JPS6011905B2 - 2-(substituted phenoxy)propionic acid derivatives and herbicides containing the same as active ingredients - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel 2-(substituted phenoxy)propionic acid derivatives and herbicides containing them as active ingredients. More specifically, the present invention is directed to the general formula: (wherein R.
represents a hydrogen atom or a chlorine atom, R2 represents a hydrogen atom or a lower alkyl group) (hereinafter referred to as the compound of the present invention) and herbicides containing these as active ingredients That's about it. Although many acid amides containing aliphatic amines and aromatic amines have been synthesized and tested as herbicides, there are almost no examples containing isoxazolidine, a unique heterocyclic amine. The present inventors focused on isoxazolidine, synthesized various derivatives thereof, and examined their herbicidal activity. It was discovered that it has extremely excellent properties as a drug. Until now, JP-A-52-83615
In the publication, it is known that 2-[4-(4-trifluoromethyl)phenoxy]phenoxypropionic acid represented by the following formula, its salts, esters, amide derivatives, etc. have herbicidal activity. [In the formula, R is a hydrogen atom or a halogen atom, R2 is hydroxy, (C
,-4) alkoxy, cyclohexyloxy, phenyloxy, phenylthio, hydrazino, amino, (C,-
4) alkylamino, di(CM)alkylamino/, phenylamino (the phenyl group may also be substituted by halogen or trifluoromethyl), or the radical Kat (where Kat is the cation of an inorganic or organic base); ion). ] Since the compound described in the above publication has an asymmetric carbon atom adjacent to the carbonyl group, it exists in the optically active d-form and the 1-form. It is known that this d-isomer has a herbicidal effect in Samurai Sekisho 54-112.
It is known from the publication No. 82. The isoxazolidine derivative of 2-(substituted phenoxy)propionic acid provided by the present invention is not described in the above-mentioned publication, and is a novel compound that has not yet been reported in the literature. Furthermore, the compounds of the present invention are superior to known compounds in terms of herbicidal effects and phytotoxicity to useful crops. In other words, the compound of the present invention has an excellent herbicidal effect, especially against weeds of the genus family, in both soil treatment and foliage treatment, but it has no effect on broad-leaved crops such as soybean, beet, radish, and orchid, or on cotton. On the other hand, there is almost no chemical toxicity, and there is no toxicity to animals or fish, so it can be used safely.The compound of the present invention of formula [1] also has the same optical activity as the compound known in the above publication. There are d- and 1-isomers.It is commonly seen that the physiological activity of the optically active d- or 1-isomer is superior to the optically inactive racemic form, which is a mixture of equal amounts of the d-isomer and 1-isomer. However, even in the compound of formula [1], the effect of the d-form is superior to that of the racemic form.However, the compound of the present invention can be used as a herbicide not only in the racemic form but also in the d-form or one form alone or in the d-form. It goes without saying that the compound of the present invention can be used in the form of a mixture of the following reaction formula 'a', 'b or {c) in any ratio. These production methods are also applicable to the production of either racemic or optically active compounds. Reaction formula 'a1
: General formula

In [0], R has the same meaning as above,
And x indicates a halogen atom. The compound of formula [b] is a known compound and can be easily produced. In the general formula [blood], R2 has the same meaning as above. The compound of the formula [blood] is itself a new compound, but it also includes N-(2-halopropionyl)isoxazolidine obtained in Reference Production Example 1 and N-[(2-tosyloxy)propionyl]isoxazolidine obtained in Reference Production Example 2. and hydroquinone as shown in Reference Production Example 3 or Reference Production Example 4. Reaction formula 'Small compound [m and compound [m
