JP2756550B2 - Oxirane derivatives and herbicides containing them as active ingredients - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel oxirane derivative and a herbicide containing the same as an active ingredient.

Background Art Herbicides are extremely important drugs for labor saving of weed control work and improvement of productivity of agricultural and horticultural crops.Therefore, research and development of herbicides has been actively carried out for many years, and a wide variety of chemicals are currently in practical use. However, even today, there is a demand for the development of new drugs having even more excellent herbicidal properties, in particular, drugs capable of controlling only the target weeds selectively and at a low dose without causing phytotoxicity to cultivated crops. ing.

On the other hand, in the paddy field, together with rice, various weeds, such as annual grasses such as Nobie, annual cyperaceae weeds such as stag beetle, annual broadleaf weeds such as oak and kikasigusa, urikawa, hirumushiro, heramodaka, firefly, pine bye, swordfish, and so on. , Omodaka,
It is known that perennial weeds such as seri grow.
It is extremely important for rice cultivation to efficiently remove these weeds with a small amount of spraying without damaging the paddy rice, and because of the problem of environmental pollution. In particular, since Nobie is a grass weed, chemicals that have herbicidal activity against Nobie tend to cause harm to paddy rice. The development of highly potent drugs has become an important issue.

Oxirane derivatives having herbicidal activity include, for example, those of the formula Or a compound represented by the formula [Generic name: tridipha (tridipha
ne), Dow Chemical Company, tandem: (Tandem)] is known.

However, the compound represented by the formula (I) is effective in pre-emergence treatment against grasses such as Bigweed, Crabgrass, Johnsongrass, Wild Oat, Yellow Foxteal, etc., but has a herbicidal activity. It is low, and no specific example of use for paddy rice is given. On the other hand, the compound represented by the formula (II) has already been put to practical use in corn fields as a herbicide for controlling grass weeds. However, when used as a herbicide for paddy rice, it has poor selectivity. May cause phytotoxicity.

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

The present inventors have paid attention to the fact that the oxirane derivative has herbicidal activity against grasses, and has excellent herbicidal activity and selectivity against other paddy weeds, such as annual grasses such as grasshoppers. As a result of intensive studies on oxirane derivatives having a nitro group, a novel oxirane derivative having a specific nitrogen-containing allyloxyphenyl skeleton has been developed by Novier,
It has excellent herbicidal activity against P. japonicus, Spodoptera mori, annual broadleaf weeds, etc. and has high selectivity, especially excellent intergeneric selectivity between paddy rice and Nobies, and efficiently removes the paddy weeds with a low dose. In addition, they found that they could hardly cause phytotoxicity to paddy rice, and completed the present invention based on this finding.

DISCLOSURE OF THE INVENTION The present invention provides: (Where R ¹ is X ¹ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an acid amide group, and a 1 to 1 carbon atom. 4 represents an acylamino group or an alkylsulfonyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4. When n is plural, each X ¹ may be the same or different. R ² is a hydrogen atom or an alkoxyl group having 1 to 4 carbon atoms. An oxirane derivative represented by the formula: and (2) a general formula (Where R ¹ is X ¹ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an acid amide group, and a 1 to 1 carbon atom. 4 represents an acylamino group or an alkylsulfonyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4. When n is plural, each X ¹ may be the same or different. R ² is a hydrogen atom or an alkoxyl group having 1 to 4 carbon atoms. The present invention provides a herbicide containing the oxirane derivative represented by the formula (1) as an active ingredient.

The oxirane derivative of the present invention is a compound having a novel nitrogen-containing allyloxyphenyl skeleton and can be effectively used as a herbicide. Furthermore, the herbicide of the present invention has excellent herbicidal activity against paddy weeds such as Nobie, Tamayatsuri, Suzumeyatsuri, annual broadleaf weed, etc., and has high selectivity, especially intergeneric selectivity between paddy rice and Nobie. It has almost no phytotoxicity to paddy rice, and can effectively control the above weeds such as nobies at a low dose.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has a general formula (Where R ¹ is X ¹ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an acid amide group, and a 1 to 1 carbon atom. 4 represents an acylamino group or an alkylsulfonyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4. When n is plural, each X ¹ may be the same or different. R ² is a hydrogen atom or an alkoxyl group having 1 to 4 carbon atoms. ) And an oxirane derivative represented by the general formula III as an active ingredient.

