JPS61180759A - Phenoxybenzylurea derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 and R2 are H, alkyl, alkenyl, alkynyl, alkoxy, etc.; R1 and R2 may together form a carbon ring; X1, X2 and X3 are H, Cl or trifluoromethyl). EXAMPLE:3-(alpha,alpha-Dimethyl-m-phenoxybenzyl)-1-methyl-1-phenylurea. USE:Herbicide exhibiting excellent effect against a wide variety of weeds especially by applying immediately before or after sprouting of the weeds. It has no phytotoxicity to various crops and paddy rice plant, and selectively controls the weeds. PREPARATION:The compound of formula I can be prepared by reacting the compound of formula II with the compound of formula R1NCO in an inert solvent such as benzene in the presence of a base (e.g. pyridine, NaOH, etc.) at a temperature between 0 deg.C and the refluxing temperature of the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a phenoxybenzylurea derivative represented by the following general formula and a herbicide containing the compound as an active ingredient.

[In the formula, R1+R2 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aralkyloxy group, a cycloalkyl group, an aralkyl group, or a phenyl group (halodan atom, (or may be substituted with a methyl group) fjr-, or R1 and 82 may form a carbon ring. Xl r X2 a Xs represents a hydrogen atom, a chlorine atom, or a trifluoromethyl group. ] (Effect of the invention) The phenoxybenzylurea derivative represented by the above general formula of the present invention is a new compound not described in literature, patents, etc.
After synthesizing this compound and carrying out various studies, it was found that it has excellent effects as a herbicide.

That is, the compound of the present invention exhibits strong herbicidal activity against a wide range of weeds, and the active ingredient is administered at a dose of 0.1 to 20 kg per hectare, preferably 0.0 kg, immediately before the weeds germinate or at the early stage of their growth. If .5 to 10k19 is applied, a wide range of weeds as described below can be killed in about 1 to 2 weeks.

In addition, if the amount of this compound is limited or if an appropriate application method is applied, corn, potato, etc.
Sugarcane, peanuts, soybeans, sunflowers, barley, wheat,
Weeds can be selectively controlled in fields where specific crops such as trumpet gum, paddy rice, cotton, and fruit trees are grown. In particular, in paddy fields, the product is capable of controlling strong weeds such as Japanese field weed, fireweed, and Japanese cyperus without causing any chemical damage to the rice.

(Structure of the Invention) Typical examples of the compounds of the present invention are shown in Table 1.
Examples include the following.

Incidentally, the compounds are indicated by the symbols in the above general formula.

mp represents uncorrected melting point. Moreover, nD indicates a refractive index. Others follow conventional expressions.

The compound of the present invention can be synthesized, for example, according to the following formula.

[In the formula, R1 is an alkyl group, an alkenyl group, an alkynyl group, a Schiff's alkyl group, an aralkyl group, or a 7-enyl group (which may be substituted with a halodane atom or a methyl group)
-, Xl = X2 e X3 represents a hydrogen atom, a chlorine atom, or a trifluoromethyl group. ] [During the ceremony,
R,, R2 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aralkyloxy group, a cycloalkyl group, an aralkyl group, or a phenyl group (a halodane atom or a methyl group) ), or R
1 and R2 may form a carbon ring. X,a X2
r X3 represents a hydrogen atom, a chlorine atom, or a trifluoromethyl group. ] In formula C, R represents an alkyl group, a cycloalkyl group, or a phenyl group (which may be substituted with a halodef atom or a methyl group), and Xl e X2 + Xs is a hydrogen atom, a chlorine atom, or a trifluoro represents a methyl group] [wherein R1 represents an alkyl group, a cycloalkyl group, or a phenyl group (which may be substituted with a halodane atom or a methyl group); R represents an alkyl group, an alkenyl group, or an alkynyl group; group, or an aralkyl group, haA represents a chlorine atom, a bromine atom, or an iodine atom, and Xl e
X2 e X3 represents a hydrogen atom, a chlorine atom, or a trifluoromethyl group] Steps (1), (2) # (
Regarding 3) or (4). The solvent is appropriately selected from inert solvents such as benzene, toluene, chloroform, dichloromethane, dioxane, ethyl ether, tetrahydro7rane, acetone, methyl ethyl ketone, dimethyl formamide, dimethyl sulfoxide, acetonitrile, and tertiary amines used as bases. and can be used. Alternatively, the reaction can be carried out without a solvent depending on the case. As a base, tertiary amines such as bald lysine, triethylamine, N,N-dimethylaniline, potassium carbonate, sodium carbonate, sodium hydroxide,
Alkalies such as potassium hydroxide, sodium hydride, etc. are suitable.

