JPS5859958A - Novel urea compounds and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound of the formula (Z is -N=, -CH=; X is H, Cl; R is methyl, methoxy). EXAMPLE:2-(2,4-Dichlorophenoxy)ethyl 4-nitrophynyl ether. USE:Herbicide: is has very good herbicidal activity to control undesired weeds efficiently by treating soil or treating the soil in irrigated lands Especially, strong weeds causing troubles in rice paddies or crop fields and broad-leaf weeds are controlled and the crops ane kept safely. PREPARATION:2-(2,4-dichlorophenoxy)ethanol and p-chloronitrobenzene are dissolved in DMF, potassium carbonate is gradually added and the reaction is carried out by keeping the temperature at 120-130 deg.C under stirring for 20hr to give the exemplified compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel urea compound and its uses. Specifically, a novel urea-based compound represented by the general formula ([) (wherein, Z represents -N- or -CH-, X represents a hydrogen atom or a chlorine atom, and R represents a methyl group or a methoxy group, respectively.) The present invention relates to a herbicide characterized by containing at least one of these compounds as an active ingredient.

The compounds represented by the general formula (D) have an extremely excellent herbicidal effect, and harmful weeds can be efficiently controlled by treating them with soil destruction treatment, flooding soil destruction treatment, or foliage treatment. Excellent herbicidal activity against harmful weeds that are particularly problematic in rice paddies and fields, such as bulrushes, snails, cypresses, Cyperaceae, Cyperaceae, and broad-leaved weeds such as morning glories, Japanese fir trees, Aobifolia, and Shiroza. and is highly safe for crops.

Next, intermediates required for the production of the compounds of the present invention and synthesis examples of representative compounds of the present invention will be explained below. Note that the compound number matches the compound number in Table 1 below.

Synthesis Example-1 (Reference) 2-(2,4-dichlorophenoxy)ethyl-4-nitrosenyl ether 2-(2,4-dichlorophenoxy)ethanol 41.
4 f (0.2 mol) and 31.5 f (0.2 mol) of parachloronitrobenzene are dissolved in 200 ml of dimethylformamide and, with stirring, potassium carbonate 3
4°6f (o, 25 mol) was added gradually. after that,'
The reaction was completed by stirring for 20 hours while maintaining the blackness at 120-130°C. After cooling the reaction solution, it was discharged into cold water of 500 mρ, and when it was left to stand for a while, crystals were precipitated. This was taken and recrystallized with ethanol to obtain the target product 2-(2,4-dichlorophenoxy)ethyl-4-nitrophenyl ether, 31f (yield 47.2%). .

mpH3-114℃ Elemental analysis value (%) C51.28, H333, C crime 2
1.66, H4,27C,,H,,CQ2No,Calculated values ■)C51,22, H3,35, Cυ21.
65, H4,27DMSO-D6 NMRδ; 4.48 (4H,S, -CH2C
H2-)+OoMl(Z Synthesis Example-2 (Reference) 2-(2,4-dichlorophenoxy)ethyl-4-amytsukenyl ether 2-(2,4-dichlorophenoxy)ethyl-4-nitrophenyl Ether 29 y (o, oss mol) was dissolved in 500 mfl acetic acid at 70°C, and reduced iron 39 y was dissolved therein.
3r (0.7 mol) was added gradually. Then at the same temperature 3
The reaction was completed after stirring for 0 minutes. After cooling, the reaction solution was passed through the mouth, and the solution was concentrated under reduced pressure and drained into cold water to precipitate an oily substance. The oil was extracted by shaking with 300 mQ of ethyl acetate, washed with a dilute aqueous potassium carbonate solution and then with water, dried over anhydrous sulfuric acid, and the ethyl acetate was distilled off under reduced pressure. The residue was isolated and purified by silica gel column chromatography (developing solution: benzene 9/ethyl acetate 1) to obtain the desired 2-(2,4-dichlorophenoxy)ethyl-4-aminophenyl ether 18.1 f(
A yield of 69.0%) was obtained.

mp-101~102℃ Elemental analysis value (%) C56,41H4,34CQ2
3.94 H4,70clau13c (calculated value (%) as 12”on) C56,38H4,36Cρ23.8
3 H4,7ONMR confidence; 3.24 (2H,S,
-NH2) 4.26 (4H.