The compound represented by the general formula III is a novel compound. Where R ¹ is X ¹ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an acid amide group, and a 1 to 1 carbon atom. 4 represents an acylamino group or an alkylsulfonyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4. When n is plural, each X ¹ may be the same or different. R ² is a hydrogen atom or carbon number 1-4
Is an alkoxyl group.

Representative examples of the oxirane derivative of the present invention include 2-
[3- (5-trifluoromethyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (compound No. 1), 2- [3- (6-trifluoromethyl- 2-pyridyloxy) phenyl] -2- (2,2,
2-trichloroethyl) oxirane (Compound No. 2), 2-
[3- (5-trifluoromethyl-6-chloro-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 3), 2- [3- (5- Chloro-2-pyridyloxy) phenyl] -2- (2,2,2
-Trichloroethyl) oxirane (Compound No. 4), 2-
[3- (2-pyridyloxy) phenyl] -2- (2,2,
2-trichloroethyl) oxirane (Compound No. 5), 2-
[3- (6-Cutoto-2-pyridyloxy) phenyl]
-2- (2,2,2-trichloroethyl) oxirane (compound No. 6), 2- [3- (6-bromo-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl ) Oxirane (Compound No. 7), 2- [3- (6-methoxy-2)
-Pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 8), 2- [3- (5
-Bromo-2-pyridyloxy) phenyl] -2- (2,
2,2-trichloroethyl) oxirane (compound No. 9), 2
-[3- (6-Methyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 10), 2- [3- (5-nitro-2-pyridyl) Oxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 11), 2- [3- (6-fluoro-2-pyridyloxy) phenyl] -2- (2,2, Two
-Trichloroethyl) oxirane (Compound No. 12), 2-
[3- (6-ethoxy-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (compound No. 13), 2- [3- (5-methyl-2-pyridyloxy) ) Phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 14), 2- [3- (3,5,6-trifluoro-2-pyridyloxy) phenyl] -2-
(2,2,2-trichloroethyl) oxirane (Compound No. 1
5), 2- [3- (5-trifluoromethyl-2-pyridyloxy) -5-methoxyphenyl] -2- (2,2,2-
Trichloroethyl) oxirane (Compound No. 16), 2-
[3- (3,5,6-trifluoro-4-methyl-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 17), 2- [3-(- Trifluoromethyl-2-pyridyloxy) phenyl] -2-
(2,2,2-trichloroethyl) oxirane (Compound No. 1
8), 2- [3- (4-Aminocarboxy-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 19), 2- [3- (3- Chloro-2-pyridyloxy) phenyl] -2- (2,2,2-
Trichloroethyl) oxirane (Compound No. 20), 2-
[3- (5-cyano-2-pyridyloxy) phenyl]
-2- (2,2,2-trichloroethyl) oxirane (compound No. 21), 2- [3- (6-methylsulfonyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloro Ethyl) oxirane (Compound No. 22), 2- [3- (3-
Fluoro-2-pyridyloxy) phenyl] -2- (2,
2,2-Trichloroethyl) oxirane (Compound No. 23), 2
-[3- (5-bromomethyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 24), 2- [3- (5-fluoromethyl-
2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 25), 2- [3-
(5-Difluoromethyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (compound No. 26), 2- [3- (5-fluoro-2-pyridyloxy) phenyl ] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 27), 2- [3- (5-acetylamino-pyridyloxy) phenyl] -2- (2,
2,2-Trichloroethyl) oxirane (Compound No. 28), 2
-[3- (thiazol-2-yloxy) phenyl]-
2- (2,2,2-trichloroethyl) oxirane (compound N
o.29), 2- [3- (Benzothiazol-2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 30), 2- [3- (pyrimidine-2
-Yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 31), 2- [3- (6-
Chloro-pyrimidin-4-yloxy) phenyl] -2
-(2,2,2-trichloroethyl) oxirane (Compound No.
32), 2- [3- (2-Chloro-pyrimidin-4-yloxy) phenyl] -2- (2,2,2-trichloroethyl)
Oxirane (Compound No. 33), 2- [3- (5-bromo-
Pyrimidin-2-yloxy) phenyl] -2- (2,2,
2-trichloroethyl) oxirane (Compound No. 34), 2-
[3- (5-Methyl-pyrimidin-2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (compound No. 35), 2- [3- (pyrazin-2-yloxy) phenyl ] -2- (2,2,2-trichloroethyl)
Oxirane (Compound No. 36), 2- [3- (6-chloro-
Pyrazin-2-yloxy) phenyl] -2- (2,2,2
-Trichloroethyl) oxirane (Compound No. 37), 2-
[3- (6-Chloro-pyridazin-3-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 38), 2- [3- (benzoxazole-
2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 39), 2- [3- (5
-Chlorothiazol-2-yloxy) phenyl] -2
-(2,2,2-trichloroethyl) oxirane (Compound No.
40), 2- [3- (5-Chloropyrazin-2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 41), 2- [3- (quinoxaline-
2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 42), 2- [3- (quinolin-2-yloxy) phenyl] -2- (2,2,2 −
Trichloroethyl) oxirane (Compound No. 43), 2-
[3- (3-chloropyrazin-2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 44), 2- [3- (4-methylthiazole-
2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (compound No. 45), 2- [3- (6
-Fluoropyrazin-2-yloxy) phenyl] -2
-(2,2,2-trichloroethyl) oxirane (Compound No.
46), 2- [3- (4-Chloro-1,2,5-thiadiazol-3-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 47), 2- [3-
(6-Fluoropyridazin-3-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 48), 2- [3- (5-trifluoromethyl-1,3,4 -Thiadiazol-2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (compound No. 49), 2- [3- (5-fluoropyrazine-
2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 50), 2- [3- (3
-Fluoropyrazin-2-yloxy) phenyl] -2
-(2,2,2-trichloroethyl) oxirane (Compound No.
51), 2- [3- (5-Methyl-1,3,4-thiadiazol-2-yloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (Compound No. 52), 2- [3-
(4-chlorothiazol-2-yloxy) phenyl]
-2- (2,2,2-trichloroethyl) oxirane (Compound No. 53) and the like, but are not limited to these compounds only.