The reaction temperature is suitably from the general KO°C to the reflux temperature of the solvent.

Regarding process (5). As a solvent, methanol, ethanol, n-7'rotJ? lower alcohols such as nol,
It can be appropriately selected from dimethylformamide, benzene, toluene, etc. and used.

Suitable bases include sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium hydroxide, potassium hydroxide, and sodium hydride. The reaction temperature is generally from 0°C to the reflux temperature of the solvent.

Typical synthesis examples are shown below and will be explained and explained in more detail.

Luurea (compound product 6) α,α-dimethyl-m-phenoxypenzyl isocyaner) 2.511 N-methylaniline 1. Add IJF and heat under reflux for 3 hours.

After cooling, the mixture is washed with a 2N hydroxide aqueous solution, 2N hydrochloric acid, and water in this order. After drying with magnesium sulfate, the solvent is distilled off under reduced pressure to obtain crystals. When this crystal is recrystallized from benzene-n-hexane, the target compound (A
6) is obtained at 2.91.

(Compound shop 5) p-) Lylisocyaner) 1.3.9 cyclohexane 5QmJ? Add α,α-dimethyl-m-phenoxybenzylamine 2.3.9 to the solution and leave it at room temperature overnight. The obtained crystals were mixed with 2N aqueous potassium hydroxide solution, 2N
- Thorough washing in the order of hydrochloric acid, water, and n-hexane yields 3.31 of the target compound (Ban 5).

Compound 9) α,α-dimethyl-m-phenoxypenzyl isocyaner) 1.0 g of n-butylamine was added to the chloroform solution of 2.5.9 and heated under reflux for 2 hours.

Then, the solvent is distilled off under reduced pressure to obtain crystals. When this crystal is thoroughly washed with n-hexane, the target compound (A
9) yields 2.9I.

Chilurea (compound product 19) To a solution of 1.0 I of N-methyl-n-butylamine in 20 rLl of dichloromethane was added 2.51 l of α,α-dimethyl-p-phenoxybenzyl isocyanate, and the mixture was heated under reflux for 1 hour. From now on, 2N-hydrochloric acid, 2N-hydroxide)
After washing with an aqueous solution of IJ and water, and drying with magnesium sulfate, treatment with florisil column chromatography (dichloromethane solvent) yields 2.9I of the target compound (Y19) as a transparent sill-like substance.
~m -(2,4-dichlorophenoxy)-α, α-
Dimethylbenzylamine 3.0.9 and triethylamine 1, dissolved in 25 ml of igt-toluene and stirred at room temperature, N,N-dimethylcarbamoyl chloride 1.11
1 toluene 5r! The solution of Ll is added dropwise over 15 minutes.

Next, the mixture was stirred at room temperature for 30 minutes, heated to 60°C, and stirred for t-6 hours. After cooling, water is added to separate the organic layer, and the resulting organic layer is washed with 2N hydrochloric acid, 2N sodium hydroxide, and water in this order, and dried over magnesium sulfate. The solvent is removed under reduced pressure to obtain crude crystals. When this crude crystal was recrystallized from a benzene-n-hexane mixed solvent, the target compound (A47) was obtained as white crystals.
．． 6I is obtained.

N-phenylhydroxylamine 3.4.91-tF
Pour a solution of 20 ml of ethyl ether into a 100 mJ 3 flask, stir well at room temperature, and add 7.6 mL of α,α-dimethyl-m-phenoxybenzyl isocyanate.
A solution of 30 ml of benzene containing I is added dropwise. Next, the reaction is carried out at room temperature for 1 hour and heated at 35° C. for 3 hours. After the reaction, the reaction solution was washed twice with water, dried over magnesium sulfate, and the solvent was distilled off to give 3-(α,α-dimethyl-m
10.511 of -phenoxybenzyl)-1-hydroxy-1-phenylurea are obtained as crude product. This 3
-(α,α-dimethyl-m-phenoxybenzyl)-1
Add 3.6 g of -hydroxy-1-phenylurea to a solution of 20 g of methanol containing 0.5.5 N of sodium methyl chloride to make a homogeneous solution, and then add allyl bromide at room temperature.
．． 3Ji't-add. Stir at room temperature for 2 hours, then heat under reflux for 30 minutes.Then, the solvent is distilled off under reduced pressure, dichloromethane and water are added to the resulting residue, and the organic layer is separated. Salt the organic layer! , 10M aqueous sodium carbonate solution, and water in this order. After drying with IJum (sulfuric acid), the solvent is distilled off.

