JPS5955882A - 2-(substituted phenoxy)propionic acid derivative and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is 3,5-dichloro-2-pyridyl or 5-trifluoromethyl-2-pyridyl; R2 is H or lower alkyl). EXAMPLE:N-{ (+ or -)-2-[ 4-( 3,5-Dichloro-2-pyridyloxy)phenoxy ]propionyl}isoxazolidine. USE:Herbicide exhibiting excellent activity especially against gramineous weeds, and little phytotxicity to the broad-leaved crops such as soybean, beet, radish, cabbage, etc. or cotton etc., and having high safety. PROCESS:The compound of formula I can be prepared by reacting the compound of formula R1-X (X is halogen) with the novel compound of formula II in an organic solvent in the presence of an acid acceptor (e.g. triethylamine, potassium carbonate, etc.) at room temperature - the boiling point of the solvent. The novel compound of formula II can be obtained easily e.g. by the reaction of N-(2-halopropionyl)-isoxazolidine with hydroquinone.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel 2-(substituted phenoxy)zolopionic acid derivatives and herbicides containing them as active ingredients.

More specifically, the present invention relates to the general formula: (wherein, Tt
+ represents a 3,5-dichloro-2-pyridyl group or a 5-trifluoromethyl-2-pyridyl group, and R2 represents a lower alkyl group). This invention relates to the compounds of the present invention) and herbicides containing these as active ingredients.To date, many acid amides containing aliphatic amines and aromatic amines have been synthesized and tested as herbicides. #1 There are very few examples containing isomekitzolidine, which is a unique hederocyclic amine.

The present inventors focused on inoxutuzolidine, and each fl.
As a result of synthesizing nN8'j+ forms and examining their herbicidal activity, it was discovered that the derivative of 2-1j substituted phenoxy)noropionic acid represented by the general formula [I] has extremely excellent properties as a herbicide. Ta.

Until now, in JP-A-52-125626, alkoxyalkyl amides of 2-[4-(3,5-dichloro-2-pyridyloxy)soqnoxy]propion ω represented by the following formula have been reported. , morpholinamides, etc. are known to exhibit herbicidal activity.

[In the formula, R is a hydroxyalkyl group, a lower alkoxy group, a lower alganyloxy group, an acyl group, an amino group, an aralkyl group, a chloro-substituted aralkyl group, -R
C0OR group (in the formula, I (is a lower alkylene group),
R is hydrogen, a lower alkyl group, a salt-forming atom or a salt-forming residue) or 6-CON<.

is a group (in the formula, R and R are 7, a lower argyl group, or a lower alkoxy group), and! l), '12 is hydrogen, a lower alkyl group, a lower alkoxy group, a hydro-dialkyl group, a phenyl group or a chloro-substituted phenyl group.

A cyclic group such as a ren group or an ld acid group may be formed.

Compound 1 described in the above publication has a carunyl group with 1 k
Since it has a non-f1 carbon atom that is 4i 4&, there are optically active p, l = 76 bodies and 4 bodies. It is known from JP-A-54-11282F3 that these six species have a herbicidal effect.

In Japanese Patent Application Laid-Open No. 54-122728, 4-(5-fluoromethyl-2-pyridyloxy)phenoxyalkanecarboxylic acid of the following formula ii+ and its derivative 2,4 derivative exhibit herbicidal activity. It has been known.

(In the formula, X is a chlorine atom or a fluorine atom, Y is a hydrogen atom, R is a hydrogen atom, a methyl group, or an ethyl group, n is O or 2, and z' is a hydroxyl group, a lower alkoxy group optionally substituted with a halocene atom, a lower alkoxyalkoxyno, a lower alkenyloxy group, a lower alkylthio group,
cycloalkoxy group optionally substituted with lower alkyl group, lower alkoxycardfnylalkoxy group,
Halo atom 1 is a phenoxy group optionally substituted with a lower alkyl group, a benzyloxy group, 11, a glycidyl-oxy group, a lower alkylthio group, a lower alkenylthio group, kJ with a halokene atom removed, a lower alkyl group a phenylthio group which may be substituted or unsubstituted, an amino group, a lower alkylamino group, a lower alkoxy7carponylmethylamino group, a hydroxycarvinylmethylamino group, an anilino group which may be substituted with IF/a halokene atom, 2-pyridylamino group, -
〇-It is a halogen atom that spans a carbon atom).