] It is usually preferable to use an organic solvent for the reaction. Examples of organic solvents include hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloroethane, enals such as ethyl ether and tetrahydrofuran, esters such as methyl acetate and ethyl acetate, acetone, Ketones such as methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide and N-methylformamide, or dimethyl sulfoxide can be used. As acid binders, organic amines such as triethylamine and pyridine or potassium carbonate,
Inorganic bases such as sodium hydroxide and potassium hydroxide can be used. Further, the compound of formula [m] can also be used in the form of a sodium salt or a potassium salt in advance with metallic sodium, metallic potassium, sodium hydride, sodium amide, or the like. Although the reaction proceeds at room temperature, heating increases the reaction rate, so a temperature between room temperature and the boiling point of the solvent is usually used. After completion of the reaction, when an acid binder is used, the salts of the acid binder precipitated in the reaction solution are taken up in a furnace, and the solvent of the furnace solution is removed by shaving to obtain the compound of the present invention. In some cases, the desired product can be obtained by adding a solvent such as benzene, chloroform, ether or tetrahydrofuran and water, separating the organic layer, and distilling off the organic solvent. Examples 1 and 2 show a method for producing the compound of the present invention according to reaction formula {a. Reaction formula 'bl: In the general formula [W], R has the same meaning as above, and Y represents a halogen atom. The compound of formula [m] is, for example,
It can also be easily obtained by reacting the known compounds disclosed in Publication No. 8 with a halogenating agent such as thionyl halide or phosphorus oxytrichloride. In general formula [V], R2 has the same meaning as above. The compound of formula [V] is usually prepared by a method known per se, for example, by reacting hydroxyurethane with 1,3-dihaloalkane to give a carbamate having an isoxazolidine nucleus, and hydrolyzing this with stannic acid. Easily obtained in the form of an acid salt. In the reaction of compound [W] and compound [V] according to reaction formula 'b}, an organic solvent is usually used. As the organic solvent, hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, nitriles, etc. similar to those used in the reaction according to reaction formula 'a) can be used. As acid binders organic amines such as triethylamine and pyridine or inorganic bases such as potassium carbonate and sodium hydroxide can be used. Since the reaction proceeds rapidly at temperatures ranging from ice-water cooling to room temperature, there is no particular need for heating. The target product can be obtained by carrying out the treatment after the reaction is completed according to the reaction formula {a--. A method for producing the compound of the present invention according to the reaction formula is shown in Example 3. Reaction formula 'c): In the general formula [in], R has the same meaning as above. The compound of formula [W] is a known compound, such as 1-halogeno-4-(trifluoromethyl)benzene or 1.
2-dihalogeno 4-(trifluoromethyl)benzene can be easily obtained by reaction with hydroquinone. In the general formula [skin], R2 has the same meaning as above, and Z
represents a halogen atom or a tosyloxy group. Formula [W]
The compound is a new compound, but as shown in Reference Production Examples 1 and 2, it can be produced by reacting 2-halo or 2-tosyloxypropionyl halide with isoxazolidines. Compound [W] according to reaction formula 'c}
When reacting with a compound [skin], an organic solvent is usually used. As the organic solvent, hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, and nitriles similar to those used in the reaction according to the reaction formula can be used. As acid binders organic amines such as triethylamine and pyridine or inorganic bases such as potassium carbonate and sodium carbonate can be used. The reaction proceeds at room temperature, but since heating increases the reaction rate, temperatures between room temperature and the boiling point of the solvent are usually used. The target product can be obtained by carrying out the treatment after the reaction is completed according to the reaction formula {a--. Example 4 shows a method for producing the compound of the present invention according to reaction formula {c}. Reference manufacturing example
