JPS61200976A - Oxadiazol-2-one derivative and hericide comprising same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is alkyl, or benzyl; R' is phenyl or alpha-naphthyl which may be replaced with halogen, etc.) EXAMPLE:3-Methyl-5-(4-chlorophenoxy)-1,3,4-oxadiazol-2-one. USE:A herbicide. PREPARATION:A carbazinic ester (novel substance) shown by the formula II is reacted with phosgene ina solvent such as benzene, CCl4, THF, etc., at -20-100 deg.C to give a phosgene derivative shown by the formula III, which is further subjected to ring formation by adding a base such as pyridine, triethylamine, etc., at -20-150 deg.C to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel oxadiacyl-one derivative and a herbicide containing the same as an active ingredient.

[Prior art]

It is known that certain oxadiazole-coionic enzyme conductors have herbicidal activity, for example,
1F No. 91 describes 3-(co, dichloro-!-improboxyphenyl-1-1-butyl-/, ?
, 4I-oxadiazole-coon is described.

On the other hand, it is also known that some oxadiazole-one derivatives have insecticidal activity; for example, in Japanese Patent Application Laid-Open No. 12-12-12-1! -Ethoxy 3-
Benzyl/, j, 4t-oxadiazolin-kion is written.

[Problem that the invention seeks to solve]

The present inventors have discovered that the herbicidal activity is higher than that of conventional herbicides.
In order to obtain a herbicide with a high degree of selectivity and less phytotoxicity, we have conducted intensive studies on oxacyazolone derivatives having various substituents. We have discovered that leucon derivatives have extremely excellent characteristics as herbicides.

[Means for solving problems]

The gist of the present invention is the general formula (1) (wherein R represents an alkyl group or a benzyl group, and R'
is a phenyl group optionally substituted with a halogen atom, an alkyl group, an alkoxyl group, an alkylthio group, a phenoxydyl group, a nitro group, a dialkylamine group, an alkoxycarbonylamino group, a cyano group or a trifluoromethyl group, or α-naphthyl The present invention relates to an oxadiazole-coon derivative represented by the following formula (representing a group) and a herbicide containing the same as an active ingredient.

The present invention will be explained in more detail below.

In the general formula (1), R represents an alkyl group that may be linear or branched, or a benzyl group, and the alkyl group preferably has a carbon number/~, more preferably a carbon number/
~q.

R/ represents an optionally substituted phenyl group or an α-naphthyl group, and the substituent of the phenyl group is a halogen atom such as fluorine, chlorine, or bromine; a straight chain or an alkyl group; a straight chain or branched A good alkoxyl group, preferably carbon number/~! , more preferably an alkoxyl group having from 1 to 2 carbon atoms; an alkylthio group which may be linear or branched, preferably an alkylthio group having 1 to 3 carbon atoms, and even more preferably an alkylthio group having 1 to 3 carbon atoms; a trifluoromethyl group; An optionally substituted phenoxylamino group: a dialkylamino group with a total carbon number of -~tei; an alkoxycarbonylamino group that may be linear or branched, preferably a total carbon number of 2 to S, more preferably a total carbon number of 2 to S; An alkoxycarbonylamino group having from 0 to 2 carbon atoms; a cyano group or a trifluoromethyl group. When the phenyl group represented by R has a substituent, /~! Although any substitution is possible, /~J substitution is preferred, and these may be the same or different from each other. In the general formula (1), compounds in which ν has a halogen or a trifluoromethyl group at the hydroxyl position are particularly preferred.

Specific compounds of the present invention include, for example, the following compounds in addition to the compounds listed in Table 7 below.

J-:Lf-(cuchloro-3-fluorophenoxy)-/, ? , lI-oxadiazole-coon, J-methyl-1-(gubromo-3-fluorophenoxy) /*Jw"-oxadiazole-coon, J -n-propyl-t-(ll-bromo-3 -fluorophenoxy)-i,3.q-oxacyazole-λ-
1, 3-methyl-5-(3-fluoro-trifluoromethylphenoxy)-/, 3. 'I-oxadiazole-one, J-ethyl-5-(3-7/I/Oroder trifluoromethylphenoxine-/, 3.'I-oxadiazole-one, j -n- Propyl-,1-(II-chlorocofluorophenoxy)-/,J,'l-oxadiazol-one.

3-Methyl-5-(4t-bromofluorophenoxy)-i,,y,tI-oxadiazole-kone, j-n-butyl-1-(II-bromo-2-fluorophenoxy)- /, j, tI-oxydiazole-λ-one, 3-methyl-5-(-monofluorauder trifluoromethylphenoxy) -/, 3. 'I-oxadiazole-coon.

3-Ethyl-yo-(co-fluoroder trifluorometherphenoxy)-/, 3.41-oxadiazole-
The compound of the present invention represented by the above general formula (1) is a phosgene derivative represented by the general formula (1) by reacting a carbazic acid ester represented by the general formula (old) with phosgene, and then a base is added. In addition, it can be obtained by cyclization.