The 2-(substituted), enoki 7) isomexa” silydine derivative of formula (I) provided by the present invention is not described in the above-mentioned publication and is a novel compound that has not been described in any literature. The compounds of the present invention are superior to known compounds in terms of herbicidal effect and phytotoxicity against useful crops.In other words, the compounds of the present invention are particularly effective against weeds of the genus family in both soil treatment and foliar treatment. Although it has an excellent herbicidal effect, it does not cause any chemical damage to broad-leaved crops such as soybeans, beets, radish, and kaffrans, or to cotton. It is safe to use and does not cause any damage or burns.

The compound of the present invention of formula CI] also exists in the 2c optically active 4-isomer and 2-isomer like the compounds known in the above-mentioned publication.
Normally d! The physiological activity of the optically active form of fitt is (1
It is often seen that the formula [1
Even in the case of compound 1, the effect of 4 forms is superior to that of racemic form. [2 However, chemical formula A'1 of the present invention. ＃／、、
), herbicides and 1-7 racemic V, l Of course, only 6 herbicides can be used alone or in the form of a mixture of 4 and 2 in any ratio. not.

Examples of the compounds of the present invention of formula [I] include those shown in the following table 1. The compounds of the present invention have the following reaction formula:
(can be produced by the method of cl. These production methods 6
The filtration method is applicable to the production of both racemic and optically active compounds.

1i reaction formula; (al: (J [:l+] [1111CI] General formula [In 10, IL1ij' has the same meaning as above, , -f: 5 and X) represents a location atom.Formula [ 11] compound+11t+), 1: It is a known compound and can be easily prepared. General formula [11]
In R2it: Same hemp and taste as above. Compound V1 of the formula [1++] is itself a new compound, but N-(2-halopropionyl)ine oxazolidine obtained in Reference Production Example 1 or N-4 obtained in Reference Production Example 2
It is easily produced by reacting 2-)siloxypropionyl)isoxazolidine and hydroquinone as shown in Reference Production Example 3.

When reacting compound [■] with compound [■] according to the reaction formula (al), it is usually preferable to use an organic solvent. Examples of organic solvents include hydrocarbons such as benzene and toluene, chloroform, carbon tetrachloride, and dichloroethane. Halocarbonated hydrocarbons such as ethyl ether, ethers such as detrahydrofuran, methyl acetate,
Esters such as ethyl acetate, acetone, ketones such as methyl isobutyl ketone, acetonitrile,
Nitriles such as zolobionitrile, amide compounds such as dimethylformamide, N-methylformamide, dimethyl sulfoxide, and the like can be used.

As acid binders, organic amines such as triethylamine and pyridine or inorganic bases such as potassium carbonate, sodium hydroxide and potassium hydroxide can be used. Further, the compound of the formula [rll, If can be used in advance by converting it into a sodium salt or a potassium salt with metal sodium, metal potassium, sodium hydride, sodium amide, or the like. Although the reaction proceeds at room temperature, the reaction rate is affected by addition, so a temperature between room temperature and the boiling point of the solvent is usually used.

After completion of the reaction, if an acid binder is used, the salts of the acid binder precipitated in the reaction solution are removed by a furnace, and the solvent of the p solution is distilled off to obtain the compound of the present invention.

Depending on the case, the desired product can be obtained by adding a solvent such as benzene, chloroform, decyl or detrahydrofuran and water, separating the organic layer, and distilling off the organic solvent.

Example 1 shows the method for producing the compound of the present invention according to the reaction formula fa).
It was shown to.

Reaction, formula (b): [IV] [V] (J D In the general formula [IV], old has the same meaning as above, and Y represents a halodane atom. The compound of formula [1v] is, for example, 11 Publication No. 52-128377 and l
[! ? It can also be easily achieved by reacting acids, which are known compounds described in JP-A-54-122728, with a halokenizing agent such as thionyl halide or phosphorus oxytrichloride.

In general formula [v], R2 has the same meaning as above. Compounds of formula [v] can be prepared by methods known per se, for example by reacting hydroxy/cretanes with 1,3-dino-alnonone to derive the isoxazolidine nucleus into carbamates, which are then hydrolyzed with mineral acids. In particular, it is usually readily available in the form of mineral salts! 1 lane. In the reaction of compound [IV] and compound [V] according to reaction formula fbl, an organic solvent is usually used.

