JPS6169763A - Hydantoin derivative and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X is H or halogen; Y is halogen; R1 is H or 1-6C alkyl; R2 is (lower alkoxy-substituted) lower alkyl, allyl or 3-6C cycloalkyl; R3 is H, CH3 or C2H5; X is O or S]. EXAMPLE:3-(2-Flouoro-4-chloro-5-methoxycarbonylphenyl)-1-isopropyl-hyd antoin. USE:Herbicide. PREPARATION:The compound of formula I can be prepared by reacting the compound of formula II (R4 is cyano, hydroxycarbonyl or alkoxycarbonyl) with the compound of formula III in an inert solvent such as benzene, n-hexane, chloroform, etc. at 0-50 deg.C, and heating the resultant compound of formula IV at 100-150 deg.C in the reaction mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Degradation] The present invention relates to novel hydantoin derivatives. The derivatives are useful as herbicides.

[Conventional technology]

It is known that some hydantoin derivatives have herbicidal activity. For example, the special public service 1973-306
Publication No. 95.51-36332, JP 57-5867
2.57-197268.58-219167.

[Problem that the invention seeks to solve]

Conventional hydantoin derivatives do not have a sufficient herbicidal effect against harmful weeds such as staghorn deer, Japanese staghorn, and staghorn weeds that occur in fields, and there has been a desire for a compound that can kill these weeds at low doses.

[Means for solving problems]

As a result of studying various hydantoin derivatives, the present inventor found that the formula (where X is a hydrogen atom or a halogen atom, Ytd is a halogen atom, and R+ is a hydrogen atom or a linear or branched C5 to C6 straight chain) an alkyl group, ILz is a lower alkyl group which may be substituted with a lower alkoxy group, an allyl group or a C3-C6 cycloalkyl group, a 1 mo3 hydrogen atom, a methyl group or an ethyl group, and Z is an oxygen atom. The inventors have now completed the present invention by discovering that a hydantoin derivative represented by (or sulfur atom) exhibits strong herbicidal activity at low doses and can be used as a practical herbicide.

The hydantoin derivative represented by formula (1) can be obtained, for example, by the method shown below.

X R3R,a that is, formula (2) (wherein R2 and R3 are the same as formula (1),
R4 represents a cyano group, a hydroxycarbonyl group, or an alkoxycarbonyl group) and amines represented by the formula (
3) (wherein X, Y, at, and Z are the same as in formula (1)) is reacted with a substituted phenyl isocyanate or substituted phenyl inthiocyanate to produce formula (4) (
In the formula, X, Y, [1, t, IT, z, 11, 3, Z are the compounds represented by I (4 is the same as in formula (2)) in formula (1), which is not taken out and used as is. The cyclization reaction may be continued by heating or the compound of formula (4) may be taken out, but the compound obtained is cyclized by heat treatment or by adding a suitable acid catalyst to form the compound of formula (1). The compound shown can be k i'4).

Although it can also be carried out using anti-E, t:L, n; ltl, l;, it is generally preferable to use a tit-monoproprietary solvent.

The reaction temperature is directly operated Q'C to 150°C. That is, when Z is an oxygen atom, the formula (2) is usually obtained at O0C to 50℃.
The compound of formula (3) is reacted with the compound of formula (4)?
l) and then cyclized by heating to a temperature Vζ, preferably from 100 to 1500C, and by adding an acid catalyst to a temperature of 5 to 100°C.
When heated at C, the compound of formula (1) can be easily cyclized into 1()
can be done. Also, when Z is a sulfur atom, formula (4)
The compound can be cyclized by heating preferably at room temperature to 500 C in the presence of an acid catalyst or in the absence of an acid catalyst.

Inert solvents include benzene, toluene, xylene,
Aromatic hydrocarbons such as chlorobenzene, aliphatic hydrocarbons such as -hegisane, n-hebutane, and petroleum ether, alicyclic hydrocarbons such as cyclohexane, halogenated carbons such as chloroform, carbon tetrachloride, and perchloride. Hydrogens, ketones such as acetone and methyl ethyl ketone, ethers such as ethyl ether, tetrahydrofuran and dioxane, esters such as methanol and ethanol, amides such as dimethylformamide, or water are used.