1 Production of N-[(±)-2-chloropropionyl]isoxazolidine (raw material) isoxazolidine hydrochloride 11.
To a mixture of 200 g of chloroform and 13.3 g of (±)-2-chloropropionyl chloride was added under ice-water cooling, and then 22.2 g of triethylamine was added dropwise. After dropping, water was added and the organic layer was diluted with IN aqueous hydrochloric acid solution, then 5%
After washing with an aqueous sodium bicarbonate solution, it was dried over anhydrous sodium sulfate. When the solvent is distilled off under reduced pressure, N-[(±
) 15.0 ta of 12-chloropropionyl isoxazolidine was obtained as a pale yellow oil. When purified by silica gel column chromatography, it becomes a colorless oil with n color. =1.4918. Reference Production Example 2 Synthesis of N-[1-(1)-(2-tosyloxy)propionyl]isoxazolidine Add 1-(1-(1)-(1-) ) 26.3 hours of mono(2-tosyloxy)propionyl chloride were added, and then 22.2 hours of triethylamine was added dropwise. After the dropwise addition, the mixture was allowed to stand at room temperature for 20 minutes, water was added to the reaction mixture, and the organic layer was separated. The organic layer was washed with IN aqueous hydrochloric acid solution, then with 5% aqueous sodium bicarbonate solution, and then dried over anhydrous sodium sulfate. When the solvent is distilled off under reduced pressure, N-[1-(
1) 28.7 tons of 1(2-tosyloxy)propionyl]isoxazolidine was obtained as a pale yellow oil. This substance soon crystallizes, and when recrystallized from a mixed solvent of n-hexane/ethyl acetate, it becomes white crystals with a melting point of 61~
6 or ○ and Q customers showed -32.70. Reference production example 3N-[(Sat)-2-(4-hydroxyphenoxy)
propionyl]isoxazolidine ([m] formula compound:
Production of N-[(±)-12-chloropropionyl]isoxazolidine (see Reference Production Example 1) 16.4 times, hydroquinone 13.2 times, anhydrous potassium carbonate 29.0 times and dimethylformamide 100 times While worshiping the mixture 1
The reaction was carried out at 20 qo for 2 hours. After cooling, solid matter was removed by suction furnace filtration, and the furnace liquid was concentrated under reduced pressure. Chloroform and IN hydrochloric acid were added to the residue to refine it, followed by further washing with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to give N-(earth)-[2-(4-
Hydroxyphenoxy)propionyl isoxazo 1
21.6 g of gin was obtained as a pale yellow oil. Purification by silica gel column chromatography gave a colorless oil with n = 1.5412. Reference production example 4 N-[d1(10)121(4-hydroxyphenoxy)
Preparation of propionyl]isoxazolidine (compound [m]: raw material) N1[11(1)1(2tosyloxy)propionyl]isoxazolidine 29.9 times (see Reference Production Example 2), hydroquinone 12. 1 night, 29.0 degrees of anhydrous potassium carbonate and 100 degrees of acetonitrile.
The mixture was flooded with water and refluxed for 3 hours with stirring. After cooling, solid matter was removed using a suction furnace, and the furnace liquid was concentrated under reduced pressure. After washing the residue with chloroform and IN-hydrochloric acid, the organic layer was washed with a 5% aqueous sodium bicarbonate solution. After drying over anhydrous sodium sulfate, the solvent was removed under reduced pressure to obtain 20.4 tons of N-[d-(1)121(4-hydroxyphenoxy)propionyl]isooxazolidine as a pale yellow oil. It was done. Purification by silica gel column chromatography gave a colorless oil.
It crystallized shortly after being left at room temperature. When the crystals are recrystallized with a mixed solvent of n-hexane/benzene, they become white crystals with a melting point of 119-124°C and a Q customer = 121.7q.
It showed 0. Example 1 Compound No. Production of 5 (method a) 1,2-dichloro-4-(trifluoromethyl)benzene 21.5 minutes, N-[(Sat)-121(4-hydroxyphenoxy)propionyl]isoxazolidine 23.7
(see Reference Production Example 3), anhydrous potassium carbonate 14.5
a mixture of 200' and dimethyl sulfoxide.
I worshiped flies for 3 hours with 30k. After cooling, water and benzene were added to the reaction solution, and the organic layer was separated. The organic layer was purified with IN sodium hydroxide, then water, and then dried over anhydrous sodium sulfate. When the solvent was distilled off under reduced pressure, N-[(±)-2-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy] was obtained. 39.9 tons of pionyl isoxazolidine were obtained as light brown crystals. Recrystallization from a mixed solvent of n-hexane/ethyl acetate gives white crystals with a melting point of 66.5-
It read 67.5:00. Example 2 Compound No. Production of 6 (method a) 1,2-dichloro-4-(trifluoromethyl)benzene 21.5 minutes, N-[d-(10)121(4-hydroxyphenoxy)propionyl]isoxazolidine 23
．． 7 yen (see reference production example 4), potassium hydroxide 6.6
a mixture of 200' and dimethyl sulfoxide.