The compound of the present invention has an optical isomer and is usually obtained as a racemate, but it is also possible to obtain each enantiomer by a known method such as asymmetric synthesis. The compound of the present invention can be used as a herbicide whether it is a racemate or each optical isomer alone.

 Next, the structural formula of the oxirane derivative is shown.

Table 1 shows the infrared absorption spectrum and the nuclear magnetic resonance spectrum.

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

(In the formula, R ¹ and R ² have the same meanings as described above.) There is no particular limitation on the peroxide used in this reaction, and those usually used for epoxidation of ethylenic double bonds, for example, cumene hydro Peroxide, t-
Perorganic carboxylic acids such as butyl-hydroperoxide, cyclohexyl hydroperoxide and peracetic acid, α-hydroperoxyisobutyric acid, perbenzoic acid and m-chloroperbenzoic acid can be used. And perorganic carboxylic acids, especially peracetic acid and m-chloroperbenzoic acid. The reaction is usually carried out in an inert solvent, preferably at a temperature in the range from 0 to 80C. As the inert solvent, for example, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloromethane, 1,1,1-trichloroethane, and o-dichlorobenzene are preferably used. If desired, a buffer such as sodium acetate or sodium benzoate may be added to the reaction system to carry out the reaction. As for the use ratio of the butene derivative (IV) and the peroxide, it is desirable to use the peroxide in a ratio of 1 to 3 equivalents to the butene derivative (IV). The reaction time varies depending on the reaction temperature, the type of peroxide used, and the like, and cannot be determined uniquely, but is usually about 1 to 30 hours.

The oxirane derivative generated by the reaction can be recovered by a usual method, but if necessary, may be purified by a known means, for example, column chromatography or the like.

The butene derivative (IV) is a propene derivative (V)
Can be used as a raw material and can be produced by the following process.

(R ¹ and R ² have the same meaning as described above.) That is, in the presence of a catalyst such as cuprous chloride and an amine such as piperidine and cyclohexylamine, the propene derivative (V) and bromotrichloromethane are Usually 0
The desired butene derivative (IV) or bromotrichlorobutane derivative (VI) can be obtained by reacting at a temperature in the range of from 0 ° C. to the boiling point of bromotrichloromethane for about 1 to 20 hours. In this case, the reaction may be led directly to the butene derivative (IV) or the bromotrichlorobutane derivative (VI) by appropriately selecting the reaction conditions. When the bromotrichlorobutane derivative (VI) is obtained, it is converted into a solvent such as o-dichlorobenzene or 1,2-dichloroethane in the presence of a catalyst such as cuprous chloride or ferric chloride. By heating to an appropriate temperature,
It can lead to the desired butene derivative (IV).

Further, the propene derivative (V) can be produced by the following two processes using easily available raw materials.