As the acid catalyst, P-)luenesulfonic acid, sulfuric acid, hydrogen chloride, etc. are used.

The compound represented by formula (2), which is a raw material, is a known compound. In addition, the compound represented by formula (3) is a compound represented by the formula Z=CCLz (where X, Y, 1 (・1 is the same as in formula (1)) and the formula (6). (In the formula, Z is an oxygen atom of 4 and 1 (-Uhara "-Sake: T + Wasu)" by reacting with phosgene or thiophosgene or trichloromethyl chloroformate shown in formula (7). ) can be done.

Reaction &, 1. It can be carried out without a solvent, but preferably using an inert solvent as described above, and is generally carried out between -20°C and the boiling point of the mixture, preferably at r, zooC-
It is carried out between 120°C. Further, although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure.

Examples of halogen atoms in formula (1) include chlorine, bromine, and fluorine.

Examples of C1 to C6 straight chain or branched alkyl groups,
Examples include methyl, ethyl, n-propyl, 1-propyl, lobutyl, S-butyl, i-7'' thyl, 11-hentyl, 2-methylbutyl, fl-hexyl, 2-ethylbutyl, etc.Lower alkoxy Examples of groups include groups such as methoxy and nidoxy.

Examples of the 03-C6 cycloalkyl group include cyclopropyl, cyclopentyl, cycloalkyl, and the like.

When the compound of the present invention is used as a herbicide, depending on the purpose of use, it can be used as it is or mixed with agrochemical adjuvants to enhance or stabilize the effect, and can be prepared as a powder by a method commonly used in the field of agrochemical manufacturing. It can be used in the production form of fine granules, granules, aqueous phase preparations, flowable preparations, emulsions, and the like.

In actual use, these various preparations can be used as they are or diluted with water to a desired 62°C.

The agrochemical auxiliary agents referred to herein include carriers (diluents) and other additives such as spreading agents, emulsifiers, wetting agents, dispersants, fixing agents, and disintegrants.

Liquid carriers include toluene, xylene, etc. ”i
' group hydrocarbons, alcohols such as methanol, butanol, glycol, keto7j]'l such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexane, animal and vegetable oils, fatty acids, fatty acid esters etc. can be mentioned,
-1 Solid carriers include clay/kaolin, talc, diatomaceous earth,
Examples include silica, calcium carbonate, montmorillonite, pet/tonite, feldspar, quartz, alumina, and sawdust.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, and lauryl betaine, and cationic surfactants that occupy cationic interfaces. Available are surfactants, nonionic surfactants, and amphoteric ionoactive agents.

All formulations can not only be used alone, but also mixed with fungicides, insecticides, plant growth regulators, acaricides, agricultural and horticultural fungicides, soil fungicides, soil conditioners, and nematicides. It can also be used in combination with fertilizers and other herbicides.

The content of the active ingredient compound in the herbicide of the present invention varies depending on the formulation form, method of application, and other conditions. In some cases, the content of the active ingredient compound may be 0, but it is usually 0.
．． R/i is preferably in the range of 5 to 95 (heavy fan) and 2 to 50% (east end).

In addition, when weeding with the herbicide of the present invention, its use varies depending on the compound used and the location of application, etc.
! j'; 1 to 100 active ingredient compounds per are
a It is used in the range of 17 to 75 g.

[IT2 with my ability] The present invention will be explained below with reference to Examples.

Synthesis Example Synthesis Leli 1 3-(2-Fluoro-4-chloro-5-methoxycarbonylphenyl)-1-isopropylhydantoin (Synthesis of compound N002 = N-1 tube O virglycine ethyl ester 4.4 g (0, 03mol) Woturue 780ml
Add 6.9 g (0.0:3 mol) of L,2-fluoro-4-10-5-methoxycarbonylphenyl incyanate dissolved in the solution and stir at room temperature for 30 minutes, then blow hydrogen chloride into the mixture and heat to 80-100°C. After stirring for 1 hour at room temperature, the mixture was cooled to room temperature, washed with a saturated aqueous solution of sodium bicarbonate, washed with water, dried over anhydrous sulfuric acid, and concentrated, and the resulting oil was subjected to silica gel column chromatography. When purified with , white crystals s, ig (yield 61.
8%) of the desired product was obtained. The melting point was 92-9400.