The candles were lit for 5 hours at 20℃. After cooling, water and benzene were added to the reaction solution, and the organic layer was washed with water and dried over anhydrous sodium sulfate. When the solvent was removed under reduced pressure, 38. I got a fish. When purified by silica gel column chromatography, it becomes a colorless oil with n color o=
1.5374 and Q color 0=-19.10. Example 3 Compound No. Production of 1 (method b) Isoxazolidine hydrochloride 11.0 ml and chloroform 2
00' mixture under ice-water cooling (Sat)-2-[4-(
34.5 hours of 4-trifluoromethylphenoxy)phenoxypropionyl chloride were added, and then 22.2 hours of triethylamine was added dropwise. After dropping, leave at room temperature for 30 minutes, add water to the reaction solution,
The organic layer was separated. The organic layer was diluted with IN aqueous hydrochloric acid, then I
After polishing with N sodium hydroxide, it was dried with anhydrous sodium sulfate. When the solvent was removed under reduced pressure, 37.3 tons of N-[(4-trifluoromethylphenoxy)phenoxy]propionyl]isoxazolidine was obtained as white crystals. Recrystallization from a mixed solvent of n-hexane/acetone gave white crystals with a melting point of 105-1070. Example 4 Compound No. Production of 2 (method c) 4-(4-trifluoromethyl)phenoxyphenol 25.4 hours, N-[1-(1)-2-tosyloxypropionyl]isoxazolidine 15.0 hours (reference production example) 2), add a mixture of 15.2 ml of anhydrous potassium carbonate and 300 ml of acetonitrile, and add 5.
Refluxed for an hour. After cooling, solid matter was removed by suction furnace filtration, and the furnace liquid was concentrated under reduced pressure. Water and benzene were added to the residue for purification, and the organic layer was separated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, yielding 36.8 tons of N-[d-(1)-21[4-(4-trifluoromethylphenoxy)phenoxy]propionyl]isoxazolidine as a light brown oil. It was done. When purified by silica gel column chromatography, it becomes a colorless oil, n color o = 1.53
15 and. color. =-22.90. Table 1 shows representative examples of compounds of general formula [1] produced by the same method as in the above examples. In addition, compound No. is also referred to in the following test examples and examples. Table 1 The herbicide of the present invention can be prepared by preparing the compound of the general formula [1] in a conventional formulation as an emulsion, a wettable powder, a liquid, a flowable (sol), a powder, a driftless (DL) powder, a granule, or a fine granule. It can be prepared into an appropriate form such as a drug or a tablet. As the carrier, any solid or liquid carrier commonly used for agricultural and horticultural chemicals can be used, and the carrier is not limited to a specific carrier. For example, solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, white carbon slaked lime, silica sand, ammonium sulfate, urea, etc.); Vegetable powders (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resins, polyvinyl chloride, ketone resins, dammargum, etc.), alumina, silicates, sugar polymers, Examples include highly dispersed silicic acid and waxes.
Examples of liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, lso-propyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, ethylbenzene, chlorobenzene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorodifluoromethane, etc.),
Ethyl ether (derived from ethers, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate,
amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetamide), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.),
Sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycomonomethyl ether, ethylene glycomonoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), Industrial gasoline (petroleum oil, solvent naphtha, etc.), petroleum distillates (paraff, fins, kerosene,
light oil, etc.). In addition, surfactants (or emulsifiers) are used for the purposes of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading, etc. when preparing formulations such as emulsions, wettable powders, and flowables. Such surfactants include nonionic types (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.) and anionic types (alkylbenzene sulfonate, alkyl sulfonate, etc.). succinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, etc.), cationic type [alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.), polyoxyethylene alkylamines] , amphoteric type [carboxylic acid (betaine type), sulfuric acid ester salt, etc.], but of course the present invention is not limited to these examples. In addition to these, various adjuvants such as polyvinyl alcohol, hydroxymethylcellulose, gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, and gum tragacanth can be used. In the present invention, when manufacturing the various preparations described above, the compound of the present invention is added at 0.1 to 9
It can be formulated to contain 5% (weight: the same applies below), preferably in the range of 0.5 to 90%. For example, for regular powder, DL powder, and fine powder, 0.1
It can be contained in the range of 5% to 5%, 1 to 10% in the case of granules, and 5 to 95% in the case of wettable powders, emulsions, and solutions.
