JPH01153682A - Substituted phenylurea derivative and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The N'-phenyl-N-methylurea derivative of formula I (A is alkylene; R<1> is methyl or methoxy; R<2> is H or methyl). EXAMPLE:1-[4-(2,3-Dihydro-2-methyl-5-benzofuranylmethyloxy)pheny-l]-3- methoxy-3-methylurea. USE:A herbicide. PREPARATION:The objective compound can be produced e.g. by reacting a compound of formula II [e.g. 4-(2,4-dihydro-2-methyl-5-benzofuranylmethyloxy) aniline] with a compound of formula III (Z is halogen) (e.g. N-methoxy-N- methylcarbamoyl chloride) optionally in a solvent (e.g. acetone) in the presence of a base (e.g. pyridine) at 0-150 deg.C.

Description

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

[Problems to be solved by conventional technology and invention]

It has been known that benzyloxyphenylurea derivatives have herbicidal activity (JP-A-Sho!; 3-'I'l#).
(Refer to 'll1 publication). It is also known that phenethyloxyphenylurea derivatives have herbicidal activity (see Japanese Unexamined Patent Publication No. 3-10g3-1O). However, these compounds do not have sufficient selectivity for crops or strong herbicidal activity. Chemical substances often differ significantly in their herbicidal activity, strength, or selectivity due to slight modifications in their structure, and due to the mere similarity of their chemical structures,
It is difficult to predict the herbicidal activity or selectivity of new compounds.

On the other hand, Tokukai Sho S Ku/! RG733 describes compounds having a benzofuranyloxyphenylurea moiety as bicyclooxyphenylurea having insecticidal activity, but these are compounds having insecticidal activity, and the above-mentioned urea derivatives having herbicidal activity are No relationship is shown.

The object of the present invention is to provide new benzofuranylalkyloxyphenylurea derivatives having excellent herbicidal activity.

[Failure to solve the problem]

That is, the gist of the present invention is as follows (1) [In the above formula, A represents an alkylene group, R1 represents a methyl group or a methoxy group, and R2 represents a hydrogen atom or a methyl group. ] and herbicides containing this as an active ingredient.

Next, the present invention will be explained in detail.

In the above-mentioned (1), A is an alkylene group, specifically, for example, -CH2-1-CH2CH2-1-CH
-1-CH2CH2CH2-1-CHCH27, zo.

-CH2CH2CH2CH2-1-(t)CH2CH2
Straight chain or branched alkylene groups such as -, preferably -C
H2-1H3 ■ Represents -CH2CH2-1 or -CHCH2-. or,
R1 represents a methyl group or a methoxy group. R2 represents a hydrogen atom or a methyl group, preferably a methyl group.

Although the compound of the present invention represented by formula (1) is a new compound, it can be produced using various raw materials, for example, according to the following reaction formula.

(n) (I) [In the above reaction formula, A, R'' and R2 have the same meanings as above, and Z represents a halogen atom.] The above reaction can be carried out without a solvent or with a ketone such as acetone or ethyl methyl ketone. in solvents such as aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether and tetrahydrofuran; aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone; The reaction is carried out in the presence of an organic base such as triethylamine, pyridine, N,N-diethylaniline, or an inorganic base such as sodium carbonate or sodium hydroxide at a temperature of 0 to 130°C.

(I) [In the above reaction formula, A, R'' and R2 have the same meanings as above.] The above reaction can be carried out without a solvent or with aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; ethyl acetate, ibutyl acetate. acetic acid derivatives such as diethyl ether, diimpropyl ether, tetrahydrofuran,
Ethers such as dioxane; Aprotic polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolitone; Ketones such as acetone and ethylmethylketone; methanol, ethanol,
The reaction is preferably carried out in an alcohol such as butanol; a solvent such as water, or a mixed solvent thereof in a temperature range of -10-/θO'C.

Incyanate (Ill), which is a raw material for the above reaction, can be produced from the raw material aniline derivative (II) in reaction formula (1) according to the following reaction formula.

