JPS62205054A - Urea derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R is (alkyl-substituted) phenyl or pyridyl; X is O, S or methylene; Y is H or F] and its salt. EXAMPLE:N-ethyl-N-methyl-N'-[4-(2-(4-methylphenyl)ethoxy)phenyl]urea. USE:A herbicide exhibiting strong herbicidal effect against weeds, free from phytotoxicity to crops such as soybean, wheat, etc., and having excellent safety. PREPARATION:The compound of formula II is made to react with the carbamoyl halide of formula III (Z1 is halogen) in a solvent optionally in the presence of an acid acceptor at 10-50 deg.C for 0.5-10hr to obtain the objective compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD OF THE INVENTION This invention relates to novel urea derivatives useful as herbicides.

Prior Art Conventionally, N'-(8,4-dichlorophenyl)-N,N-
Dimethylurea (diuron) and N'-14-(4-chlorophenoxy)phenyl 1-N,N-dimethylurea (
Although urea derivatives such as chloroxuron are known to have herbicidal effects, the selectivity between crops and weeds in their herbicidal effects is not always sufficient, and it is still difficult to use herbicides with high selectivity. Development is awaited.

In recent years, various studies have been carried out to improve this drawback, and some slightly improved compounds are being obtained, such as the compound described in Patent Publication No. 56-119460. However, these compounds still cannot be said to be sufficient in herbicidal action and safety for crops.

Problems to be Solved by the Invention The present inventors further improved these points and continued research to find a highly selective herbicide with higher activity and less phytotoxicity. As a result, the following compound [I] and its salts were developed. The compound described in the above-mentioned patent publication No. 56-139460, which is structurally similar,
For example, it has higher herbicidal activity than N'-[4-(3-(8-pyridyl)propoxy]phenyl)-N,N-dimethylurea, and has significantly lower phytotoxicity to crops such as soybeans and wheat. I found that it is excellent.

That is, the present invention provides urea derivatives and salts thereof that exhibit high herbicidal activity against weeds and are highly safe for useful crops.

Structure of the Invention The present invention relates to il1 formula [1] [wherein R is phenyl or pyridyl which may be substituted with alkyl, X is oxygen atom, sulfur atom or methylene, and Y is hydrogen atom or fluorine atom] ] and its salts.

The present invention further provides (2) reacting a metal compound or a salt thereof represented by the general formula [the symbols in the formula have the same meanings as above] with a compound represented by the general formula [wherein Zl represents a halogen atom]. A method for producing a compound represented by the general formula [11] or a salt thereof, characterized by:

(3) A carbonyl compound represented by the general formula %formula%] [wherein Zt and Zs each represent a halogen atom or a nitrogen-containing aromatic 5-membered ring group] and a compound represented by the general formula [rll (or a salt thereof) )
A method for producing a compound represented by general formula [I] or a salt thereof, which comprises reacting with ethylmethylamine (or a salt thereof). .

(4) Compounds represented by the general formula [Symbols X and Y in the formula have the same meanings as above] and the general formula %] (wherein R has the same meanings as above, Q is a halogen atom, alkylsulfonyloxy or aryl A method for producing a compound represented by formula [I] or a salt thereof, which comprises reacting the compound represented by formula [I] with a compound represented by sulfonyloxy.

(5) The present invention relates to a herbicide containing a compound represented by general formula [I] or a salt thereof.

In the above general formula [11(IT)tVI], R is, for example, methyl, ethyl, isopropyl, or n-butyl.

A phenyl group optionally substituted with an alkyl group such as n-hexyl, preferably 1 to 2 times, or a phenyl group optionally substituted with such an alkyl group, preferably 1 to 2 times ( , represents a good pyridyl group.More preferably, R is methyl and 1 is phenyl or 2-pyridyl substituted with lower alkyl such as ethyl.In this case, the number of fractionated alkyl groups is 1 or 2. be.