As the organic-soluble IL, hydrocarbons similar to those in the reaction according to reaction formula FAT, halodanized hydrocarbons, ethers, Nisdels, tritons, nitriles, and the like can be used. As the acid binder, organic amines such as triethylamine and L-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 processing after the reaction is completed is according to the reaction formula (
The desired product can be obtained by performing the same procedure as in case a).

Example 2 shows the method for producing the compound of the present invention according to the reaction formula (bl)
It was shown to.

Reaction formula (C): Su[V[] C■] General formula [VD
In , Ttl has the same meaning as above. Formula CV
1. ] is a known compound, and can be easily obtained, for example, by reaction of 3,5-dichloro-2-pyridylno-1lide or 5-trifluoromethyl-2-pyridylnolide with hydroyanone. In the general formula [■], R2 has the same meaning as above, and 2 represents a halogen atom or a tosyloxy group. The compound of formula [■] is a new compound, but as shown in Reference Production Example 1.2, 2
It can be produced by the reaction of -7- or 2-tosyloxyzolopionyl halide with imexazolidi/. Compound [■] and compound [■] according to reaction formula (c)
] In the reaction of 7, an organic solvent is usually used for V. As the organic solvent, similar to the reaction according to the reaction formula (at), external hydrocarbons, halogenated hydrogen hydride, ethers, esters, ketones, nitriles, etc. can be used.

As acid binders it is possible to use amines such as triethylamine and pyridine or inorganic bases such as potassium carbonate and sodium carbonate. Although the reaction proceeds at room temperature, the reaction linkage is impaired by heating, so temperatures between room temperature and the boiling point of the solvent are usually used.

The desired product can be obtained by performing the treatment after the reaction is completed in the same manner as in reaction formula (a). A method for producing the compound of the present invention using the reaction formula (cl) is shown in Examples 3 and 4.

Production of N-[(,t:l-2-chloroprobimenyl]isoxazolidine (raw material) ``Isoxazolidine hydrochloride + 1.O,ii' and 200 ml of chloroform! +7) mixture under ice-water cooling. (
JJ-2-chloropropionyl chloride +3.3. l
i+ was added, and then 22.2 g of triethylamine was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, water was added to the reaction mixture, and the organic layer was separated. The organic layer was washed with an aqueous IN hydrochloric acid solution, then with a 5% bicarbonate solution, and then dried with anhydrous sulfuric acid and an IJ cum solution. The solvent was distilled off under reduced pressure to obtain 15.0 g of N-[ex-2-chlorozolopionyl]isoxazolidine as a pale yellow oil. When purified by silica cell column chromatography, it became a colorless oil with nDl of 4918.

Synthesis of N-[t-(-1-(2-tosyloxy)propionyl]isoxazolidine) To a mixture of 11.0 g of inoxazolidine hydrochloride and 200-!=dichlororum was added 1.-(/1.-() under ice-water cooling. 26.3 l of -1(2-tosyloxy)propionyl chloride was added, and then 22.211 l of triethylamine was added dropwise. After the first drop, the mixture was stirred at room temperature for 20 minutes, water was added to the reaction solution, and the filtrate layer was separated into L7.

The 4a layer was washed with an aqueous IN hydrochloric acid solution, then with a 5% aqueous sodium bicarbonate solution, and then dried over anhydrous sodium sulfate. When the solvent was distilled off under reduced pressure, N-[t-(-1-(2-
28.7 g of )siloxy)propionylcoinoxazolidine was obtained as a pale yellow oil. This product crystallized for a while, and when recrystallized from a mixed solvent of n-hexane/ethyl acetate, it showed white crystals with a melting point of 61-62tC and αD=-327°.

N-C mountain-2-(4-hydroxyphenoxy) f robionil] isomegizazorisone (C11D formula compound: raw material)
Production of N-CtJJ-2-10 ruglobionil] 16.4 g of isooxysilidine (see Reference Production Example 1), 13.2 g of hydroquinone, 29.9 g of anhydrous potassium carbonate. OI and dimethylformamide l OO#I/! The mixture was reacted at 120°C for 2 hours with stirring. After cooling, I'i! by suction cape 3t'4! After removing the carving, the P solution was removed under reduced pressure. The residue was washed with chloroform and IN hydrochloric acid, and then further washed with water. After drying with anhydrous sodium sulfate, the fj medium was distilled off under reduced pressure to produce N-
[2-(4-Hydroxyphenoxy)propionylcoin oxazolidine forms a pale yellow oil 721.69 (I
It was done. Purification by silica gel chromatography gave a colorless oil with a value of 0 nD=1.5412.