S, -CH2CH2-) Synthesis Example-3N-4-(2-(2,4-dichlorophenoxy)ethoxy]phenyl-N',N'-dimethylurea (compound-3) 2-(2,
4-Dichlorophenoxy)ethyl-4-aminophenyl ether IVf (0.06 mol) was dissolved in 130 m of ethyl acetate.
The solution dissolved in ρ was added dropwise to 100 mQ of ethyl vinegar that had been saturated with phosgene while blowing phosgene into it (the amount of phosgene used was 0.6 mol). After that, 30
The excess phosgene was replaced with nitrogen gas by stirring under reflux, and the acetic acid was distilled off under reduced pressure to leave a residue (4-[2
-(2,4-dichlorophenoxy)ethoxy]phenylisocyanate) was dissolved in 200 mff of toluene.

Add 15% dimethylamine to this solution at room temperature while stirring.
r (0.2 mol) was gradually blown into the mixture.

After stirring for 1 hour, the precipitated crystals were collected and recrystallized with ethanol to obtain the desired compound (chill).

Synthesis Example-4, N-4-C2-(2,4-dichlorophenoxy/)ethoxy]phenyl-N'-methyl-N'-methoxyurea (compound-4) Hydroxyamine・till 3.6! (0,05
2 mol) in 8 mR of water, and at 20°C or below, 7 mρ
Sodium hydroxide dissolved in water of 2.75' (0,
068, EL) was added. 25 m of dichloromethane (4-[:2-(
2,4-Dichlorophenoxy)ethoxy]phenylisocyanate (42 g, Q13 mol) was added dropwise at room temperature.

Thereafter, the reaction was completed by stirring at the same temperature for 1 hour.

Pass the crystals through your mouth, then add 200ml of methanol to the crystals.
Add 5v of 40% sodium hydroxide aqueous solution, add 6.6f of dimethyl sulfate (0,
052 mol) was added dropwise and allowed to react at room temperature for 1 hour. After filtering out insoluble matter, the oral liquid was concentrated under reduced pressure, the residue was discharged into cold water, and extracted by shaking with 200 mfl of ethyl acetate. The ethyl acetate layer was thoroughly washed with water, then dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue obtained at that time was isolated and purified by silica gel chromatography (developing solution: toluene 4/ethyl acetate 1).
, 2,9f (yield 579% vs. 4-(2-(2,4-dichlorophenoxy)ethoxy)phenylinocyanate) Other compounds and intermediates can also be synthesized according to Synthesis Examples 1 to 4. Table 1 below shows compounds representative of this invention and their physical properties.

In order to use the compound of the present invention as a herbicide, the active ingredient compound represented by the general formula (D) may be used as it is, but in general, depending on the purpose of use, it may be mixed with a suitable liquid carrier. (e.g. organic solvent) or mixed or adsorbed onto a suitable solid carrier (e.g. diluent, filler). At this time, various auxiliary agents (e.g. emulsifier, stabilizer, dispersant, suspending agent, spreading agent,
By appropriately adding a wetting agent, penetrating agent), it can be used in various dosage forms such as emulsions, aqueous agents, granules, and powders.

When the compound of the present invention is used as a herbicide, other herbicides or pesticides such as fungicides, insecticides, and plant growth regulators,
Not only can it be used in combination with soil conditioners or fertilizing substances, but also mixed formulations with these are possible, and synergistic effects can be expected in some cases.

The content of the active ingredient of the compound of the present invention is 1 to 10% in granules.
It is desirable that the amount is 20 to 80% for irrigation agents, and 10 to 50% for emulsions (all percentages are by weight).

Next, formulation examples and physiological activity test examples of herbicides containing the compound of the present invention as an active ingredient will be shown, but the present invention is of course not limited to these. In the example,
The active ingredient compound represented by the general formula (I) is represented by the compound number in Table 1, and "1 part" represents "part by weight."

Example 10 Granule compound 35 parts, bentonite 72 parts, talc 20 parts
1 part of sodium dodecylbenzenesulfonate and 1 part of sodium ligninsulfonate were mixed, mixed with water of a suitable acid, and then granulated in a conventional manner using an extrusion granulation mold to produce 100 parts of granules. get.