In the above general formula [■]], 21 is, for example, chlorine.

Indicates halogen atoms such as bromine, iodine, and fluorine.

In the above general formula [IV], Zt and Za are, for example, halogens such as chlorine, bromine, and iodine, triazole,
Indicates a nitrogen-containing aromatic 5-membered ring group such as imidazole, benzotriazole, benzimidazole, pyrazole, etc., and on the ring of the nitrogen-containing aromatic 5-membered ring group, for example, phenyl or a lower alkyl group such as methyl, ethyl, propyl etc. Any number of substitutions may be made. Such compounds [■1
Preferred specific examples include phosgene, '1.1'-carbonyldi(1,2,4-triazole), 1.1'
-carbonyldiimidazole, 1.1'-carbonyldibenzotriazole, 1. l'-Carponylsimitasol, 1. l'-carbonylbis-(3,5-dimethylpyrazole), 1゜1'-carbonyldipyrazole, 1.1'-carbonylbis-(2-methylimitasole), 1゜1'-carbonyldiimidazole, 1.1'-carbonylbis-(2-phenylimitasol)nato.

The halogen atom represented by Q is, for example, chlorine, bromine + iodine, the alkyl of alkylsulfonyloxy is, for example, methyl, ethyl, propyl, etc., and the aryl of arylsulfonyloxy is, for example, phenyl, paratolyl, mesityl, parachlorophenyl, Examples include parabromophenyl.

In the compound of the present invention [11], when R is unsubstituted or alkyl-substituted pyridyl, for example, hydrochloric acid or sulfuric acid.

It may be an acid addition salt with an inorganic acid such as phosphoric acid or an organic acid such as p-1-luenesulfonic acid, formic acid, acetic acid, propionic acid, tartaric acid, malic acid, succinic acid, fumaric acid, etc. (Hereinafter, the compound (1) of the present invention and its salt will be simply referred to as compound CD.) When the compound [I] of the present invention is used as a herbicide, one or more of the compounds [I] may be used for the intended use. dissolved or dispersed in a suitable liquid carrier (e.g. a solvent) and mixed with or adsorbed onto a suitable solid carrier (e.g. diluent/filling agent) and, if necessary, an emulsifier. ,
Suspending agents 9 Adding spreading agents, penetrating agents, wetting agents, mucilage agents, stabilizers, etc., oil agents, emulsions.

It is used in dosage forms such as wettable powders, powders, 9 grains, 9 tablets, sprays, and ointments. These formulations can be prepared by methods known per se.

The content ratio of the active ingredient in the herbicide varies depending on the purpose of use, but for emulsions, wettable powders, etc., it is appropriate to range from 10 to 90% by weight, and for oils, powders, etc., it is 0.1 to 10% by weight.
Approximately 1% to 20% by weight is appropriate for granules.
Although the degree is appropriate, these concentrations may be changed as appropriate depending on the purpose of use. In addition, when using emulsions, hydrating agents, etc., dilute them with water as appropriate (for example, 100 to 100
00 times) and then scattering.

Examples of liquid carriers (solvents) used in herbicides include water, alcohols (such as methyl alcohol, ethyl alcohol, and ethylene glycol), and ketones (
(e.g., acetone, methyl ethyl ketone, etc.), ethers (e.g., dioxane, tetrahydrofuran, Cellsolve, etc.), aliphatic hydrocarbons (e.g., gasoline, kerosene, kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (e.g., benzene, , toluene, xylene, solvent naphtha, methylnaphthalene, etc.), other halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, etc.), acid amides (e.g. dimethylformamide, etc.), esters (e.g. ethyl acetate, butyl acetate ester) .

Suitable solvents include glycerin esters of fatty acids, nitriles (eg, acetonitrile, etc.), and one or a mixture of two or more of these solvents are used. Solid carriers (diluents, bulking agents) include vegetable powders (eg soybean flour, tobacco flour, wheat flour, wood flour, etc.), mineral powders (eg kaolin).