Example 1 Production of compound M1 (method a) 18.3 g of 2.3.5-trichloropyridine, N-((
:f) -2-(4-hydroxyphenoxy)propionylcoin oxazolidine 23.7,! i+ (see Reference Production Example 3), anhydrous potassium carbonate+ 4.5 g and dimethyl sulfoxide 200III/mixture 1
4 hours at 200C? Stirred. After cooling, water and benzene were added to the reaction solution, and the organic layer was separated. Organic layer I
After washing with N7 and sodium oxide and then with water, it was dried with anhydrous sodium sulfate. Dissolved under reduced pressure
Pyridylmexy)phenoxy]propionylcoin oxazolidine was obtained as pale yellow crystals (31.19%).

n-hexane/ethyl acetate point 105.5 107-5cc
Show L? C0 implementation 5!12 Kaizo of compound A5 (method b) To a mixture of 5-methylisoxazolidine hydrochloride + 3.6.9 and 200 ml of chloroporm was added () under ice water cooling.
J-2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionyl chloride 34
．． 6.9, then triethylamine 22.2,
V was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, water was added to the reaction mixture, and the organic layer was separated.

The organic layer was washed with an aqueous IN hydrochloric acid solution and then with an INK sodium oxide solution, and then dried with anhydrous sulfuric acid (IJ).

When the solvent was distilled off under reduced pressure, N-[yama-2-C4-(5-
) 17Fluoromethyl-2-HiIJzyloxy)Noenoki/]70Bionyl]-5-methylisoxazolidine was obtained as white crystals as 3B, Ojg. Recrystallization from a mixed solvent of n-hexane/acetone gave white crystals with melting points m and p of 94-97°C.

Example 3 Production of compound 4 (method a) 4-(5-)lifluoromethyl-2-pyridyloxy)
A mixture of 25.6 g of noenol, N-[yama-2-chlorpionyl]inoxazolidine+6.4, p (see Reference Production Example 1), 15.2 g of anhydrous potassium carbonate, and 300 me of acetonitrile was heated. The mixture was refluxed for 5 hours with stirring. After cooling, the solid carvings were removed by λ suction filtering, and the furnace liquid was concentrated under reduced pressure. After washing the residue with water and benzene, the organic layer was separated and dried over anhydrous sodium sulfate.

When the solvent was distilled off under reduced pressure, N-1n-2-[4-(5
-)lifluoromethyl-2-pyridyloxy)noenoxy]propionyl]isoxazolidine as pale yellow crystals at 35.5 g fc. When recrystallized with a mixed solvent of n-hexane/ethyl acetate, white crystals are obtained, single point 83-
It shows 85 houses.

Fruit+i fil 4 Production of compound genus 2 (C method) 4
-(3,5-dichloro-2-pyridyloxy)phenol 25.69, N-Ct-(-12-toyloxyprobionyl)isoxazolidine 30.0g (see Reference Production Example 2), anhydrous potassium carbonate A mixture of +5.2.9 and acetonitrile 300 was heated and refluxed for 5 hours while stirring.After cooling, the solid particles were removed by suction filtration, and the r liquid was concentrated under reduced pressure. After washing the residue with water and benzene, separate the organic layer and add anhydrous sulfuric acid) IJ
Dry with cum. When the solvent is distilled off under reduced pressure, N-(d
-(-)-2-[4-(3,5-fuchloro-2-pyridyloxy)phenoxy]broonyl]isoxazolidine as pale yellow crystals 34.9,9. Obtained.

Recrystallization with a mixed solvent of n-hexane/acetone gives white crystals with a melting point of 93-94"C and α.-13
．． It showed 3°.