Elemental analysis value CI4 HI3 FCtN204 calculated value C: 51,15 H: 4,29 N: 8
．． 52 actual measurement value C: 51.39 H: 4.31
N: 8.41 Synthesis Example 2゜Synthesis: N-methoxypropylgrine ethyl ester 4.4
g (0,0246 mol) dissolved in 80 ml of toluene tW L, 2-fluoro-4-10-5-ethquine carbonyl phenyl isocyanate 6 g (0,0246 mol) fJ: addition chamber nn'r VC"C After stirring for 30 minutes Blow in hydrogen chloride, stir at 80-1000C for 1 hour, cool at room temperature 1, wash with saturated aqueous sodium bicarbonate solution, wash with water, dry over anhydrous sulfuric acid, and concentrate to obtain an oily substance. was purified by silica gel column chromatography to yield 5.2 g (yield 59.2%) of the desired product 11) as a pale brown oil.

The refractive index of each bow was 51,5312.

Elemental analysis value CI6 mountain 8FCtN204 calculated value C:
53.86 II: 5.08 N: 7.
85 actual measurement C: 54.05 11: 5.21
N: 7.74 Synthesis Example 3. Synthesis of 3-(2-70O-4-chloro-5-n-propoxycarbonylphenyl)-1-methylhygnotoy/(Compound No. 9): Water 50+ul if sodium hydroxide 5. Dissolve 9g (0,1395 mol) of N-
Add 12.4 g (0,1395 mol) of methylglyzino and heat at 40 to 50°C for 2-70 rows 4-10 rows 5-
After adding 8 g (0,031 mol) of normal propogine carbonylphenyl inocyanate and stirring for 1 hour,
Add 45 ml of % hydrochloric acid, stir at 80-100°C for 102 hours, cool at room temperature, and add 100 ml of methylene chloride.
The resulting oil was purified by silica gel column chromatography to give light brown crystals. 2g (yield 31.
3%) of the target product was obtained.

The melting point was 98-100°C.

Original 4., min++1 value C+4114FC1N204 actual value C: 51,15 1-1: 4.29 N
: 8.52 J-dake 4 rivers [Direct C: 51.
26 II: 4.36 N:
8,67 Synthesis Example 4 3-(2-4-dichloro-5-inglobogysicalbenylphenyl)-1-n-propylhydantoin (
Synthesis of compound No. 17): 3.2 g (0,02]9 mo/l of N-normal propylcrinone ethyl ester
/) f) Dissolved in Luxun 3Q+nl, 2-4-
After adding 6 g (0,0219 mol) of dichloro-5-inopropoquinecarboxylphenyl inocyanate and stirring at room temperature for 30 minutes, hydrogen chloride was blown in to give a solution of 80 to 1
After stirring at 00° C. for 2 hours, the mixture was cooled to room temperature, washed with a saturated aqueous solution of sodium bicarbonate, washed with water, dried over anhydrous sodium sulfate, and concentrated.

Elemental analysis value C+6H+5CtN204 calculated value C:
51,48 1-1: 4,86 N: 7.
50 actual d111 value C: 5'1.53 ) (: 4
．． 88 N: 7.56 Synthesis Example 5゜Synthesis of 3-(2-fluoro-4-chloro-5-inobroboxy7carbonylphenyl)-1-methylhydantoin (compound No. 19): N-methylanoacetonitrile 1. 4 g (0.02 mol) was dissolved in 80 ml of toluene, 5.2 g (0.02 mol) of 2-fluoro-4-chloro-5-ingropoquinecarbonylphenyliso/anate was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, hydrogen chloride was blown into the mixture, and the mixture was stirred at 80 to 100°C for 2 hours at 1°1°C, cooled to room temperature, washed with a saturated aqueous solution of sodium bicarbonate, washed with water, dried over anhydrous sodium sulfate, and concentrated. The obtained oil was purified by silica gel column chromatography to obtain 4 g of pale brown crystals (yield: 60.8
悌)'s objective was obtained. The melting point was 106-107.5°C.

