethyl ether, washed with saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure (3
2.20 g (yield 98%) of -isopropenylphenyl) ethyl ketone O-methyl oxime was obtained.

Production Example 25 [Example of production of starting material compound (VI) of Production Example 1 by the above-mentioned third process] Step 1 [Compound (XII) → Compound (XIII)] In Step 3 of Production Example 23, The same operation as in Step 3 of Production Example 24 was performed except that 3-cyanobenzaldehyde was used in place of 3-isopropenylphenylethylketone, and 3.00 g of 3-cyanobenzaldehyde O-methyloxime (yield 99% ) Got.

Step 2 [Compound (XIII) → Compound (X
IV)] 3-Cyanobenzaldehyde O-methyl oxime 3.
00 g (18.7 mmol) of tetrahydrofuran 30
It was dissolved in ml, and 8.0 ml (24.0 mmol) of a solution of methylmagnesium bromide in diethyl ether (3.0 mol / 1) was added dropwise at 0 ° C., followed by stirring at room temperature for 7 hours. Then, a saturated aqueous solution of ammonium chloride was added at 0 ° C., the mixture was extracted with diethyl ether, washed with saturated saline, and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 20) to obtain 2.15 g (yield 65%) of 3-acetylbenzaldehyde O-methyloxime.

Step 3 [Compound (XIV) → Compound (V
I)] In Step 1 of Production Example 24, 3-acetylbenzaldehyde was used instead of 3-cyanoacetophenone.
Production Example 24 except that O-methyloxime was used.
The same operation as in Step 1 of Example 3 was conducted to obtain 1.00 g of 3-isopropenylbenzaldehyde O-methyloxime.
(Yield 72%) was obtained.

Production Example 26 (Production Example of Starting Material Compound (VI) of Production Example 4 by Fourth Process Above) Step 1 [Compound (XII) → Compound (XVI)] 10.0 g of 3-cyanobenzaldehyde (76 (3. 3 mmol) was dissolved in 100 ml of toluene, and 10.0 ml (179.3 mmol) of ethylene glycol and 0.30 g (1.6 mmol) of p-toluenesulfonic acid monohydrate were sequentially added to the resulting water. Then, the mixture was heated under reflux for 20 hours while removing water, extracted with diethyl ether, washed with saturated brine and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give 3-cyanobenzaldehyde ethylene glycol acetal 13. 0.37 g (yield 100%) was obtained.

Step 2 [Compound (XVI) → Compound (XV)
II)] The same operation as in Step 2 of Production Example 25 is performed except that 3-cyanobenzaldehyde ethylene glycol acetal is used in place of the 3-cyanobenzaldehyde O-methyloxime used in Step 2 of Production Example 25. , Intermediate 3-acetylbenzaldehyde ethylene glycol acetal was obtained. Next, Production Example 2 was repeated except that 3-acetylbenzaldehyde ethylene glycol acetal was used in place of 3-cyanoacetophenone in Step 1 of Production Example 24.
The same operation as in Step 1 of 4 was performed to obtain 0.54 g (yield 31%) of 3-isopropenylbenzaldehyde ethylene glycol acetal.

Step 3 [Compound (XVII) → Compound (VIII)] 3-isopropenylbenzaldehyde 1.25 g (6.6 mmol) of ethylene glycol acetal was dissolved in 15 ml of tetrahydrofuran, and 10 ml of 5% hydrochloric acid was added,
Stir at room temperature. Next, water was added and the mixture was extracted with diethyl ether, washed with saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.96 g (yield 100%) of 3-isopropenylbenzaldehyde.

Step 4 [Compound (VIII) → Compound (VI)] 3-isopropenyl benzaldehyde was used in place of 3-isopropenyl phenyl ethyl ketone used in Step 3 of Preparation Example 24, and O-hydrochloride was used. The same operation as in Step 3 of Production Example 24 was performed except that hydroxylamine hydrochloride was used instead of methylhydroxylamine to obtain an intermediate 3-isopropenylbenzaldehyde oxime (yield 98%). 0.43 g (2.7 mmol) of this intermediate was dissolved in 15 ml of acetone, and then 1.5 ml (11.2 mmol) of normal butane bromide, 0.75 g (5.4 mmol) of anhydrous potassium carbonate, and 0 g of potassium iodide were dissolved. 0.01 g was sequentially added, and the mixture was heated under reflux for 30 hours. Next, add water and extract with chloroform,
It was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and 3
0.57 g (yield 98%) of isopropenylbenzaldehyde O-normal butyl oxime was obtained.