The herbicide of the present invention can be prepared by preparing a compound of the general formula [e.g.
It can be prepared in an appropriate form such as powder, driftless (DL) powder, granules, fine granules, and tablets. 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, carbonate lucivum, apatite, white carbine, slaked lime, silica sand, ammonium sulfate,
urea, etc.), vegetable powders (soybean flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, divinyl dinitride, ketone resin, dammar gum, etc.), alumina, silicic acid Examples include salts, sugar polymers, highly dispersed silicic acid, and waxes. In addition, liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-f propyl alcohol, 1so
-f lobil alcohol, phthanol, ethylene glycol, pencil al-1-lunato), aromatic Wk hydrocarbons INB () luene, benzene, xylene, ethylbenzene, methylbenzene, etc.), hydrogenated hydrocarbons'J
G-types (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorodifluoromethane, etc.), Godels (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone) , methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone), esters (
ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetamide), and nitriles (
Acetonitrile, propionitrile, acrylonitrile), sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomer: r--5', ethylene glycol monoethyl ether, etc.), aliphatic compounds Qi? Cyclic hydrocarbons (n-hexane/cyclohexane, etc.), industrial gasoline (petroleum needle, nrupent naphtha, etc.),
Examples include petroleum fractions (-4' rough-ins, kerosene, light oil, etc.).

Furthermore, surfactants (or emulsifiers) are used for the purposes of emulsification, dispersion, solubilization, wetting, foaming, lubrication, and spreading in the preparation of emulsions, wettable powders, flowable preparations, and the like. Such surfactants include nonionic types (polyoxyethylene alkyl ether, I-lyoxyethylene alkyl ester, 3-lyoxyethylene rubitan alkyl ester, nrupitan alkyl ester, etc.);
Anionic type (alkylbenzene sulfonate, alkylsulfosuccinate, alkyl sulfate, ?lyoxyethylene alkyl sulfate, aryl sulfonate, etc.), cationic type [alkylamine 1 (
s? lyoxyterenealkylamines], and amphoteric types (carbic acid (betaine type), sulfuric acid ester salts, etc.), but of course they are not limited to these examples. Also, these? t
KaKs'! Rivinyl alcohol, carboxymethylcellulose, gum arabic, No.? ribinyl acetate, gelatin, casein, sodium alginate,
Various adjuvants such as gum tragacanth can be used.

In the present invention, when producing the various preparations described above, 0.1 to 95 inches of the compound of the present invention (weight: the same hereinafter) is used.
, preferably in the range of 0.5 to 90%. For example, d1 regular powder, D L powder,
For fine granules (F), O, 1-5, for granules, 1-5
In the case of wettable powders, emulsions, and liquids, it can be contained in a range of 5 to 95%. For example, in the case of a granule, the preparation prepared in this way can be sprayed as is on the soil surface, in the soil or in water at a dosage of about 2 to 5 kg (approximately 5 to 1000 g as the amount of active ingredient) per 10 ares of Formulation 1. Bye. In the case of emulsions, solutions, and wettable powders, dilute 500 to 2000 times with water or a suitable base agent.
l 000 pp+n, preferably 50-500 p
pm, and spray this diluted solution in the range of 100 to 300 tons (approximately 5 to 1000 g as the amount of active ingredient) per 10 are.