[In the above reaction formula, A and R2 have the same meanings as above. ] In a solvent such as aromatic hydrocarbons such as bene/yne, toluene, xylene, and chlorobenzene; acetate esters such as ethyl acetate and isobutyl acetate; and ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane. , triethylamine, pyridine, quinoline, N,N-diethylaniline, etc., in the presence or absence of an organic base such as -20-1g0°C.

(IV) (V) (I) [In the above reaction formula, A, R'' and R2 have the same meanings as above, and Y represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group.] The above reaction is , solvent-free or keto/types such as acetone and ethyl methyl ketone; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether and tetrahydrofuran; acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl in a solvent such as an aprotic polar solvent such as pyrrolidone; an organic base such as triethylamine, pyridine, N,N-diethylaniline; an inorganic base such as sodium carbonate, sodium hydroxide; an alkali metal hydride such as sodium hydride; or , in the presence or absence of an alkali metal such as metallic sodium at 0 to iso°C.

Incidentally, the aniline derivative (II) which is the reaction raw material in the reaction formulas (1) and (2) above can be produced by the method (a) or (ra) below.

(a) [In the above reaction formula, AlZl and R2 have the same meanings as above. ] (II) [In the above reaction formula, A1Z1R2 and Y have the same meanings as above. ] The compound of the present invention thus obtained can be used as a herbicide as it is, but it is usually mixed with an inert liquid or solid carrier, and a suitable surfactant etc. added thereto to form an emulsion, powder, or granule. , used in the form of irrigation agents, 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, oxtail water, etc., and solid phase carriers include viscosity, kaolin clay, talc, bentonite, diatomaceous earth, silica, calcium carbonate, soybean flour, and wheat flour. Examples include vegetable powders such as In addition, if necessary, other active ingredients, such as agricultural fungicides, insecticides, nematicides or other herbicides,
It can also be used in combination with plant growth regulators, soil conditioners, fertilizers, etc. In addition, in order to obtain a reliable weeding effect,
It is preferable to appropriately mix auxiliary agents such as spreading agents, emulsifiers, wetting agents, and fixing agents.

The application amount of the herbicide of the present invention depends on the type of compound used,
Although it varies depending on conditions such as target weeds, treatment time, treatment method, and soil properties, it is usually appropriate for the active ingredient to be in the range of 5 to 5, preferably 1 to SO .

〔Effect of the invention〕

The present inventors have found that the compound of the present invention exhibits high herbicidal activity 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,
Golden millet, purslane, chickweed, hotokenoza, yellowtail grass, blackberry grass, cyperus japonica, cyperus japonica, and in rice fields, for example, azalea, cyperus japonica,
Abu Tsume, Mizono 1 Kobe, Heraomodaka, Tainubie,
It is possible to control weeds such as Japanese cypress and Japanese cypress with both pre-emergence treatment and growing season treatment.
In addition, it has almost no effect on crops such as rice, sunflower, potato, wheat, barley, sugarcane, and corn, so it can be used as a selective herbicide in the cultivation of these crops.

As described above, the compound of the present invention has the excellent property of being able to control many weeds without causing much harm to crops.

Moreover, the compounds of the present invention can be used against weeds that have been difficult to control using current herbicides, such as Japanese croaker, Japanese trumpet, wild mustard, Japanese violet, orocha chrysanthemum, etc. in upland fields. It was found that it has high pesticidal activity. As described above, the compound of the present invention has a very broad herbicidal spectrum and is highly safe for crops.

The scope of application of the compound of the present invention is not limited to the above-mentioned types of plants, and it can be used for other plants by the same application method.

〔Example〕

Next, the present invention will be explained in more detail by giving examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example//-(4-(core 3-dihydro-methyl-
3-Benzofuranylmethyloxy)phenyl]-3-methoxy3-methylureahiro-(,2,,?-dihydro-methyl-S-benzofuranylmethyloxy)aniline b, s 11 k, 3
Dissolved in 0ml of pyridine and cooled with water, N-methoxy
31 g of N-methylcarbamoyl e-loride was gradually added dropwise. After stirring for several hours, pyridine was distilled off under reduced pressure, and the remaining oil was dissolved in 100-100 of toluene. After washing with water, diluted hydrochloric acid, and saturated saline, the toluene was distilled off and the residue was dissolved. By subjecting the product to silica gel column chromatography using ethyl acetate:n-hexane=/:l as a developing solvent, 7.3I of the compound (4/) listed in the table was obtained.