Clays such as bentonite and acid clay, talcs such as talcum powder and waxite powder, silicas such as diatomaceous earth and mica powder, etc.) Furthermore, alumina, sulfur powder, activated carbon, etc. are also used, and one or more of these are used. using a mixture of

Examples of ointment bases include polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate,
For example, cellulose derivatives such as methylcellulose, alginic acid, etc.

Bentonite, higher alcohols, polyhydric alcohols such as glycerin, petrolatum, white petrolatum, liquid paraffin, pig intestine, various vegetable oils, lanolin, dehydrated lanolin,
One or more of hydrogenated oils, waxes, resins, etc., or those containing various surfactants and the like can be selected as appropriate.

In addition, as surfactants used as emulsifiers, spreading agents, penetrating agents and dispersants, soaps, polyoxyalkylaryl esters (e.g. nonal
, manufactured by Takemoto Yushi Ni), alkylumi E salts (e.g., Emar 10■, Emar 40■, manufactured by Kao Atlas), alkyl sulfonates (e.g., Neogen ■, Neogen T■)
, manufactured by Dai-Kogyo Seiyaku; Neoperex ■, manufactured by Kao Atlas KK), polyethylene glycol ethers (e.g.,
Nopole 85■, Nonipole 100■, Nonipole 1
60■, manufactured by Sanyo Kasei KK), polyhydric alcohol esters (eg, Toqueen 20■, Toqueen 80■, manufactured by Kao Atlas Co., Ltd.), and the like.

When compound [1] is used as a herbicide, the amount used is about 1 to 100 y/are of field, more preferably about 2 to 40 y/are of paddy field, and more preferably about 1 to 100 y/are of paddy field. 2-4 (l. Also, compound [11
is suitable for use as a post-emergence treatment agent.

In addition, other types of herbicides may be added to the herbicide containing compound [I],
Plant growth regulators, fungicides (e.g. organochlorine fungicides,
(organic sulfur fungicides, antibiotics, etc.), insecticides (organic phosphorus insecticides, natural insecticides, etc.), other acaricides, nematicides, synergists, attractants, repellents, pigments, lE agents, etc. It is possible to mix and substitute.

The compound [I] of the present invention is, for example, an aniline derivative represented by the general formula [■] or a salt thereof (hereinafter simply compound [11
) and a carbamoyl halide represented by the general formula [111].

This reaction is commonly performed with eg benzene, toluene.

Hydrocarbons such as xylene, ligroin, hexane, ether, isopropyl ether, tetrahydrofuran,
Ethers such as dioxane, ethylene glycol dimethyl ether, and methyl cellosolve; halogenated hydrocarbons such as chloroform, carbon tetrachloride, and methylene chloride; dimethylformamide, dimethyl sulfoxide, and acetonitrile.

It may be carried out in a solvent such as ethyl acetate. These solvents can be used alone or 1. In addition, if necessary, two or more types may be mixed in an appropriate ratio, e.g. 1:1 to 1:1.
They may be mixed at a ratio of 1:1O. When a mixed solvent or the like is used and the mixed solvent is not a homogeneous phase, the reaction may be carried out in the presence of a phase transfer catalyst.

The reaction may be carried out in the presence of a deoxidizing agent. Examples of deoxidizing agents include alkali metal hydrogen carbonates (sodium hydrogen carbonate,
potassium hydrogen carbonate), alkali metal carbonates (sodium carbonate, potassium carbonate, etc.), alkali metal hydroxides (potassium hydroxide, sodium hydroxide, etc.), trimethylamine,
Inorganic and organic bases such as triethylamine, tributylamine, N-methylmorpholine, N-methylpiperidine, N,N-dimethylaniline, pyridine, picoline, lutidine, etc. can also be used. The organic base itself can also be used as a solvent.