The obtained silica, stick-like substance was subjected to silica gel column crawler)
The target compound (445) was obtained as white crystals by treatment with a toluene-n-hexane mixed solvent system.
．． 2.9 is obtained.

The active compounds according to the invention can be made into dosage forms such as emulsions, aqueous solutions, yeast preparations, floatable preparations, powders, granules, etc. by applying conventional formulation methods.

Furthermore, the compounds of the present invention can be mixed with other herbicides. Furthermore, in order to expand the range of action, it can be used in combination with agricultural chemicals other than herbicides, such as insecticides and fungicides.

(Example) Next, an example of a typical dosage form will be given. "Parts" in the description indicate parts by weight.

Example 1 50 parts of the compounds shown in Table 1 as active ingredients for a wettable powder, 10 parts of diatomaceous matter, 35 parts of clay, 3 parts of sodium polyoxyethylene alkyl allyl ether sulfonate, and 2 parts of sodium alkylnaphthalene sulfonate were mixed. It is pulverized to obtain an aquarium containing 501 active ingredient compounds.

When using, dilute with water to the specified concentration and spray.

Example 2 Granules 10 parts of the compound shown in Table 1, 20 parts of bentonite, 68 parts of clay
1 part and 2 parts of sodium dodecylbenzenesulfonate are mixed together, about 20 parts of water is added, and the mixture is kneaded with a mixer, then granulated through a granulator, and then dried and sized to obtain granules containing the active ingredient IOS. get the agent.

The novel thiophene derivative of the general formula χ has excellent herbicidal activity and is therefore suitable for controlling weeds growing in rice fields, fields, orchards, non-agricultural lands, etc.

When this active compound is applied to the soil surface or mixed into the soil, it can significantly inhibit the growth of weeds and cause them to die. Weeds can also be controlled by spraying the main agent on the stems and leaves of growing weeds.

The dosage of this compound C is regulated and the application amount is 90% per hectare.
0.5~20kl? Select from paddy rice, corn, wheat, barley, sugarcane, rhubarb, peanuts,
It can be used as a selective herbicide in cultivated fields such as sunflowers, potatoes, cotton, or fruit trees. It can also be applied as a non-selective herbicide by increasing the application rate.

The compounds of the present invention can be used, for example, to control the following weeds: That is, dicotyledonous plants such as Stellaria media, C.
henopodium album)-Sa
ginajapaniea), Koa Turnip (Chonop)
odium ficifolium), Japanese knotweed (
Polygonum nodosum) + 1 Portulaca oleracea - Shepherd's purse (
Capsella bursa-pastoris),
Lepidium virgini
cum) s Porippa 1ndi
ca), Tanetsukepana (Cardamine fl.
xuosa) %ichibi (Abutllon avic
ennae) % American Golden Deer (Sida 5p
inosa), Ammanniamul
Tiflora), Malpa Morning Glory (Ipomoeap)
urpurea) sノ? Logik (Senecio v.
ulgaris) 1 Sonchus as
per), Bidens fr.
ondosa), Butafusa (Ambrose i)
aartemisiifolia)
ster 5ubulatus).

Hotokenoza (Lamium amplexic4ule)
), Kata/Nilmi (Oxalis cornicul
ata) - Amaranthus retro
flexus), crow tree pea (Viciasat
iva), Yaemugura (Galium aparine)
), Solanum nigrum
- Datura stramon
ium) % Monochoriavagin
Poa annua s, Poa annua s, Poa annua s, etc.;
opaculus aequalis) sMehishi/4
(Digitaliaadacendens) %Ohishi/4 (Eleuaine 1ndiea)%
Setaria viridis,
Golden millet (Echinochloa erusgall)
i), Agropyron kamoji
) Lo 1 i um perenne
)% Bromus unioloides
), Oat (Avena fatua), Polypogon Higagaweri % Panicum dichotomiflo
rum ), Cyperaceae weeds, such as Cyperus m1croiria s Scirupus 1uncoides , Cyperus serotinus % Cyperus diformia % Hamas l' (Cyperus rotundus), Cyperus rotundus (Cyperus 1ria), Cyperus rotundus (
Eleocharisacicularis) et al.