Example 2 l-[Cu(su,3-dihydro-comethyl-S-benzofuranylmethyloxy)phenyl)-3,3-dimethylurea y'-(x,3-dihydro-cotatyl-3-benzofuran Nylmethyloxy) aniline Otsu,! 1fIO-N,
Dissolved in N-dimethylformamide and then added triethylamine s, g g'6. N,N-dimethylcarbamoyl chloride 3, g g'i, was gradually added dropwise to this solution. After continued stirring at room temperature, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off. The residue was subjected to silica gel column chromatography using ethyl acetate:n-hexane as a developing solvent to obtain the compounds listed in the table (A).

Example 3 s-
H/7”furanyl)ethyloxyphphenylisocyanate/0gI was dissolved in 20-g of toluene, and 3
- N dissolved in toluene.

O-dimethylhydroxylamine2. θI was gradually added dropwise at room temperature. After stirring at room temperature for one hour, toluene was distilled off.
The residue was subjected to silica gel column chromatography using ethyl acetate:n-hexane=2=3 as a developing solvent to obtain compounds (4,7) listed in the table.

Example #/-(,?-(co,3-dihydrocomethyl-left-benzofuranylmethyloxy)phenylcou 3-methoxy-3-methylurea, 3-dihydrocomethyl-S-benzofuran 2.gE of nylmethyl chloride and 3.0 g of /-(3-hydroxyphenyl)-3-methoxy-3-methylurea were dissolved in 20-g of dry N,N-dimethylformamide, and then 2.g of anhydrous potassium carbonate was dissolved. 3g was added.This mixture fgO℃
After stirring for a while, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off. The residue was diluted with ethyl acetate:n-hexane=
/:By subjecting to silica gel column chromatography using λ as a developing solvent, the compound (A7
)i, r-7g was obtained.

Example A; 3-
Methyl urea, θI, was dissolved in dry N,N-dimethylformamide, 20- and 60% hydrogenated sodium chloride.
g6 added. After stirring for 30 minutes, under water cooling, 2-(3-dihydro λ-methyl-S-penzofuranyl)'ethyl p
-) Ruensulfone) 3.3,! il' i dripped. After stirring at room temperature for 5 hours, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off.

By subjecting the residue to silica gel column chromatography using ethyl acetate:n-hexane=/: as a developing solvent, the compound (A6.9) listed in Table 2 was obtained with 3.3
,! I got i+.

The compounds listed in Tables 1 and 2 were produced in the same manner as in Examples 1 to 5 above. Moreover, the melting point or refractive index of each compound is also shown in Tables 7 and -.

Table 1 Next, examples of formulations of the compounds of the present invention are shown. In addition, "department" below,
"r*" means "1 part by weight" and "% by weight," respectively.

Production example / Wettable powder table / and tio part of the compound of the present invention, Carplex +
20 parts of go (trade name, Shionogi & Co., Ltd.), 35 parts of N,N kaolin clay (trade name, Ueya Kaolin Co., Ltd.), and 3 parts of higher alcohol sulfate ester surfactant Tsurupol goto (trade name, Toho Chemical Co., Ltd.) were blended. The mixture was uniformly mixed and pulverized to obtain an irrigation agent containing the active ingredient yO.

Formulation Example Koni Granule Table 1 and Table 1 Compound of the present invention 7 parts, clay (manufactured by Nippon Talc Co., Ltd.) 3 parts, bentonite (manufactured by Toyojun Yoko Co., Ltd.) SS part, succinate surfactant Eyarol CT-/(Toho Chemical Co., Ltd.) Company (trade name) 7 parts, mixed and pulverized, then water f2
0 parts were added and kneaded. Further, this was extruded through a hole with a diameter of 0.1-am using an extrusion granulator, dried at 60°C for an hour, and then cut into lengths to form granules containing 1% of the active ingredient. obtained the drug.