It's so big, Honja! When using lft compounds as herbicides, they can be mixed with known herbicides, insecticides, or plant regulators to expand the range of application, and in some cases. A synergistic effect can also be expected. In particular, such herbicides include
4-ethylamino-6-inzolobylamino 1,3.
5-) riazine, 2-chloro-4,6-bis(ethylamine)-1,3,5-triazine, 2-methylteme 4-ethylamino-6-isozolobylamino-1,
3.5-) riazine, 2,4-bis(isopropylamine)-6-methylthio-1,3,5-) riazine,
2-(4-chloro-6-nitylamino-1,3゜5-triazin-2-ylamino)-2-methylpropionitrile, 4-amino-6-tart-butyl-4,5
-NohyP-low 3-methylthio-1゜2.4-trianon-5-one, 3-cyclohexyl-6-dimethylamino-1-methyl-1゜3.5-)ryanone-2,4-
dione, 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one, 6-tert-butyl-4-imbutylideneamino-3-methylthio-1 ,2,4-triazine-5-
Triazine herbicide, 3-(3,4-
sochlornoenyl)-1-methoxy-1-methylthurea, 3-(4-chlorphenyl)-1,1-dimethylthurea, 3-(3,4-dichlorophenyl)-1,
1-dimethyl flare, 1,1-dimethyl-3-(α
, α, α-trinorol-methacryl) flare,
3-(4-isozolobylphenyl)-+, +-nomethylvrea, 3-[:4-(4-chlorophenoxy)phenyl]-1゜1-dimethylflair, 1-(benzothiazol-2-yl)- 3-methylvrea, 1-
(benzothiazol-2-yl)-1,3-dimethyl flare, l -(5-tert-butyl-1,3,4
flare herbicides such as -deadiazol-2-yl)-1,3-dimethyl flare, inpropyl 3-chlorenylcarpamate, 1-methylproa'-2-
Inyl-3-chlorocarbanilate, methyl 3-
methatrileuryloxyphenylcarpamate,
Methyl 4-aminebuenylsulfonyl carpamate, s-ethyl diisobutyl diocarpamate,
S-ethyl dipropylthiocarpamay), 5-
(4-chlor)pencil diethylthimechamate,
S-ethyl N-cyclohexyl-N-ethyl-thiocarbamate, S-2,3,3-trichloroallyl
Carbamate herbicides such as diisoprobyl thiocarpamate, α, α, α-trifluoro-2,6-sinitro-N, N-sifu'robi-/e-ra-)luidine,
N-(2-chloroethyl)-α,α,α-trinorol-2,6-sinitro N-7′ lovir-paratoluidine, N-(+-ethylpropyl)-2,6-sinitro-3,4-xylidine, N -(Cyclopropylmethyl)-α,α,α-trinorol-2,6-sinitro-N
-Zoropyrus? Toluidine herbicides such as latluidi/methyl 5-(2,4-dichlorophenoxy)
-2-Nitrobenzoate, sodium 5-[2-chloro-4-(trifluoromethyl)-phenoA”/]
-2-nitrobenzoate, 2-chloro-1-(3-
Diphenyl ether systems such as ethoxy-4-nitrophenoxy)-4-()riflumermethyl)4zene
agents, 2,4-dichlorophenoxyacetic acid and its salts or methyl, ethyl or butyl esters, 4-chloro-2-methylphenoxy7acetic acid and (cv salts U, S
-ethyl 4-chloro-2-methphenoxythioacede), 2-(4-chloro-2-methylphenoxy)noropionic acid and its salts, methyl 2-[4-
(2,4-dichlorophenoxy)phenoxy]propionate, butyl 2-44-(5-)lifluoromethyl-2-pyridyloxy)phenoxy]propionate and other phenoxy 11-acid-indicating herbicides, 2-chloro- 2',6'-noethyl-N-(nodoxymethyl)-
Acetanilide, 2-r1-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide 3r,4r-)
/l, noenylzolohimenani IJI', N-1-naphthyltuthalamic acid, N-benzoyl-N-
(3,4-dichlorophenyl)-1), amide herbicides such as L-alaninate, 5-tert-butyl-3-(2,4-dichloro-5-imprJνj?xyphenyl)-1,3,4, -oxadiazole-2-one, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolin-2,5-dione,
Diazine derivatives such as 3-inpropyl-(III)-2,1,3-benzothiadiazine-4-(3n)-or-2,2-dioxide, O-ethyl 0
-(6-nito1:1-mecutril) 5ec-butylphosporamidoduoate, N-(phosphonomethyl)glycine, 2-amino-4-methylphosnoinoglyl)-alanylalanine monosodium 11λ
Anti-weeping agents such as 3-amino-2゜5-
Benzoic acid herbicides such as dichlorobenzoic acid and dimethyldetrachlorterenotate; nitrile herbicides such as 2゜6-nochlorobenzonitrile and 4-hydroxy-3,5-noiodopenzonitrile; 5- Bromo-3-aec-butyl-6-methylethyl, 3
-7 Clohexyl-6,7-nohydro IJ-IH-7 Chlopontabiliminone - Chlorine herbicides such as 2,4-dione, 1,1'-tumethyl-4,4'-bipyridylicum ion, 1,1' - Viridilicum J-type herbicides such as ethylene-2,2'-Viridyrivno ion;
Arsenic herbicides such as dinatrium methanarsonate, monosodium methanarsonate, or
, 2-5oc-butyl-4,6-sinitrophenol,
7-oxocyclo[2,2,1]buta/-2,3
-Zical 1? methyl 3[1-(allyloxyimino)butyl]=4-hydroxy7-6.6-
Dimethic acid -2-oxocyclohex-3-enecarboxylate, 2-(N-ethoginebutyridyl)-5-(
Agents such as 2-ethylpropyl)-3-hydroxy-2-hydroxy, clohegycin-1, etc. can be mentioned.