The molar ratio of compound [1rll to raw material compound [111] is 0, usually 11, but in some cases one of the raw materials can be used in excess (for example, 1:5 to 5:1).

The reaction is usually carried out under water cooling to 120°C, preferably at 10°C.
It can be carried out at a temperature of ~50°C.

The reaction time can be set appropriately depending on the reaction temperature, but is in the range of several minutes to several tens of hours, preferably 0.5 to 10 hours. Examples of the salts of the compound [rll include salts with inorganic acids such as hydrochloric acid and salts with organic acids such as P-toluenesulfonic acid.

Compound [I] can also be produced by reacting carbonyl compound [■], compound [nl], and ethylmethylamine.

The reaction between carbonyl compound [IV] and compound [rll and ethylmethylamine (or its salt) can be performed using, for example, benzene, toluene, xylene, chloroform, acetonitrile, methylene chloride, tetrahydrofuran, acetone, ethyl acetate, dimethylsulfoxide, dimethylacetamide. , dimethylformamide, hexamethylphosphoramide, etc. alone or in a mixed solvent thereof. The reaction temperature is generally -20 to 40°C, preferably -10 to 20°C. The reaction usually proceeds quickly and is complete in about 0.5 to 3 hours. Typical reaction times are 1 to 2 hours.

Compound [nl] versus carbonyl compound [IV].

It is preferable to use approximately equimolar amount of ethylmethylamine, but it may also be used approximately 1.1 to 2.0 times as much. Further, the reaction may be carried out in the presence of a deoxidizing agent, and as a deoxidizing agent,
For example, triethylamine, tributylamine, N-methylpiperidine, N-methylmorpholine, N,N-
Using organic bases such as dimethylaniline, pyridine, picoline, lutidine, collidine, and inorganic bases such as alkali metal bicarbonates (e.g., sodium bicarbonate, potassium bicarbonate), alkali metal carbonates (e.g., sodium carbonate, potassium carbonate). It's okay.

In this reaction, compound [fT] and compound [ff] first react in a solution to form a compound represented by the general formula [■1 (each symbol in the formula has the same meaning as above) or a salt thereof ( A compound represented by the general formula [■] (symbols in the formula have the same meanings as above) or a salt thereof (hereinafter simply referred to as compound (abbreviated as Vll)) is produced. , then these compounds [■] or/and compounds [■]
is reacted with ethylmethylamine to produce compound [1], and compound [1] and compound 1] may be isolated.

In addition to the method described above, the compound [I] of the present invention can also be produced, for example, by the following method.

That is, a compound represented by the general formula [V711 % formula % [) (symbols in the formula have the same meanings as above) or a salt thereof (hereinafter simply abbreviated as compound [■].) and the general formula [v] (in the formula, Compound [1] can also be obtained by reacting with a compound represented by (X, Y are the same as above, @) or a salt thereof (hereinafter simply referred to as compound EV). The reaction can be carried out using organic solvents such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, methanol, ethanol, impropatol, dimethyl sulfoxide, N-methylformamide, acetonitrile, or water. or in a mixed solvent thereof,
Also pyridine, triethylamine, sodium hydroxide,
This can be carried out in the presence of a deoxidizing agent such as potassium hydroxide, sodium carbonate, potassium carbonate, or the like. The reaction is carried out under cooling, at room temperature, or under heating, and the reaction time varies depending on the reaction temperature and the type of reagent used, but the reaction time is 0.5~
It takes about 10 hours.

The compound [I] or a salt thereof obtained in this way is
Known means such as concentration, vacuum concentration.

It can be isolated and purified by one-fraction distillation, solvent extraction, liquid conversion, dissolution, chromatography, crystallization, recrystallization, etc.

When the compound [[1] is obtained in the form of a free base, it can be converted into the above-mentioned salt, and when the compound [N] is obtained in the form of a salt, it can be converted into the free base according to methods known per se. Compound [rl
Examples of ethylmethylamine include salts with inorganic acids such as hydrochloric acid, and salts with organic acids such as P-toluenesulfonic acid.