(R ¹ and R ² have the same meanings as described above, and X ² is a halogen atom.) That is, the nitrogen-containing allyl derivative (VII) and the α-methylstyrene derivative (VIII) are usually dissolved in an alkali in the presence of an alkali.
The propene derivative (V) can be obtained by heating and reacting at a temperature in the range of -120 ° C. This reaction is usually carried out in a polar solvent such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like. As the alkali, for example, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate , Sodium bicarbonate and the like are preferably used.

(R ¹ and R ² have the same meaning as described above, and X ² is a halogen atom.) That is, first, the nitrogen-containing allyl derivative (VII) and the acetophenone derivative (IX) are usually treated with an alkali in the presence of alkali to form
The reaction is carried out by heating to a temperature in the range of 120 ° C. to obtain a nitrogen-containing allyloxyacetophenone derivative (X). This reaction is usually carried out in a polar solvent such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like. As alkalis, potassium hydroxide, sodium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, hydrogen carbonate Potassium, sodium hydrogen carbonate and the like are preferably used.

Next, the nitrogen-containing allyloxyacetophenone derivative (X) was added to diethyl ether, diisopropyl ether,
In an ether such as tetrahydrofuran, a Grignard reagent of methylmagnesium halide or methyllithium is usually reacted at room temperature to obtain a carbinol compound (XI), which is then preferably reacted with a polymerization inhibitor such as t-butylcatechol and potassium sulfate. In the presence of inorganic salts such as
The desired propene derivative (V) can be obtained by heating and dehydrating usually at a temperature in the range of 100 to 150 ° C.

The oxirane derivative of the present invention has excellent herbicidal activity against annual grasses such as paddy field grasses such as Nobie; annual grass weeds such as cyperaceae; annual broadleaf weeds such as stag beetle and oak; With high selectivity, for example 10
These weeds can be effectively controlled with a dose of about 100 g per are, and the above dose does not cause any harm to paddy rice.

The herbicide of the present invention contains the oxirane derivative described above, that is, the novel oxirane derivative of the present invention represented by the general formula (III) as an active ingredient. It can be mixed with a solid carrier such as mineral fine powder and formulated into a wettable powder, emulsion, powder, granule or the like and used. A surfactant may be added in order to impart emulsifiability, 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 10 to 55% by weight of the oxirane derivative of the present invention and 40 to 50% by weight of a solid carrier.
A composition may be prepared by blending 88% by weight and 2 to 5% by weight of a surfactant and used. When used in the form of an emulsion, the oxirane derivative of the present invention is usually 20 to
It may be prepared by mixing 50% by weight, 35 to 75% by weight of a solvent and 5 to 15% by weight of a surfactant.

On the other hand, when used in the form of a powder, it may be usually prepared by blending the oxirane derivative of the present invention at a ratio of 1 to 16% by weight, a solid carrier at a ratio of 80 to 97% by weight and a surfactant at a ratio of 2 to 5% by weight. Further, when used in the form of a powder, the oxirane derivative of the present invention may be prepared by blending at 1 to 15% by weight, 80 to 97% by weight of solid carrier and 2 to 5% by weight of surfactant. Here, fine powder of mineral substances is used as the solid carrier,
Examples of the fine powder of this mineral substance include oxides such as diatomaceous earth and slaked lime, phosphates such as apatite, sulfates such as gypsum, talc, viroferrite, clay, kaolin, bentonite, acid clay, white carbon, Examples thereof include silicates such as quartz powder and silica stone powder.

In addition, an organic solvent is used as a solvent, and 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; ketones such as isophorone, cyclohexanone, cyclohexenyl-cyclohexanone, and butyl cellosolve;
Examples thereof include ethers such as dimethyl ether and methyl ethyl ether, esters such as isopropyl acetate, benzyl acetate and methyl phthalate, amides such as dimethylformamide, and mixtures thereof.

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

In the herbicide of the present invention, the above-mentioned general formula (II)
In addition to the oxirane derivative represented by I), other herbicidal active ingredients can be contained as necessary. Examples of such other herbicidally active ingredients include conventionally known herbicides such as phenoxy, diphenyl ether, triazine, and the like.
Examples thereof include urea, carbamate, thiol carbamate, acid anilide, pyrazole, phosphoric acid, sulfonylurea, and oxadiazon, and can be used by appropriately selecting from these herbicides.