Formulation Example 3: Emulsion 30 parts of the compound of the present invention shown in Table 1 and 2 are dissolved in a mixed solvent consisting of 30 parts of xylene and 2S parts of dimethylformamide, and the polyoxyethylene surfactant Tsurupol 3oosxc (Toho Kagaku Co., Ltd., trade name) is dissolved in this. ) Add the lS part,
An emulsion containing 30'% of the active ingredient was obtained.

Formulation Example 1I: Flowable agent 3 parts of ethylene glycol and 3 parts of ethylene glycol mixed in advance with 30 parts of the compounds of the present invention shown in Tables 1 and -, Tsurpol AC303
1 (Toho Chemical Co., Ltd. trade name), 0 parts of xanda gum, and 36.9 parts of water were well mixed and dispersed. Next, this slurry-like mixture was wet-milled using Dyno Mill (Shinmaru Enterprises) to obtain a stable flowable agent containing 30% of the active ingredient.

Next, test examples of the compounds of the present invention will be shown.

Test Example/Flooding Treatment Test A resin vat of 2 soo/R was filled with paddy alluvial clay loam, and after fertilization, an appropriate amount of water was added and plowed. Seeds of Novie, Kikashigusa, and Konagi were collected from the soil surface. !
; Contaminated in the cm layer.

On the other hand, paddy rice seedlings (variety: Akinishiki, seedling quality: good) at the ;t and S leaf stages were placed in a bat, 3 plants/f2 plants, insertion depth/crn.
Soaking was carried out. Thereafter, the water depth was kept at about 3.3 cm, and 3 days after transplantation, the granules containing the compound of the present invention as an active ingredient obtained in Formulation Example 1 and the comparative compound obtained in the same manner as in Formulation Example Granules containing -y-[x-(q-methylphenyl]ethyloxy]phenyl-3-methoxy-3-methylurea as an active ingredient are 70 and S
A predetermined amount of water was dropped onto the flooded surface so that the ratio was gram/R. After treatment, the plants were given a water reduction property of 3 tm to 7 days, and then cultivated in a greenhouse, and on the 27th day after the chemical treatment, the herbicidal effect and herbicidal damage were investigated.

The results are shown in Table 3. In addition, the evaluation of herbicidal effect is as follows: was calculated and expressed as a herbicidal effect coefficient according to the following criteria.

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

Table 3 Flooded soil treatment test results Test example Stalk and leaf treatment test Small polyethylene pots of ygso / are filled with upland black soil, and after fertilization, various types of Japanese knotweed, white locust, Japanese crocodile, hotokenoza, yamgrass, corn, and barley were grown. The offspring were sown in separate pots.

Cultivation management continued in the greenhouse, and the growth levels of the test plants were as follows: Inutade-leaf stage, Shiroza 3-leaf stage, Ichibiko-leaf stage, and Hotokenoza λ.
When the leaf stage, Yaemugura eight leaf stage, corn three leaf stage, and barley lambda leaf stage are reached, the water conservancy and formulation example containing the compound of the present invention as an active ingredient are prepared in the same manner as in Formulation Example. A comparative compound/-y-(s-(lI-methylphenyl)ethyloxy)phenyl-3-methoxy-3-methylurea as an active ingredient was diluted with water in a controlled room so that the active ingredient became a predetermined amount. The herbicidal effect and phytotoxicity were investigated on day 1 after spraying the herbicide.The results are shown in Table 1.The herbicidal effect and phytotoxicity were evaluated in the same manner as in the test example. Ta.

Claims (2)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the above formula, A represents an alkylene group, R^1 represents a methyl group or a methoxy group, and R^2 represents Indicates a hydrogen atom or a methyl group. ] N'-phenyl-N-methylurea derivative. (2) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the above formula, A represents an alkylene group, R^1 represents a methyl group or methoxy group, and R^2 represents Indicates a hydrogen atom or a methyl group. A herbicide containing an N'-phenyl-N-methylurea derivative represented by the following as an active ingredient.