Elemental analysis 1st shift C14I-I14FCtN204 calculation fll'j C: 51.15 1-(: 4,29
N: 8.52 actual value C: 51,32 I
f: 4.40 N: 8,42 Synthesis Example 6 Synthesis of 3-(2-fluoro-4-chloro-5-isobrophoquinecarbonylphenyl)-1-allylhydantoin (compound No. 26): Add N to 3Qml of toluene -Allylglycine ethyl ester 4.3 g (0.03 mol) was dissolved to give 2-fluoro-4-chloro-5-ia 7'
Lohoki/carbonylphenylino7anate 7.7 g
(0.03 mol) was added and stirred at room temperature for 30 minutes, then hydrogen chloride was blown in, stirred at 80 to 100°C for 1.5 hours, cooled to room temperature, and washed with saturated sodium hydrogen carbonate solution. The oil obtained by washing with water, drying with anhydrous sulfuric acid, and condensation was purified by silica gel column chromatography to yield 8.2 g of pale yellow oil (yield δ 77.1). Base). The refractive index is n.

It showed 1.5280.

Elemental analysis value C161116FCtN204 calculated value
C: 54,17 H: 4,54 N: 7,
89 Real D River 1st shift C: 54,44 1(:
4.65 N: 7.76 Synthesis Example 7゜Synthesis of 3-(2-fluoro-4-chloro-5-inobropoquinecarbonylphenyl)-1-methyl-5-methylhydantoin (Compound No. 30) : Dissolve 4 g (0.03 mol) of N-methylalanine ethyl ester in 80 ml of toluene, and dissolve 2-Sololow 4-
Chloro-5-isopropoxyphenylisonanate 7
．． 7 g (0,'03 mol) wo1111,'-'+
< nl, l for 30 minutes Kt Stir L fc Methi 4 (
After blowing in hydrogen and stirring at 80 to 100°C for 1 hour, it was cooled outside room temperature, washed with saturated sodium bicarbonate, r# 7i, and water, and then with anhydrous sodium sulfate. When the crystals obtained by condensing the dried K 72 are tri-crystallized from toluene, 7.5 g of white crystals (yield 72
．． 9%) of the desired product was obtained. Melting point is 127-128.
It showed 5°C.

Original-(so analysis 611j, C+5[(mFCtNz
o4al Calculation [direct C: 52,56 (
-1: 4.70 N: 8,17 Actual value C: 52,74 tl: 4.93 N:
8.26 Synthesis Example 8 Synthesis of 3-(2-fluoro-4-bromo-5-impropoxycarbonylphenyl)-1-tert-butylhydantoin (compound No. 38): N-tert-butyl chrysine in 3Q ml of toluene 4.7 g (0,0291 mol) of ethyl ester were dissolved and 8.8 g (0,0
After stirring at room temperature for 30 minutes,
Add 3 ml of dihydrochloric acid, stir at 80 to 100°C for 3.5 hours, cool to room temperature, and remove hydrogen carbonate.) Wash with a saturated aqueous solution of IJ, water, dry over anhydrous sodium sulfate, and concentrate. The obtained crystals were recrystallized from a mixture of n-hexane and toluene to obtain 5.8 g (yield: 48%) of the desired product as white crystals.

The melting point was 103-104°C.

Elemental analysis value C17H20FBrN204, calculated value C: 49.17 H: 4.85 N:
6.75 Actual value C: 49.35 H: 4.7
6N: 6.44 Synthesis Example 9 3-(2-Fluoro-4-chloro-5-secondary-butoxycarbonylphenyl)-1-cyclopropylhyguntoin (Compound No.