Further, the herbicide of the present invention can be mixed with an insecticide, a fungicide, a plant growth regulator, a fertilizer, and the like, if necessary.

[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 2- [3- (5-trifluoromethyl-2-pyridyloxy) phenyl] -1-propene 5.58 g (0.02 mol)
Was dissolved in 50 ml of bromotrichloromethane, and cuprous chloride was added.
After addition of 12 g, 1.70 g (0.02 mol) of piperidine was added dropwise under ice-cooling, followed by stirring at room temperature for 6 hours. Next, 5
To the mixture was added hydrochloric acid (by weight), extracted with chloroform, and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 10) to give 2-bromo-2- [3- (5-trifluoromethyl-2-pyridyloxy) phenyl] -4,4. 6.69 g (70% yield) of 1,4-trichlorobutane was obtained as a colorless oil.

Step 2 2-bromo-2- [3- (5-trifluoromethyl-
2-pyridyloxy) phenyl] -4,4,4-trichlorobutane (2.39 g, 0.01 mol) in o-dichlorobenzene (50 ml)
And 1.43 g (0.01 mol) of cuprous chloride was added thereto, and the mixture was heated under reflux for 1 hour with stirring. After cooling, the o-dichlorobenzene layer was washed with water and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 10) to give 2- [3- (5-trifluoromethyl-2-pyridyloxy) phenyl] -4,
3.89 g (70% yield) of 4,4-trichloro-1-butene was obtained as a colorless oil.

Step 3 2- [3- (5-trifluoromethyl-2-pyridyloxy) phenyl] -4,4,4-trichloro-1-butene
1.98 g (0.005 mol) was dissolved in 20 ml of methylene chloride, a solution of 0.28 g of sodium acetate dissolved in 3.48 g of a 40% by weight aqueous solution of peracetic acid was added dropwise, and the mixture was stirred at room temperature for 4 hours. Further, the same amount of a sodium acetate-peracetic acid solution was added dropwise, and the mixture was stirred at 35 to 40 ° C for 5 hours. After cooling, the methylene chloride layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 10) to give 2- [3
-(5-Trifluoromethyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane (1.58 g, yield 75%) was obtained as a colorless oil. The analytical values and structural formula of this product are shown in Table 3.

Production Examples 2 and 3 In Production Example 1, the substituted nitrogen-containing oxyphenylpropene shown in Table 2 was used instead of 2- [3- (5-trifluoromethyl-2-pyridyloxy) phenyl] -1-propene. Was carried out in the same manner as in Production Example 1 except that the corresponding oxirane derivatives were obtained in the yields shown in Table 2. Table 3 shows the analytical values and structural formulas of these oxirane derivatives.

Production Example 4 Step 1 Dissolve 4.91 g (0.02 mol) of 2- [3- (5-chloro-2-pyridyloxy) phenyl] -1-propene in 50 ml of bromotrichloromethane and add 0.12 g of cuprous chloride After that, 1.70 g (0.02 mol) of piperidine was added dropwise, and the mixture was heated under reflux for 2 hours. Next, 5% by weight hydrochloric acid was added, extracted with chloroform, and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 10) to give 2- [3- (5-chloro-2-pyridyloxy) phenyl] -4,4,4-trichloro-1. -Butene 7.01 g (97% yield) was obtained as a colorless oil.

Step 2 3.62 g (0.01 mol) of 2- [3- (5-chloro-2-pyridyloxy) phenyl] -4,4,4-trichloro-1-butene is dissolved in 20 ml of methylene chloride, and 70% by weight of m-methylene chloride is dissolved. Add 4.00 g (0.016 mol) of chloroperbenzoic acid and heat to 40 ° C
Stirred for hours. Next, the methylene chloride solution was washed with a 20% by weight aqueous solution of sodium hydrogen sulfite, a 5% by weight aqueous solution of potassium carbonate and a saturated aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 10) to give 2- [3- (5-chloro-2-pyridyloxy)
[Phenyl] -2- (2,2,2-trichloroethyl) oxirane (1.41 g, yield 37%) was obtained as a colorless oil.

 The analytical values and structural formula of this product are shown in Table 3.

Production Examples 5 to 53 In Production Example 4, 2- [3- (5-chloro-2) was used.
-Pyridyloxy) phenyl] -1-propene was replaced with the substituted nitrogen-containing allyloxyphenylpropene shown in Table 2, except that the corresponding oxirane derivative was obtained. It was obtained in the yields shown in Table 2. Table 3 shows the analytical values and structural formulas of these oxirane derivatives.