(I) (In the formula, R and R' have the same meanings as above.) Examples of the reaction solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated aliphatic compounds such as chloroform, carbon tetrachloride, and dichloromethane. Examples include hydrocarbons and ethers such as dioxane, diisopropyl ether, dimethoxyethane, and tetrahydro-7rane. The reaction temperature is usually -
The temperature range is 3θ to /0'Q, preferably -2Q to ioo°C. The base used in the cyclization reaction is preferably pyridine,
These are tertiary amines such as triethylamine and N,N-diethylamine, and the reaction temperature is -koθ~l! It is appropriately selected from the range of θ°C.

Although the carbazic acid ester represented by the general formula (...) is also a new compound, it can be produced, for example, by the following synthetic route in the same way as known similar compounds.

(In the formula, R and R' have the same meanings as above, and A represents a 7-butoxycarbonyl group or a benzyloxycarbonyl group.) The compound of the present invention thus obtained can be used as a herbicide as it is, but usually, Mix with an inert liquid carrier or solid carrier, add an appropriate surfactant, etc.
It is used in the form of emulsions, powders, tablets, irrigators, etc.

Liquid carriers include: ) toluene, xylene, methylnaphthalene, cyclohexane, butanol, glycol, dimethyl sulfoxide, dimethylformamide, acetone, methyl isobutyl ketone, animal and vegetable oils, fatty acids, fatty acid esters, water, etc., and solid carriers include:
Examples include clay, kaolin clay, talc, bentonite, diatomaceous earth, silica, calcium carbonate, and vegetable powders such as soy flour and wheat flour. If you need more,
It can also be used in admixture with other active ingredients such as agricultural fungicides, insecticides, nematicides or other herbicides, plant growth regulators, soil conditioners and fertilizers. Further, in order to obtain a reliable herbicidal effect, auxiliary agents such as a spreading agent, an emulsifier, a wetting agent, and a fixing agent may be appropriately mixed.

The application amount of the herbicide of the present invention varies depending on the type of compound used, the target weed, the treatment time, the treatment method, the nature of the soil, etc., but usually the active ingredient is L.
, oi~tQ grams, preferably 0. /～! A range of 0 grams is suitable.

[Effect]

The compounds of the present invention exhibit high herbicidal activity against many weeds in upland fields and paddy fields, while having almost no effect on crops. In other words, in the field, for example, whiteweed, pigweed, Japanese knotweed, hartade,
In rice fields, weeds such as azalea, Japanese chickweed, Japanese horsetail, Japanese chickweed, Japanese grasshopper, Japanese millet, Japanese cypress, Japanese cypress, Japanese scallop, and other weeds are treated before germination and during the growing season. It can be controlled in any of the treatments. In addition, the compounds of the present invention can be used, for example, in rice, soybeans, sunflowers, cotton, potatoes, wheat, and sugarcane.

It can be used as a selective herbicide in the cultivation of crops such as corn.

Note that the scope of application of the compound of the present invention is not limited to one or more seed plants, and can be used for other plants by the same application method.

〔Example〕

Next, the present invention will be explained in more detail with reference to production examples, backing agent examples, and test examples of the compounds of the present invention.

The present invention is not limited to the following examples unless it exceeds the gist thereof.

Actual Mft example/? -) Synthesis of f-5-(4I-chlorophenoxy)-/, J, II-oxadiazole-kion 3-Methylcarbazic acid-(1-/ lorophenyl]-ester/Il'1 dimethoxyethane/ZOr
A solution of 2O1) phosgene in toluene/I was added dropwise to the solution while stirring. After stirring at room temperature for one hour,
Excess phosgene was degassed through N gas. Next, after distilling off the solvent, dichloromethane/101111 was added.

The mixture was cooled to 10°C and 10 ml of pyridine was added dropwise. After being left in the apparatus for one night, the mixture was washed with dilute hydrochloric acid and brine, dried over anhydrous sodium sulfate, and then concentrated. The obtained solid was purified by silica gel column chromatography.
The compound (Aj) listed in Table 7 was obtained by cleavage.

Example 2.7-t-butyl-! -(Darklorphenoxy)-/, J, Synthesis of 41-Oxadiazole-Cone, 7-t-7'Tylcarbazic Acid-(4'-Chlorophenyl) Ester! , 9 and phosgene in 3 g of ttrts toluene solution was stirred at room temperature for 3 hours, and then the solvent was distilled off. Next, 1 gN of dichloromethane was added, and after cooling to -10°C, triethylamine O03I was added and left overnight. Post-treatment was carried out in the same manner as in Example 1, and the compound (A1
0) was obtained.