Synthesis of 41): 3.7 g of N-cyclopropylglycine ethyl ester (
0,0258 mol) to 80 ml of toluene.
L,2-nororo-4-chloro-5-secanglyptoxylponylphenyl isocyanate 7 g (0,0
258 mol) and stirred for 10 minutes at room temperature.
Add 3 ml of 5% hydrochloric acid, stir at 80-100°C for 5 hours, cool to room temperature, wash with saturated aqueous sodium bicarbonate solution, wash with water, dry over anhydrous sulfuric acid, and condense for 11 hours. The obtained oil was purified by silica gel column chromatography to give 4.2 g of brown oil (yield 4.
4.1%) of the target product was obtained.

The refractive index was II, l;'1.5328.

Elemental analysis value Cl7k (rs FCtN 204 calculated value C: 55.36 II: 4.92 N
: 7.59 actual value C: 55,51 i-I:
4.97 N: 7.34 Synthesis Example 10 3-(4-from-3-ethoxycarbonylphenyl)
-1-71J-2-thiohydantoin (compound No.
, 46): 2.3 g (0,0157 mol) of N-71J lucrisin ethyl ester was added to 50 m of toluene.
4.5 g of 4-fum-3-ethoxycarbonylphenylinothio7anate (0,0157
After stirring at 40-50°C for 1 hour, the crystals obtained in 11) were recrystallized from toluene to obtain 4.2 g (yield: 69.8%) of the desired product as white crystals. Ta.

The melting point was 132-134°C.

Elemental analysis value C+5H+513rNz03s (
Direct C: 47,00 [-[: 3,9
4 N: 7.31 actual if (direct C
: 47,24 It : 4.06
N: 7.13 Synthesis Example 11 Synthesis of 3-(2-Fluoro-4-chloro-5-inglobinylphenyl)-1-iapropyl-2-thiohydantoin (Compound N11.52): N- 3.7g inopropylglycine ethyl ester ((
), 025 mol) dissolved in 80 ml of wotluene, 11 ff
2-Fluoro-4-10Rho5-ia Fluoropoxycarponylphenylthiocyanate (j8 g (0,
After stirring at 40-50'C for 1 hour, washing with water, drying over anhydrous sodium sulfate, and concentrating the resulting oily substance was purified by silica gel column chromatography to give 6.7 g of pink crystals (yield: 71.9)'s object 21' was found.

The melting point was 98-99°C.

Elemental analysis value C+6l-1sFCtNz (hs calculated value C: 51.54 1-I: 4.86 N:
7,51 Actual 1 rule 1 shift C: 51.72 1-1
: 4.98 N : Examples of compounds that can be obtained by the method described in 7.36 are listed in Table 1Z Next, the synthesis of substituted phenyl isocyanate and substituted phenyl inthiocyanate represented by formula (3) will be specifically explained. do.

Reference Example 1. Production of 2-fluoro-4-chloro-5-ingropoxycarponylphenyl incyanate Nitrichloromethyl chloroformate 5.4 ml (0,0
After cooling to 0°C, 13.9 g (0.06 mol) of 2-fluoro-4-chloro-5-impropoxycarbonylaniline and 25 ml of ethyl acetate were added to 30 ml of ethyl acetate. The solution was added dropwise over 15 minutes.

After stirring for 1 hour at 0-10°C, keep at reflux temperature for 2 hours. After that, it was concentrated to yield 15.45 g of the target product (yield: 99.
9) as a white crystal with a melting point of 41-43°C? given.

Reference Example 2. Production of 2-Fluoro-4-chloro-5-inopropoxycarbonylphenyl isothiocyanate = 2-Fluoro-4-chloro-5-isopropoquine carbonylaniline Totally dissolved in 10 Qml of chloroform and cooled to below 10°C After that, 17.2 g (0.15 mol) of thiophosgene was added dropwise at 1:', stirred at room temperature for 2 hours, refluxed for 3 hours, and concentrated to give 26.7 g of pale brown crystals (yield 97.5).
%) to obtain the desired object. The melting point was 46-48°C.

When using the compound of the present invention as an active ingredient of a herbicide,
One or more compounds of the present invention may be used.

Formulation Examples Next, preparation examples of the present invention will be explained in more detail.
The types and mixing ratios of additives are not limited to these, but can be varied over a wide range [・1. : III i4 ability. Note that parts refer to parts by weight.