Manufacturing Example 27 (Manufacturing Examples 5, 11, and 1)
Production Example of Starting Material Compound (VI) of 2 by the above-mentioned 5th Process] Step 1 [Ethyl 3-cyanobenzoate → Compound (XVI
II)] 4.50 g (25.7 mmol) of ethyl 3-cyanobenzoate was dissolved in 40 ml of benzene, and a solution of methylmagnesium bromide in diethyl ether (3.0 mol / 1) 4
After 2.0 ml (126.0 mmol) was added dropwise at 0 ° C,
The mixture was heated under reflux for 7 hours. 0 saturated ammonium chloride solution
The mixture was added at ℃, extracted with diethyl ether, washed with saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to give 3- (2-hydroxyisopropyl) acetophenone (3.93 g, yield 86%).

Step 2 [Compound (XVIII) → Compound (VIII)] 3.93 g (21.9 mmol) of 3- (2-hydroxyisopropyl) acetophenone, 0.02 g of potassium hydrogensulfate and 0.02 g of tert-butylcatechol. Sequentially added and heated at 120 ° C. for 2 hours. Next, water was added and the mixture was extracted with diethyl ether, washed with saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to give 3.44 g of 3-isopropenylacetophenone (yield 98%).
Got

Step 3 [Compound (VIII) → Compound (VI)] Production Example except that 3-isopropenylacetophenone was used in place of 3-isopropenylphenylethylketone used in Step 3 of Production Example 24. Two
The same operation as in Step 3 of 4 was carried out to give 0.91 g of 3-isopropenylacetophenone O-methyloxime.
(Yield 98%) was obtained.

Production Example 28 (Production Example of Starting Compound (V) of Production Examples 18 to 21 by the above-mentioned sixth process) Step 1 [Synthesis of ethyl 3-isopropenylphenoxyacetate] Step 1 of Production Example 23 In, the same operation as in Step 1 of Production Example 23 was performed except that ethyl bromoacetate was used instead of chloroacetone to obtain ethyl 3-isopropenylphenoxyacetate (yield 98%).

Step 2 [Ethyl 3-isopropenylphenoxyacetate → Compound (XIX)] 4.56 g (120.0 mmol) of sodium borohydride was suspended in 60 ml of methanol, and 8.80 g of ethyl 3-isopropenylphenoxyacetate ( 40.0 mmol)
What was melt | dissolved in 20 ml of methanol was dripped at 0 degreeC, and it stirred at room temperature for 2 hours. Next, water and 5% hydrochloric acid were sequentially added, extracted with chloroform, and dried over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure to obtain 6.48 g (yield 91%) of 2- (3-isopropenylphenoxy) ethanol.

Step 3 [Compound (XIX) → Compound (II
X)] The same operation as in Production Example 1 was performed except that 2- (3-isopropenylphenoxy) ethanol was used in place of 3-isopropenylbenzaldehyde O-methyloxime in Production Example 1, [3- (1,
1.03 g of 1,1-trichloro-3,4-epoxybutan-3-yl) phenoxy] ethanol (yield 48%)
Got

Step 4 [Compound (IIX) → Compound
(V)] 0.68 ml (9.6 mmol) of dimethyl sulfoxide was dissolved in 20 ml of methylene chloride to give 0.42 of oxalyl chloride.
ml (4.8 mmol), 1.00 g (3.2 mmol) of 2- [3- (1,1,1-trichloro-3,4-epoxybutan-3-yl) phenoxy] ethanol in 10 ml of methylene chloride. The dissolved ones were added dropwise at -50 ° C,
After 15 minutes, 2.7 ml (19.3 mmol) of triethylamine was added dropwise. Then slowly warm to room temperature and
After the lapse of time, water was added, the mixture was extracted with methylene chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and 2- [3-
(1,1,1-trichloro-3,4-epoxybutane-
3-yl) phenoxy] acetaldehyde 0.91 g
(Yield 92%).

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

[Table 5]

[0094]

[Table 6]

Further, the compound Nos. Obtained in Production Examples 1 to 22 were used.
Structural formulas 1 to 22 are shown below.

[0096]

[Chemical 16]

[0097]

[Chemical 17]

[0098]

[Chemical 18]

[0099]

[Chemical 19]

[0100]

[Chemical 20]

[0101]

[Chemical 21]

[0102]

[Chemical formula 22]

[0103]

[Chemical formula 23]

[0104]

[Chemical formula 24]

[0105]

[Chemical 25]

[0106]

[Chemical formula 26]

[0107]

[Chemical 27]

[0108]

[Chemical 28]

[0109]

[Chemical 29]

[0110]

[Chemical 30]

[0111]

[Chemical 31]

[0112]

[Chemical 32]

[0113]

[Chemical 33]

[0114]

[Chemical 34]

[0115]

[Chemical 35]

[0116]

[Chemical 36]

[0117]

[Chemical 37] Test Examples 1 to 22 (1) Preparation of Herbicide 97 parts by weight of tank (trade name: Sieglite) as a carrier, alkylaryl sulfonate as a surfactant (trade name: Neoperex, manufactured by Kao Atlas Co., Ltd.)
1.5 parts by weight and nonionic and anionic surfactants (trade name: Solball 800A, Toho Chemical Industry Co., Ltd.)
1.5 parts by weight were uniformly pulverized and mixed to obtain a carrier for wettable powder.