Example 2 Irrigation agent 1 was prepared by mixing and pulverizing 650 parts of a wettable powder compound, 40 parts of diatomaceous earth, and 10 parts of sodium dodecylbenzenesulfonate.
Get 00 copies.

Example 3. 830 parts of the emulsion compound, 33 parts of solvent naphtha, 30 parts of dimethylformamide, and 7 parts of polyoxyethylene alkyl allyl ether are mixed to obtain 100 parts of an emulsion.

Next, the herbicidal activity of the compounds of the present invention will be specifically explained using test examples.

Test example 1. Paddy field pre-emergence weed killing test A15000 Wagner Ponot was filled with soil, firefly,
Helaomodaka, other broad-leaved weeds (Konagagi, Kikashigusa,
Seeds of Azena, etc.) were sown. Afterwards, tubers of Urikawa and Cyperus japonica were transplanted to create a flooded condition. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. Three days after rice transplantation, at the beginning of weed emergence, a predetermined amount of the test compound was submerged in water using a granule according to the method described in Example 1 above. Thirty days after the treatment, weed growth and chemical damage to paddy rice were investigated, and the results shown in Table 2 were obtained.

In this table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by comparing the state of emergence or growth of crops or weeds with the air-dried type in the untreated area, and according to the following evaluation criteria.

The test compounds are indicated by the compound numbers in Table 1 above.

Evaluation Criteria 0: Life insurance rate 91-100 compared to untreated air-dry tonnage ratio
%1 71-90%
2 41-70%3
11-40%4
6-10%5
0-5% test example 2
Seeds of Soil KS=me, Firefly, Helaomodaka, and its curved broadleaf variegated leaves (Prunus elegans, Kikashigusa, and Azena nato) were sown in a water prenatal M role early test A15000 Wagner Ponototo. After that, Urikawa,
Tubers of Cyperus japonica were transplanted and flooded. Two paddy rice plants (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. A predetermined amount of the test compound was added to the above Example 1 during the weed growth period 10 days after transplanting paddy rice. It was treated under submergence using granules according to the method described in . Thirty days after the treatment, weed growth conditions and chemical damage to paddy rice were investigated, and the results shown in Table 3 were obtained.

Test Example 1 shows the degree of chemical damage to crops and herbicidal effect on weeds with this coating. Expressed using the method shown in

Trial example 3: Pre-emergence weed killing test for field crops Fill soil in an A/1000 planter, and test dive, corn, blueberry, white locust, wild mustard, Japanese fir,
Seeds of morning glory were sown. Three days after seeding, the test compound was diluted with a water powder equivalent to 10 liters per area of the test compound using a wettable powder according to the method described in Example 2 above, and sprayed using a micro-pressure sprayer. This was grown in a greenhouse, and 30 days after the treatment, the appearance and growth of crops and weeds was investigated, and Table 4 was obtained. In this table, the degree of chemical damage to crops and the herbicidal effect on weeds were expressed using the method shown in Test Example 1.

Test example 4. Field crop fresh weed killing test A/1000 planter is filled with soil, dive, corn, blueberry, whiteberry, wild mustard, Japanese fir,
Morning glory seeds were sown and grown in a greenhouse. When the test plant has grown to the 15 to 2.5 leaf stage, the test compound is diluted in an amount of water equivalent to 10 liters per are using an emulsion according to the method described in Example 3. and sprayed with a micro-pressure sprayer. The growth status of crops and weeds was investigated 30 days after the treatment, and the results shown in Table 5 were obtained. In this table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by the method shown in Test Example 1.

Claims (1)

[Claims] 1. fldlt represented by the general formula (wherein Z represents -N- or -CH-, X represents a hydrogen atom or a chlorine atom, and R represents a methyl group or a methoxy group, respectively) Urea-based compounds. 2. Effective use of the urea-based compound represented by the general formula (wherein, Z represents -N= or -CH-, X represents a hydrogen atom or a chlorine atom, and R represents a methyl group or a methoxy group, respectively). A herbicide characterized by containing it as an ingredient.