Formulation Example 1 35 parts of a mixture of xylene and methylnaphthalene (1:1) was added to 50 parts of Emulsification License No. 26 to prepare I'(7
The emulsion is broken down by mixing with 15 parts of a mixture (8:2) of polyoxyethylene alkylphenyl ether and calcium alkylbenzenesulfonate.

Formulation example 2. Powder A powder is obtained by adding 95 parts of clay to 5 parts of Compound No. 30 and mixing and pulverizing.

Formulation example 3. 50 parts of hydrating compound No. 38, diatom ± 10 parts, Kaori 732
2 parts of sodium lauryl sulfate mixed with 1 part of the carrier
．． 2- 8 parts of a mixture of sodium dinaphthyl methanesulfonate was mixed evenly and then ground to form a fine powder binding agent.

Formulation example 4. Granules Add 5 parts of fine powder of Compound No. 52 to an appropriate mixer? Using 94.5 parts of silica grains (16-32 mensius), a methanol solution of 0.5 parts of polyvinyl acetate was applied as a binder and coated to form granules (iI).

EXPERIMENTAL EXAMPLES The excellent herbicidal activity of the active ingredient compound of the present invention will be explained below using experimental examples. All experiments were conducted in duplicate, and the resulting numbers are shown as the average value of each.1゜Experimental example 1 Submergence treatment before the emergence of paddy field weeds 175,000 paddy soil was kept constant in Wagner Bonoto, Earl. The soil was planted in a fixed amount, and a certain amount of seeds of Japanese cabbage, Japanese cabbage, Japanese cypress, azalea, Japanese chickweed, and Japanese cypress were sown.

Three tubers of Sarav Kourikawa were buried per gotsu at a depth of 1 cm below the soil surface layer, and after flooding to a depth of 3 cm, a hydrating agent of the active ingredient compounds listed in Table 2 was added as an active ingredient. The diluted solution, which was adjusted to contain 1.6 to 25 g of the compound per area, was added dropwise into the water. 3 days later, 2
．． Three rice seedlings (Niho/Bare) with 5 leaves were transplanted.

Medicine-cutting place J'! The herbicidal effect of Jif & 30 pewter and the presence or absence of chemical damage to paddy rice were investigated. The investigation was conducted using the following criteria and the results shown in Table 2 were obtained.

*Weeding effect index 5: Complete weeding 4: Weeding around 80 cm 3: 60 cm 〃 2:40 cm 〃 1:20 cm 11 0: No effect ※※Phytotoxicity index 12 No Harm +: Slight harm +: Minor damage H+: Medium Harm: Severe damage ×: Withering Table 2 Experimental example 1. Control agent for submergence treatment before paddy weed emergence Ct Experimental example 2. Water 1” Growth 1 1 submerged treatment 115.00
A certain amount of paddy soil was packed in a 0 are Wagner Ponot and planted, and the cultivation of Japanese millet, Japanese staghorn, Japanese azalea, and azalea,
A certain amount of seeds of Chickweed and Cyperus japonica were sown. In addition, 3 Urikawa tubers per bot were taken from the soil surface layer.
The seedlings were buried at a depth of cm, and three paddy rice seedlings (Nihonbare) at the 2.5 leaf stage were transplanted. Fill the area with water to a depth of 3cm,
Grown in a greenhouse.

When the weeds have grown to the 2nd to 3rd leaf stage, use the hydrating powders containing the active ingredient compounds listed in Table 3.
A diluted solution adjusted to 2.5 g was dropped into the submerged water.

The pewter herbicidal effect was investigated 30 days after chemical treatment, and the results in Table 3 were also summarized. Note that the criteria for the investigation are the same as in Experimental Example 1.

As seen in the results of Experimental Rows 1.2 and 3, the compound of the present invention showed excellent herbicidal efficacy against major perennial weeds in paddy fields throughout the year in pre- and post-emergence treatments and in growing season treatments. Moreover, it was found to be highly safe for paddy rice when treated before and after transplantation.

Next, we will show an example of an experiment conducted in a field.