All of the raw materials for the method of the present invention can be produced by known methods or methods analogous thereto. Compounds [11] and [Vl are preferably produced by the following manufacturing method (wherein R, is the compound (I
X) or a salt thereof and compound [X] are reacted in the presence of a base, and examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide;
For example, alkali metal carbonates such as sodium carbonate and potassium carbonate, and inorganic bases such as sodium hydride are preferred.

It may also be a mixed base such as soda lime.

This reaction is carried out with hydrocarbons such as benzene, toluene, xylene, hexane, ligroin, ethyl ether,
Ethers such as isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether, halogenated hydrocarbons such as chloroform, carbon tetrachloride, and methylene chloride, amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

It may be carried out in a solvent such as dimethyl sulfoxide, sulfolane, acetonitrile or the like. These solvents can be used alone or, if necessary, two or more kinds can be mixed in an appropriate ratio.

The bases used in reactions using these solvents are hardly soluble in these organic solvents, so the reaction system is often a solid-liquid two-phase system, such as quaternary ammonium compounds and quaternary phosphonium compounds. The reaction can be accelerated by adding a phase transfer catalyst such as.

Moreover, this reaction can also be carried out by a liquid-liquid two-phase reaction between an aqueous solution of a base and an organic solvent. In this case as well, the reaction can be promoted and carried out advantageously by adding a phase transfer catalyst.

Raw material compound [IK] and compound [X] are usually used in a molar ratio close to 1:1, but in some cases one may be used in large excess.

The reaction can usually be carried out under water cooling or at 200°C, but an appropriate reaction temperature is selected depending on the type of compound [X] and base used, the solvent, etc.

The second step is carried out by reducing the compound [■] thus produced according to a method known per se.

For example, the nitro compound [XI] or a salt thereof is reduced using sodium sulfide, hydrazine, etc. in an organic solvent such as ethanol, ethyl acetate, water, or a mixed solvent thereof, reduction with iron, tin, etc. in the presence of an acid, or It is obtained by hydrogenation using a catalyst such as platinum dioxide or palladium. The reaction is carried out under normal pressure or under pressure.
'C to 150°C. After completion of the reaction, the target compound is obtained from the reaction mixture according to a conventional method.

The third step is the compound [XI] obtained by a known method.
Alternatively, the target compound is obtained by reducing the salt thereof according to the same method as the second step.

Examples of the salts of compounds (IX), (XI) and [υ1] include salts with the acids listed above for the salts of compound (1).

The present invention will be explained in more detail by referring to reference examples, test examples, and examples below.

Note that the symbols used in Reference Examples, Examples, etc. have the following meanings.

S, singlet, d, doublet, t, triplet, m, multiplet I qI Calcit Reference Example 1 2-(2-hydroxyethyl)-6-methylbiricine 9
．． 02 and 4-fluoronitrobenzene 8.52 to dichloromethane 100N! Add 0.62% of benzyltriethylammonium chloride to the solution.

Add 7.0y of powdered sodium hydroxide to this mixture for 20 minutes.
Add for 1 minute and stir at room temperature for an additional 4 hours.

Add 50 d of dichloromethane to the reaction mixture and add 100 d of water.
Wash 3 times with The organic layer was dried with anhydrous magnesium sulfate,
The solvent is distilled off. Recrystallization of the residue from isopropyl ether yielded 9.37 (60.0%) of 2-(6-methyl-2-pyridyl)ethyl 4-nitrophenyl ether.

Melting point 54-6℃ NMR (CDCIg) δ: 2.53 (8H, s, CHs) 8.25
(2H, t, CHg) 4.45 (2H, t,
CHg) 6.85-7.13 (4H, m, ArH)
7.53 (IH, t, ArH) 8.07-8.
10 (2H, m, ArH) Reference Example 2 10% (WA') palladium carbon was added to a solution of 2-(6-methyl-2-pyridyl)ethyl 4-nitrophenyl ether 5.2'j dissolved in ethanol 60me. 0.47 is added for catalytic reduction.