Next, Examples 7J of the method for formulating the herbicide of the present invention will be described.
However, the present invention is not limited to these examples. Parts in Examples indicate parts by weight.

20 parts of a compound of 5 wettable powders, 5 parts of polyethylene alkylaryl ether, 3 parts of lignin A calcium phonate, and diatom ±72s were uniformly ground and mixed to obtain 20 parts of the active ingredient. to obtain a hydrating agent containing. When using, the above-mentioned irrigation agent is diluted with water and sprayed on the active ingredient at a concentration of 5 to 10,009 particles per 10 are.

Minoru Pu II Ishi 116 Breasts Qi 1j Compound/
40 parts of IFL5 compound, 40 parts of Ki7 L/N and ? 20 parts of island polyoxygotylene alkylaryl ether are uniformly dissolved and mixed to obtain an emulsion containing the active ingredient AOv+. Before use, the above emulsion is diluted with water and then sprinkled with the active ingredient phase at a concentration of 5 to 1000 g per 10 ares.

Example 7 Granules: 3 parts of the compound of Compound 4, 1 part of calcitonate lignosulfonate, 10 parts of bentonite and 66 parts of clay were uniformly mixed and pulverized, granulated with 6 parts of water, and dried 1 volume.
・Si, f bale sieve 5i granules containing 3% effective 5v 4.
5=ru. When using, use the granules as an active ingredient and adjust the amount to 5 to +ooo 9 per IO area.
do.

Next, the herbicidal effect of the compound of the present invention is illustrated in Test Example 1. Test 1/2 of herbicidal effect on field weeds by germination treatment. Fill a container with field soil (alluvial loam) and add 20 seeds, 30 seeds, 20 seeds, 20 seeds, 20 seeds of each of the following weed seeds: 1crn of surface soil and 20 grains, 30 grains, 20 grains, 20 grains, 20 grains of each of the following weed seeds: Japanese grasshopper, Japanese grasshopper, Japanese grasshopper, Japanese grasshopper, silver grass, silver grass, and silver grass. 30 grains and 30 grains were mixed uniformly and the surface layer was lightly pressed. The emulsion prepared according to Example 6 was diluted with water immediately after seeding and drawing.
10 are fi to.

The soil surface was treated with a treatment solution of 1. The exam is in section 1 and 3.
? The herbicidal effect was investigated based on the following indicators 21 days after the chemical treatment. The results are shown in Table 2.

Weeding effect screening criteria 5: Maximum weeding effect (weed killing rate of 95% or more) 4:
l large (l 8o~less than 9596) 3: I medium (
#60-F30%1 2: Weeding effect small (weeding rate less than 40-60%)1
: Very small (#20-40chi#) 0;
No # less than 20%) Table 2 Table 2 (Continued) Table 2 (Continued) Comparative drug A: (Compound described in JP-A-52-125626) Comparative drug B: (Compound described in JP-A-52-125626) Comparison drug C (Compound described in Publication No. 54-122728) Comparative drug D: (Compound 9 described in Publication No. 54-122728) Comparative drug E: Nyalaflor 2-chloro, - 2t, 6-monoethyl-N-(methoxymethyl)acetanilide: commercially available product] Comparative drug F:) Rifluralin [α,α,α-trinorol-2,6-sinitro-N,N-disolovir-paratoluidine 2 commercially available product] The comparative drugs were formulated and tested in the same manner as the compounds of the present invention. As for comparison drugs E and F, commercially available products were used.

Test Example 2 Phytotoxicity of field crops due to pre-germination treatment [A 1710.000 Field soil (
5 grains each of soybean, azuki bean, beet, radish, tomato, and kono and gi crops (alluvial loam),
Sow 5 grains, 10 grains, 15 grains, 5 grains, and 10 grains in separate 15 pots, cover the surface layer with 1 m of soil, and cover the surface layer with soil for 1 m. Press down lightly. Immediately after seeding, the emulsion prepared in 6 was diluted with water, and 10 per 10 are.
The soil surface was treated by spraying with 0 t of treatment chemical solution. The exam is on the 3rd day of the 1st ward! After 21 days of chemical treatment, the degree of chemical damage to each crop was investigated based on the indicators shown below. The results are as shown in Table 3 of Fi.