For example, in the case of granules, the preparation prepared in this way can be directly placed on the soil surface, in soil, or in water at a dosage of about 2 to 5 k9 per 10 ares (an amount of active ingredients of 5 to 10 k9).
00 ta) should be sprayed. In the case of emulsions, liquids, and wettable powders, dilute with water or a suitable solvent to about 500 to 200M to give a concentration of 5 to 100%, preferably 50 to 500.
The concentration is about the same as that of a shoe plate, and this diluted solution is added at a rate of 1 per 10 ares.
What is necessary is to spray in the range of 0.00 to 300 so (the amount of active ingredient is about 5 to 1000). Furthermore, when the compound of the present invention is used as a herbicide, it can be mixed with known herbicides, insecticides, or plant regulators to expand its applicability, and in some cases, a synergistic effect can be expected. You can also do it. In particular, such herbicides include 2-chloro-4-ethylamino-6-isopropylamino-1.
3,5 triazine, 2-chloro-4,6-bis(ethylamino)-1,3,5 triazine, 2-methylthio-4-ethylamino-6-isopropylamino-1,3
・5-triazine, 2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine, 2-(
4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropionitrile,
4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one, 3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazin- 2,4-dione, 4-amino-4,5-dihydro-3-methyl-6-phenyl-
1,2,4-triazin-5-one, 61te91butyl-4-isobutylideneamino-3-methylthio-1.
Triazine herbicides such as 2,4-triazin-5-one, 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, 3-(4-chlorophenyl)-1
・1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 1,1-dimethyl-3
Ikkubi・Q・Q-trifluorometholyl)urea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-[4-(chlorophenoxy)phenyl]
-1,1-dimethylurea, 1-(benzothiazol-2-yl)-3-methylurea, 1-(benzothiazol-2-yl)-1,3-dimethylurea, 1-(5-ten-butyl-1,3,4) -thiadiazole-2-yl) urea-based herbicides such as 1,3-dimethylurea,
Isopropyl 3-chlorophenyl carnobemate, 1
-Methylprop-2-ynyl-3-chlorocar/denylate, methyl 3-methtolylcar/dimoyloxyphenylcarbamate, methyl 4-aminophenylsulfonylcarbamate, S-ethyl diisoptylthiocarbamate, S-ethyl dipropyro Carbamate herbicides such as thiocarbamate, S-(4-chlor)pendyl diethylthiocarbamate, S-ethyl N-cyclohexyl-N-ethylthiocarbamate, S-2,3,3-trichloroallyl diisopropylthiocarbamate, Q・Q・Q-trifluoro-2・6-
Dinitro-N・N-diph. ropyrupara toluidine,
N-(2-chloroethyl)-Q・Q・Q-trifluoro-2,6-dinitro N-propyl/gular toluidine, N-(1-ethylpropyl)-2,6-dinitro-
3,4-xylidine, N-(cyclopropylmethyl)-
Toluidine herbicides such as Q・Q・Q-trifluoro-2,6-dinitro-N-propylupar-toluidine,
Methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate, sodium 5-[2-chlorophenoxy
1-(trifluoromethyl)-phenoxy]-2-nitrobenzoate, 2-chloro-1-(3-ethoxy-4-
Diphenyl ether herbicides such as (nitrophenoxy)-4-(trifluoromethyl)benzene, 2,4-dichlorophenoxyacetic acid and its salts or methyl, ethyl or butyl esters, 4-chloro-2-methylphenoxyacetic acid and its salts , S-ethyl 4-chloro-2-methylphenoxythioacetate, 2-(4-chloro-2-methylphenoxy)propionic acid and its salts, methyl 2-[4-(2,4-dichlorophenoxy)phenoxy] Propionate, butyl 21 [41 (
2-Q, a phenoxy fatty acid herbicide such as 5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate; 2'-6-diethyl-N-(methoxymethyl)-acetanilide, 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide, 3',4-dichlorophenylpropionanilide , N-1 naphthylphthalamic acid, N-benzoyl-N-(3,4-dichlorophenyl)-D-L-alaninate, 5
-isopropoxyphenyl)-1,3,4-oxadiazole-2-one, 2-(3,4-dichlorophenyl)
-4-methyl-1,214-oxadiazolin-2,5
-dione, diazine herbicides such as 3-isopropyl-(IH)-2,1,3-benzothiadiazine-4(motherH)-one-2,2-dioxide, 0-ethyl ○-(
6-nitromethathonyl)sec-butylphosphoroamidothioate, N-(phosphonomethyl)glycine, 2
-amino-4-methylphosphinobutyryl) -alanylalanine Organophosphorus herbicides such as monosodium salts,
Benzoic acid herbicides such as 3-amino-2,5-dichlorobenzoic acid and dimethyltetrachloroterephthalate, 2.