Example J Synthesis of 3-methyl-t-(4I-bromphenoxy)-i,,y,q-oxadiazole-kone, 7-methylcarno(syn[(4'-bromo7enyl]
To the hydrochloride of the ester 3gt Tetrahydrofuran tOt
The suspension was suspended in til, phosgene in 32% toluene solution/11 was added dropwise, stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. After adding dichloromethane and cooling to -7°C, add pyridine and 50% dropwise.After standing overnight, the compound listed in Table 1 (A/
c)k-obtained.

Compounds listed in Table 7 were produced in the same manner.

Next, examples of formulations of the compounds of the present invention will be shown. In addition, "department" below,
"Chi" means "parts by weight" and "t% by weight", respectively.

Formulation Example /: Irrigation Table - / Compound of the Invention Grave / Koda os1 Carplex #10 (Shiono Gireku Co., Ltd., trade name) λθ parts, N, N kaolin clay [Childbirth Kaolin Co., Ltd. trade name] 33 parts, 3 parts of higher alcohol sulfate ester surfactant Tsurupol go θ (trademark name of Toho Chemical Co., Ltd.) is blended, mixed and ground uniformly,
An irrigation agent containing 4tO% of active ingredients was obtained.

Formulation Example - Two Granules Table 7 Compound A &/or parts of the present invention, 4 parts of clay (manufactured by Nippon Merck Co., Ltd.), 3 parts of bentonite (manufactured by Toyojun Yoko Co., Ltd.), 35 parts of bentonite (manufactured by Toyojun Yoko Co., Ltd.),
The succinate surfactant Eyarol O'l'-/(Toho Chemical Co., Ltd., trade name)/l(S) was blended, mixed and pulverized, and then kneaded by adding 20 parts of water.Furthermore, this was extruded and granulated. The pellets were extruded through a hole with a diameter of 0.1 mm, dried at 60° C. for an hour, and then cut into lengths of 1 to 1 to obtain granules containing the active ingredient/%.

Formulation Example J: Compound 1631 of the present invention in Emulsion Table-1. 30 parts xylene 3
0 parts of dimethylformamide and 23 parts of dimethylformamide, and add the polyoxyethylene surfactant Tsurupol 3001 Obtained.

Formulation Example 4I: Floor pull agent 30 parts of the compound A of the present invention shown in Table 7, 3 parts of ethylene glycol mixed in advance, 0.3 parts in a vine ball
03 Co. (Toho Chemical Co., Ltd., trade name) 3 parts, xafta gum 0.
1 part and 56.9 parts of water were well mixed and dispersed. Next, this slurry-like mixture was wet-milled using Dynormi/I/ (Shinmaru Enterprises) to obtain a stable flowable agent containing 30'16 of the active ingredient.

〔Effect of the invention〕

Test Example 1 Flooded Soil Treatment Test Paddy alluvial clay loam was filled into a resin knot of 250 Q/l area, water was added in an amount equal to the amount of fertilization, and plowing was performed. Seeds of Japanese millet, Konagi, and Firefly are removed from the soil surface.
．． -jt Contaminated in the Cr11 layer.

On the other hand, paddy rice seedlings at the -leaf stage (variety: Akinishiki, plant height:
/ 0-! ; Cl7L * Seedling quality; good) Two 3-part plants per t-vat were soaked at an insertion depth of about/C1l+. Thereafter, the water depth was maintained at about 3.3 mm, and the granules containing the compound of the present invention as an active ingredient were obtained in the same manner as in the formulation example - 3rd pewter after transplantation. ) as an active ingredient, the amount of active ingredient is 70%-〇%l
A drop treatment was performed on the flooded surface by a predetermined amount so that each Io was I/a. After the treatment, the plants were given a reduced water depth of 1 day after the treatment, and then cultivated in a greenhouse, and the herbicidal effect and phytotoxicity were investigated on the 1st day after the chemical treatment.

The results are shown in Table. Furthermore, the evaluation of the herbicidal effect is was determined and expressed as a herbicidal effect coefficient using the following basic unit.

In addition, the evaluation of drug damage is was calculated and expressed as a phytotoxicity coefficient according to the following criteria.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (1 other person)

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents an alkyl group or a benzyl group, and R'
is a phenyl group optionally substituted with a halogen atom, an alkyl group, an alkoxyl group, an alkylthio group, a phenoxyl group, a nitro group, a dialkylamino group, an alkoxycarbonylamino group, a cyano group or a trifluoromethyl group, or α-naphthyl An oxadiazol-2-one derivative represented by (representing a group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents an alkyl group or a benzyl group, and R'
is a phenyl group optionally substituted with a halogen atom, an alkyl group, an alkoxyl group, an alkylthio group, a phenoxyl group, a nitro group, a dialkylamino group, an alkoxycarbonylamino group, a cyano group or a trifluoromethyl group, or α-naphthyl A herbicide containing an oxadiazol-2-one derivative represented by the following group as an active ingredient.