Test Examples 1 to 53 (1) Preparation of herbicide 97 parts by weight of talc (trade name: Zikulite) as a carrier and alkylaryl sulfonate as a surfactant (trade name: Neoperex, manufactured by Kao Atlas Co., Ltd.) 1.
5 parts by weight and 1.5 parts by weight of nonionic and anionic surfactants (trade name: Solpol 800A, manufactured by Toho Chemical Industry Co., Ltd.) were uniformly ground and mixed to obtain a carrier for a wettable powder.

90 parts by weight of this wettable powder carrier and 10 parts by weight of the oxirane derivative obtained in Production Examples 1 to 53 were uniformly ground and mixed to obtain a herbicide.

(2) Biological test (flooding soil treatment test) Paddy soil was filled in a porcelain pot of 1/15500 are, and seeds of Nobie, Tamayatsuri, broadleaf weeds (Kikasigusa, Konagi) and firefly were uniformly seeded on the surface layer. Further, the tubers of the horned vine were transplanted, and the rice plants at the two leaf stage were transplanted.

Thereafter, at the time of germination of the weeds, a predetermined amount of the diluted solution of the herbicide obtained in the above (1) was uniformly dropped on the water surface and treated, and then the pot was left in a greenhouse and sprinkled as appropriate.

Table 4 shows the results of the investigation on the herbicidal effect and the chemical injury of rice cultivation 20 days after the chemical treatment. The dose was shown as the amount of active ingredient per 10 ares. In addition, the paddy rice phytotoxicity and the herbicidal effect were measured by measuring the air-dried weight, and displayed as follows.

Degree of phytotoxicity Paddy rice phytotoxicity (compared to untreated area) 0 100% 195-99% 290-94% 380-89% 4 60-79% 5 50-59% Degree of herbicidal effect 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, the oxirane derivative obtained in Production Example 1 was used instead. And the structural formula 2- (3,5-dichlorophenyl) -2- (2,
2,2-trichloroethyl) oxirane [A] (generic name:
The same operation as in Test Example 1 was performed except that Tridifan, Japanese Patent Publication No. 53-3749 was used. Table 4 shows the results.

Test Comparative Example 2 In Test Example 1, instead of the oxirane derivative obtained in Production Example 1, a structural formula was used. 2- (3-benzyloxyphenyl) -2-represented by
(2,2,2-trichloroethyl) oxirane [B] (U.S. Pat. Nos. 4,103,772 and 4,018,801)
The same operation as in Test Example 1 was performed except that was used. Table 4 shows the results.

INDUSTRIAL APPLICABILITY The oxirane derivative of the present invention can be produced by the disclosed method, is a novel compound having a specific nitrogen-containing allyloxyphenyl skeleton, and has excellent herbicidal activity against paddy weeds. It has excellent selectivity, and particularly excellent selectivity between paddy rice and Nobies, and is useful as a rice herbicide. The herbicide of the present invention can effectively control paddy weeds at a low dose, and does not cause harm to paddy rice at the dose.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 405/12 241 C07D 405/12 241 413/12 303 413/12 303 417/12 303 417/12 303 A01N 43/58 43 / 60 43/78 43/76 101 (31) Priority claim number Japanese Patent Application No. 1-177256 (32) Priority date Hei 1 (1989) July 11, (33) Priority claim country Japan (JP) (72) Invention Person Toshihiro Hirata 1280, Kamiizumi, Sodegaura-cho, Kimitsu-gun, Chiba Pref. Idemitsu Kosan Co., Ltd. (56) References JP-A-56-7766 (JP, A) US Patent No. 4018801 (US, A)

Claims (2)

(57) [Claims] (1) General formula (Where R ¹ is X ¹ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an acid amide group, and a 1 to 1 carbon atom. 4 represents an acylamino group or an alkylsulfonyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4. When n is plural, each X ¹ may be the same or different. R ² is a hydrogen atom or an alkoxyl group having 1 to 4 carbon atoms. An oxirane derivative represented by). 2. The general formula (Where R ¹ is X ¹ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an acid amide group, and a 1 to 1 carbon atom. 4 represents an acylamino group or an alkylsulfonyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4. When n is plural, each X ¹ may be the same or different. R ² is a hydrogen atom or an alkoxyl group having 1 to 4 carbon atoms. A herbicide containing the oxirane derivative represented by the formula (1) as an active ingredient.