11 “4 side dish standards for drug damage” 5: Maximum chemical damage 4: Dog 3: Medium 2° small 1: A1CI small 0　°　　　　　-&L.

Table 3 Table 3 (Continued) ゛Test Example 3 Trial of weed control effect on field weeds by growing season treatment 1/10,000 Rq) Made of bisque, dotted field soil (Oki M Loam') 'd: Tsume, Each axis of crabgrass, wildflower, sycamore, sycamore, Japanese foxtail, superhyuo, and shibishiroza, f7
1 f! 30 grains, 50 grains, 40 grains, 40 grains, 40 grains, 50 grains, and 40 grains of I, respectively, were sown in separate soils, the surface layer was covered with 1 cvn of soil, and the surface layer was lightly pressed.

Each weed germinates and grows, and the 4-leaf stage for the crabgrass, the 3-leaf stage for the grasshopper, and the sparrow gnome? When the lily grew at the 4-leaf stage, the Psyllium at the 3-4-leaf stage, the Econochora at the 4-leaf stage, the Sperhyu at the 2-leaf stage, and the Shiroza at the 2-leaf stage, the emulsion prepared according to Example 6 was diluted with water. , 10 are per, 110
The foliage of weeds was sprayed with the treatment solution No. 06. The test was conducted using a 1-plot, 3-dose system, and 21 days after the chemical treatment, the herbicidal effect was investigated based on the same index as in Test Example 1. The results are shown in Table 4. Comparative drug G has the following chemical structure, and a commercially available product was used.

Comparative drug G: alloxydi-sodium (methyl 3-
[1-(allyloxyimino)butylidene]-6.6-
Nomethyl-2,4-dioxocyclohexanecal d? Xylate/sodium salt: Commercially available product) Test Example 4 Phytotoxicity test on field crops by growing season treatment 1 / 10.000 Field soil (alluvial loam) was filled in earthen pots, and soybean, azuki beet, beet, tikon, tomato, and 5 grains, 5 chaffs, 10 grains, 10 grains, 5 grains, and 10 grains of each crop of wheat were sown into separate pots, and the surface layer was covered with soil and the surface layer was lightly pressed. Each crop has 1-4 germination growth and 3-4 tree leaves.
At the time of growth to the leaf stage, the emulsion prepared according to Example f16 was diluted with water, and the foliage of each crop was sprayed with a treatment solution of 10 are per filoot. The test was conducted using a 3-pot system in IT+ section, and the degree of chemical 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 Table 5 (Continued) Procedural amendments imported) September 19, 1980 Dear Commissioner of the Japan Patent Office■, Small case indication Showa 57 Patent Application No. 164967 2, Title of the invention 2- (Substituted phenoxy) Propionic acid derivatives and herbicides containing the same as active ingredients 3, Person making the amendment/Relationship with 1f Patent W1 Applicant Address 4-2, Nihonbashi Honseki-cho, Chuo-ku, Tokyo Name Hokuko Chemical Industry Co., Ltd. 4, Agent Person: 105 Address: Bussan Building Annex, 1-1-15 Nishi-Shinbashi, Minato-ku, Tokyo Telephone: (591) 02615 YuJ #llll Hirono! )i￥ "i'u of the scope of crystallization sought and detailed explanation of the invention"(,;I 6, Contents of amendment (11% The range of permissible hcI is amended as shown in the attached sheet.

(2) Insert ``1-hydrogen atom or'' in place of ``1ζ2 is'' in the 2nd negative line 14.

2 Bamboo H’l”l Mosquito Cape, Surrounded by 1. -Shi 2.

(In the formula, R1 represents a 3,5-dichloro-2-pyridyl group or a 5-trifluoromethyl-2-pyridyl group, and R
2 represents a hydrogen atom or a lower alkyl group).

2. General formula:

Claims (1)

[Claims] ■ General formula: (wherein)1+ represents a 3,5-dichloro-2-pyridyl group or a 5-trifluoromethyl-2-pyridyl group, and )(2 represents a lower alkyl group) 2 represented by
-(feJit+3phenoxy)propionic acid derivative. 2. General formula. (In the formula, R1 represents a 3,5-dichloro-2-pyridyl group or a 5-trifluoromethyl-2-pyridyl group, and R
A herbicide containing as an active ingredient a 2-(substituted phenoxy)propionic acid derivative represented by (2 represents a lower alkyl group).