Table 3 Experimental example 2, 1 row of submergence treatment during the growth period of Masa grass
Fill a circular plastic case with a diameter of 3° and a depth of 8 cm with a certain amount of field soil, and sow a certain amount of seeds of crabgrass, foxtail grass, goldenrod, Japanese knotweed, American yellowtail, and Japanese crocodile at 0.5~IC...( The soil was covered 7 times.After that, a diluted solution of a hydrating powder containing the active ingredient compounds listed in Table 4 was adjusted to 1.6g to 25.0g of active ingredient per area, over the entire surface of the soil. Processed.

Place+:+! i+ was grown in a greenhouse and its pewter weeding effect was investigated for 20 days. The experiment was conducted in duplicate, and the average value of each was determined. The investigation criteria were the same as in Experimental Example 1, and the results shown in Table 4 were obtained.

Table 4 Experimental Example 3 Soil treatment before weed germination Experimental example 4 A round plastic case with a diameter of 8C111 and a depth of 8cm was filled with leaves of field soil, and the seeds of foxtail grass and goldenrod were sown and allowed to grow. When grown at the four-leaf stage, the amount of hydrating powder containing the active ingredient compounds listed in Table 5 is 6.3g to 25.0g per area. The solution diluted to 0.0 g was sprayed on the plants.

The experiment was conducted in duplicate. Twenty days after the chemical treatment, the whites of the eyes were investigated using the same investigation criteria as in Experimental Example 1, and the results shown in Table 5 were obtained.

Table 5 Experiment 1&'l 4. j (I Grass Growth Experimental Example 5 Length 23cm, Width 45C1n, Depth 12cm, 5cm
Fill a plastic vat with a certain amount of field soil and place it in a plastic vat.
Seeds of rice, cotton, corn, wheat, sunflower, and rice were sown in fixed amounts and covered with soil to a depth of about 3 cm.

Immediately, a diluted solution of a hydrating powder containing the active ingredient compound shown in Table 6 was adjusted to 25 to 50 g of active ingredient per area, and 920 ml per vat was applied to the soil surface using a small sprayer. After treatment, growth was controlled in a greenhouse, and the degree of chemical damage to each pewter crop was investigated for 20 days. The experiment was conducted in duplicate, and the average value of each was determined.

The investigation criteria were the same as in Experimental Example 1, and the results shown in Table 6 were obtained.

Table 6 Experimental Example 5 [As is clear from the results of Experiments 113 and 4, the compound of the present invention exhibits an extremely excellent herbicidal effect on major weeds in fields through pre-emergence treatment and growth treatment. . Furthermore, as is clear from the results of Experimental Sha 115, there is no herbal medicine for crops, so it is suitable as a herbicide for upland fields.

Effect of the invention] The compound of the present invention not only exhibits excellent herbicidal efficacy against year-round weeds such as barnyard grass and broad-leaved weeds in paddy fields at a low dose;
It also shows strong herbicidal efficacy against perennial weeds such as cypress, bulrush, black eye, pineweed, and weed, and also shows excellent herbicidal efficacy in fields during pre-emergence treatment and treatment during the growing season. It has excellent herbicidal efficacy against broad-leaved weeds such as Japanese knotweed at low doses (1j), and on the other hand, it is effective against broad-leaved weeds such as Japanese knotweed, oats, corn, etc.
Soybean も, 1>crop's proboscis 11 (there is little chemical damage to two villages,
Practical 1517 Grass Cut]: 1F River.

Claims (1)

[Claims] (1) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, an alkyl group, R_2 is a lower alkyl group optionally substituted with a lower alkoxy group, an allyl group, or C_3
~ C_6 is a cycloalkyl group, R_3 is a hydrogen atom, a methyl group, or an ethyl group, and Z is an oxygen atom or a sulfur atom). (2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, X is a hydrogen atom or a halogen atom, Y is a halogen atom, R_1 is a hydrogen atom or an alkyl group of C_1 to C_6, R_2 is A lower alkyl group, an allyl group or a C_3 to C_6 cycloalkyl group which may be substituted with a lower alkoxy group, R_3 represents a hydrogen atom, a methyl group or an ethyl group, and Z represents an oxygen atom or a sulfur atom) A herbicide whose active ingredient is a hydantoin derivative.