6-dichlorobenzonitrile, 4-hydroxy-3.5
- Nitrile herbicides such as diiodobenzonitrile, 5
-from-3-sec-butyl-6-methyluracil,
3-cyclohexyl-6,7-dihydro-IH-cyclo
Uracil herbicides such as bentapyrimidine-2,4-dione, pyridylium salt herbicides such as 1,1'-dimethyl-4,4'-pyridylium ion, and 1,1'-ethylene-2,2-bipyridylium ion. Arsenic herbicides such as disodium methane arsonate, monobutrium methane arsonate, or 2-sec-butyl 4.
6-dinitrophenol, 7-oxabicyclo [2.2
・1] Hebutane-2,3-dicarboxylic acid, 4-chloro-2-oxobenzothiazoline-triacetic acid, methyl
3[1-(allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3
Mention may be made of herbicides such as monoene carbexylate, 2-(N-ethoxybutyridyl)-5-(2-ethylpropyl)-3-hydroxy-2-cyclohexen-1-one. Examples of the method for formulating the herbicide of the present invention will be shown next, but the present invention is not limited to these examples. Note that parts in the examples indicate parts by weight. Example 5 Wettable powder compound No. 20 parts of the compound No. 1, 5 parts of polyoxyethylene alkylaryl ether, 3 parts of calcium lignosulfonate, and ±72 parts of diatoms are uniformly ground and mixed to obtain a wettable powder containing 20% of the active ingredient. When using, dilute the above hydrating agent with water to make it effective. The amount of ingredients is 5 to 1000 per 10 ares. Example 6 Emulsion compound no. 40 parts of the compound No. 5, 40 parts of xylene and 2 parts of polyoxyethylene alkylaryl ether were uniformly dissolved and mixed to obtain an emulsion containing 40% of the active ingredient. In use, the above emulsion is diluted with water and dispersed in an amount of 5 to 1,000 active ingredients per 10 ares. Example 7 Granule Compound No. 3 parts of the compound of No. 6, 1 part of calcium lignin sulfonate, 3 parts of bentonite and 66 parts of clay were uniformly mixed and pulverized, water was added to granulate it, and after drying, it was separated to obtain granules containing 3% of the active ingredient. obtain. When used, the above-mentioned granules are dispersed in an amount of 5 to 1000 particles per 10 ares. Next, test examples will be shown to illustrate the herbicidal effects of the compounds of the present invention. Test example 1 Herbicidal effect test on field weeds by pre-emergence treatment 1'2000
Fill the earth's clay pot with field soil (Okina loam soil) and add the soil of the surface layer, crabgrass, nopie, sparrow gnome,
2 female fleas, 3 female fleas, 2 victorious weeds, and 2 each of weed seeds of Psyllium spp.
Female cry, 2-view cry, 3-view cry, and 3-female cry were mixed uniformly, and the surface layer was lightly pressed. Immediately after sowing, the emulsion prepared according to Example 6 was diluted with water, and the soil surface was sprayed with the treatment solution at a concentration of 100 per 10 are. The test was conducted using a 3-pot system in 1 area, with 21 chemical treatments.
After 1 day, the herbicidal effect was investigated based on the indicators shown below.