90 parts by weight of the carrier for wettable powder and 10 parts by weight of the oxirane derivative obtained in the above Production Examples 1 to 22 were uniformly pulverized and mixed to obtain a herbicide.

(2) Biological test (Flooded soil treatment test) Paddy soil was packed in a porcelain pot of 1/15500 are,
On the surface, Nobie, Tamagawai, broad-leaved weeds
Eels) and firefly seeds were evenly sown, and tubers of Spodoptera litura were further transplanted, and then paddy rice at the 2-leaf stage was transplanted.

After that, when the weeds germinated, a predetermined amount of the diluted solution of the herbicide obtained in the above (1) was uniformly dropped on the surface of the water for treatment, and then the pot was left at room temperature and sprinkled at appropriate times.

Table 7 shows the results of an investigation of the herbicidal effect and damage to rice crops after 20 days of treatment with the chemical solution. The dose is shown as the amount of active ingredient per 10 ares. For the damage to paddy rice and herbicidal effect, air-dry weight was measured, and the results were displayed as follows.

Degree of phytotoxicity Paddy rice phytotoxicity (compared to untreated plots) 0 100% 195 to 99% 290 to 94% 380 to 89% 460 to 79% 550 to 59% Degree of herbicidal effect Ratio to non-treated group) 0 100% 1 61 to 99% 2 21 to 60% 3 11 to 20% 41 to 10% 50% Test Comparative Example 1 In Test Example 1, oxirane obtained in Production Example 1 Instead of a derivative, the structural formula

[Chemical 38] 2- (3,5-dichlorophenyl) -2- represented by
(2,2,2-Trichloroethyl) oxirane [A]
(General name: Toridifan, Japanese Examined Patent Publication No. 53-3749), the same operation as in Test Example 1 was performed. The results are shown in Table 7.

[0123]

[Table 7]

Test Examples 23 to 30 Biological test (tube test) Novie was decompressed in water for 30 minutes and incubated at 30 ° C for 24 hours. Then, when the seeds are germinated to a state of 1 mm, the diluted solution of the herbicide obtained in the above (1) is dispensed into a sample tube bottle (volume: 50 ml), and the germinated seeds are
0 grains were placed and incubated in an artificial weather device (temperature 25 ° C., light and dark every 12 hours). Further, as a control, a sample containing only ion-exchanged water was also incubated. One week later, the length of the Novier foliage (first leaf) was measured, and the elongation disorder rate [(1-average value of each drug / average value of control) x 100] was determined.

The results are shown in Table 8 at 50% elongation inhibition concentration.

Test Comparative Example 2 In Test Example 23, instead of the oxirane derivative obtained in Production Example 1, the structural formula was changed.

[Chemical Formula 39] [3- (5-trifluoromethyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane [B] represented by the formula (JP-A-1-508736).
Publication, Compound No. The same operation as in Test Example 23 was performed except that 1) was used. The results are shown in Table 8 at 50% elongation inhibition concentration.

[0127]

[Table 8]

As is clear from Tables 7 and 8 above,
The compound of the present invention has excellent intergeneric selectivity between paddy rice and lobster and has an excellent inhibitory effect on lobster growth at a remarkably low leaf amount as compared with the comparative compound.

[0129]

INDUSTRIAL APPLICABILITY The novel oxirane derivative of the present invention has an excellent herbicidal activity against weeds in paddy fields and is excellent in selectivity, particularly intergeneric selectivity between paddy rice and Nobie. Moreover, weeds can be effectively weeded with a low dosage, and the dosage does not cause any phytotoxicity to paddy rice. Therefore,
This oxirane derivative is extremely effective as a herbicide for paddy rice.

Claims (2)

[Claims] 1. A general formula: (In the formula, X represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² represents a hydrogen atom or 1 to 1 carbon atoms. An oxirane derivative represented by the formula (6), wherein n represents 0 or 1. 2. A general formula: (In the formula, X represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² represents a hydrogen atom or 1 to 1 carbon atoms. A herbicide containing an oxirane derivative represented by the formula (6), wherein n is 0, 1.