The compound of the present invention has a herbicidal effect on a wide range of weeds as described above, and when sprayed on the field soil surface, the foliage surface of plants, or in waterlogged areas, immediately before or after the weeds germinate. , or when mixed into the soil, an excellent weed control effect can be obtained.

In particular, flooded soil treatment has an extremely high control effect on paddy field weeds.

In order to demonstrate the herbicidal effect of the herbicide according to the present invention, some representative test examples will be given and explained in more detail.

Test Example 1 A pot with an area of 100 cWL was filled with volcanic ash soil, and Mehishi/Z (Digitaria adscendens)
Golden millet (Eehinochloroa crus-ga)
Rumex japanicus
, Amaranthus retrofl
ms)% Zea mays, wheat (
Triticumaestivum) syaenari (P
haseolus radiatus)
Chrysanthemum coronarium)
, t of seeds are sown and covered with about 5 layers of soil. Immediately after that, the compounds listed in Table 1 are prepared as an irrigation agent according to Example 1, and this is diluted with water to determine the effectiveness. A dose of the ingredient equivalent to 8 ml per hectare was applied to the soil surface of each pot. Two weeks after treatment, the herbicidal effect on plants was investigated. The herbicidal effect was observed with the naked eye and is expressed in Table 2 on an 11-level index from O: no effect to 10: complete death.

Test Example 2 Weeding effect on plants in case volcanic ash soil was filled in a pot with an area of 100 cIrL2, and
)% Golden millet (Echinoehloa erus-
galli) - Rumexjaponic
us ), Amaranthus retr
Zea mays
), wheat (Trittcumaastivum)
% Yaenari (Phaseolus radiatus)
) Chrysanthemum co
ronarium) seeds, about 151'lll.
Cover with soil and place in a greenhouse, and when the weeds have 1 to 2 leaves, apply 98 kg of an irrigation agent containing the compound of the present invention per 1 hectare.
dilute the amount of drug equivalent to 1000 J/ha with water,
Sprayed using a sprayer. Ten days after the chemical spraying, the test was conducted using the same criteria as in Test Example 1, and the results were expressed using an 11-level index. The test results are shown in Table 3.

Test Example 3 A pot with an area of 120 crn2 was filled with paddy soil and cultivated with Eehinochoa crus-galli.
) s Hotarui (,6ajrphtJunwo4ans
)i, Ammanniamultif
lora), Monochoria vag
Seeds of Eleocharis aci) were mixed into soil with a surface layer of about 2 cIrL, and
eularis) and two-leaf stage paddy rice were transplanted to two locations each, and the water depth was approximately 3 cmJ. Three days later, an aquarium containing the compound of the present invention prepared according to Example 1 was administered into the water at a dosage equivalent to 8 to 9 parts per hectare. Three weeks after the chemical treatment, the herbicidal effect and the chemical damage to paddy rice were examined. The herbicidal effect and the chemical damage to crops were investigated using the same criteria as in Test Example 1, and expressed on an 11-level scale. The test results are shown in Table 4. .

Table 4 shows that the compound group I of the present invention is effective in killing weeds, which are important weeds in rice fields, such as Japanese grasshopper, Japanese bulrush, Japanese grasshopper, Japanese grasshopper, and Japanese grasshopper.

Test Example 4 Chemical damage to Echinoehoa crus-galli
), Firefly (Scirpus 1uncoides)
, Cyperus serotinus
The control effect on paddy rice and the chemical damage to paddy rice were tested in the same manner as in Test Example 3. The test results are as shown in Table 5.

Claims (1)

[Claims] 1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkenyloxy groups, and alkynyloxy groups. , an aralkyloxy group, a cycloalkyl group, an aralkyl group, or a phenyl group (which may be substituted with a halogen atom or a methyl group), or R_1 and R_2 may form a carbon ring. X_1, X_2, and X_3 represent a hydrogen atom, a chlorine atom, or a trifluoromethyl group. ] A phenoxybenzylurea derivative shown in 2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups, aralkyloxy groups, cyclo It represents an alkyl group, an aralkyl group, or a phenyl group (which may be substituted with a halogen atom or a methyl group), or R_1 and R_2 may form a carbon ring. X_1, X_2, and X_3 represent a hydrogen atom, a chlorine atom, or a trifluoromethyl group. ] A herbicide containing a phenoxybenzylurea derivative as an active ingredient.