The results are shown in Table 2. Weeding effect investigation criteria 5: Maximum weeding effect (weeding rate of 95% or more) 4:
Large (less than 80-95%) 3: Medium
(〃60~80%〃)2:〃Small (〃
40~60%'') 1: 〃 Only 4・( 〃 2
0-40%) 0: None (less than 20%) Table 2 Comparative drug A: (±) (Compound described in JP-A-52-83618) Comparative drug B: (±) (Tokusei Akira Compound described in JP-A-52-83618) Comparative drug C: (±) (Compound described in JP-A-52-83618) Comparative drug D: Alachlor [2-chloro-6-diethyl-N-(methoxymethyl)acetanilide] Commercial product] Comparative drug E: Trifluralin [Q
・Q・Q-trifluoro-2,6-dinitro-N・N-
Dipropyruparatoluidine: Commercially available product] A comparative drug was prepared and tested in the same manner as the compound of the present invention. In addition, commercially available comparative drugs D and E were used. Test Example 2 Test for phytotoxicity of field crops by pre-germination treatment A 1/10000 are clay pot is filled with field soil (Okiyokoloam), and 5 seeds each of soybean, adzuki bean, beet, radish, tomato, and wheat are placed in the pot. 5 grains, 1 eaves-tate, 1 ball-tate, 5 grains and 1 katsu-tate were sown in separate pots, the surface layer was covered with 1 c of soil, and the surface layer was lightly pressed. Immediately after sowing, the emulsion prepared according to Example 6 was diluted with water, and the soil surface was sprayed with a treatment solution of 100 per 10 are. The test was conducted using a 3-pot system in 1 area, with 21 chemical treatments.
Days later, the degree of chemical damage to each crop was investigated based on the indicators shown below. The results are shown in Table 3. Investigation criteria for drug damage 5: Maximum drug damage 4: Large 3: Medium 2: 4 1: Very small 0: None Table 3 Test example 3 Herbicidal effect test on field weeds by growing season treatment 1/1000
Fill a 0 are clay pot with field soil (alluvial loam),
Each of the weed seeds of crabgrass, japonica, sparrow gnome, sycamore, foxtail grass, purslane, and whiteweed seeds each have 3 night weeds, 50 seeds, 4 sow seeds, 4 sow weeps, 4 sow weeds,
Seeds of No. 5 and No. 4 were sown in separate pots, and the surface layer was covered with one layer of soil, and the surface layer was lightly pressed. Each weed germinates and grows, 4-leaf stage for crabgrass, 3-leaf stage for grasshopper, 4-leaf stage for Sparrow gnome, and 3-leaf stage for Sparrow gnome.
~ At the 4-leaf stage, when the green foxtail grew to the 4-leaf stage, the purslane to the 2-leaf stage, and the white grass to the 2-leaf stage, the emulsion prepared according to Example 6 was diluted with water, and 100% of the treatment solution was added per 10 ares. The stems and leaves of weeds were treated with mist. The test was conducted using a 3-pot system per plot, and the herbicidal effect was investigated based on the same index as in Test Example 1 21 days after the chemical treatment. The result is the fourth
As shown in the table. Comparative drug F in Table 4 has the following chemical structure, and a commercially available product was tested. Comparative drug F: alloxydi-sodium {methyl 3-
1-(allyloxyimino)putylidene] 16,6-dimethyl-2,4-dioxocyclohexanecarboxylate sodium salt: commercially available product} Example 4 Phytotoxicity test on field crops by growing season treatment 1/l0000 are bisque firing Fill a pot with field soil (alluvial bush) and add 5 seeds, 5 seeds, 1 seed, 1 seed, 5 seeds, and 1 of each crop seed such as soybean, adzuki bean, beet, radish, tomato, and wheat. The seeds were sown in separate pots, the top layer was covered with one layer of soil, and the top layer was lightly pressed. When each crop has germinated and grown and the main crop has grown to the 3rd to 4th hollyhock stage, the emulsion prepared according to Example 6 is diluted with water, and the stem hollyhock part of each crop is treated with 100% of the treatment solution per 10 ares. It was treated with fog. The test was conducted using a three-pot system in one section, and the degree of drug damage was investigated based on the same index as in Test Example 2 21 days after the drug treatment. The results are shown in Table 5. Table 5

Claims (1)

[Claims] 1 General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a chlorine atom, and R_
2-(substituted phenoxy)propionic acid derivative represented by (2 represents a hydrogen atom or a lower alkyl group). 2 General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a chlorine atom, and R_
A herbicide containing as an active ingredient a 2-(substituted phenoxy)propionic acid derivative represented by (2 represents a hydrogen atom or a lower alkyl group).