After the reaction was completed, the palladium on carbon was removed in an oven and the P solution was concentrated to dryness to obtain 4-(2-(6-methyl-2-pyridyl)ethoxy-1-aniline-4,3-trifluoride (94.2%)).
Melting point 87-8℃ NMR (CDCIs) δ: 2.52 (8H, s, CHs) 3.17
(2H, t, CH2) 4.25 (2H, t,
CH2) 8.31 (2H,s, Nl2) 6.
50-6.86 (4H, m, ArH) 7.01 (2
H, t, ArH) 7.48 (IH, t, ArH) Reference Example 3 ■-(4-nitrophenyl)-1-(4-methylphenyl)-2-flopen-1-one 6.2 quanoacetic acid 60I
10% (v!A) of palladium on carbon is added to the solution dissolved in IIe for catalytic reduction. After the reaction is completed, the palladium on carbon is removed, and the P solution is concentrated to dryness and washed with water. The obtained crystals were purified by silica gel column chromatography (solvent: chloroform) to obtain 4-(8-(4-methylphenyl)furobylcoaniline 4,3).

Melting point 52~4°C NMR (CDCIa) a: 1.50~2.76 (6H, m+(-CH2
-) s ) 2.21 (aH, s, CHa) 3.86
(2H, s, NHHz) 6.15~7.70 (8
H, m, ArH) Example 1 A solution prepared by dissolving 4.5 parts of 4-(2-(4-methylphenyl)ethoxy]aniline in 60 d of dichloromethane
Add 3.97 g of 1.1'-carbonyldiimidazole with stirring at 0-4°C. After stirring the mixture for 30 minutes at 5-10°C, 1.49 g of ethylmethylamine is added gradually. The mixture is stirred under the same conditions for 20 minutes and at room temperature for 30 minutes. The reaction solution was washed three times with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. Recrystallization of the residue from isopropyl ether yields N-ethyl-N
-Methyl-N'-(4-(2-(4-methylphenyl)
Ethoxy]phenyl]urea (compound number 1) 5.29
(85,8%) is obtained. Melting point 107-108.5NM
R (CDCl2) δ: 1.16 (t, all, CIlg) 3.37 (
Q+211, Ctl+) 2.3i(s, all, C
1(a) 2.94(s, 311.N-Cl1s) 2
．． 85-3.17 (m, 211.C112) 4.0
8 (S.

211, CH2) 6.13(s, III, NI
I) 6.67-7.32 (m, 811, Ar
11) Calculated elemental analysis value (%): C73.05: I7.74: N8.9
7 Actual measurement value (%): C72,84+1 (7,70:N8.
74 Example 2 In the same manner as in Example 1, 4-[2-(6-methyl-2-pyridyl)ethoxy 1 aniline 2.1 N-ethyl-
N-Methyl-N'-[4-42-(6-methyl-2-pyridyl)ethoxy]phenyl]urea (compound number 2)
2.2y is obtained.

Melting point 72-a”c NMR (CDCIg) 6: 1.11 (aH,t, C11a), 2.
47(:(II.

S,CIl! +) 2.86 (311,s, CIlg
)3.03~165 (411,m, ClI2)
, 4.26(211,t, CH2) 6.45(
III, s.

Nil) 6.60-7.60 (711, m,
Ar-It.

J'y-11) Elemental analysis value calculation rank 1: c6g, 98: HT, 40: N13.
41 actual measurement value (phrase: C69,05:I7.22:N18
．． 57 Example 3 In the same manner as in Example 1, N-ethyl-
N-Methyl-N'-[4-[2-(5-ethyl-2-pyridyl)ethoxy]phenyl 1-urea (Compound No. 3)
I got 1.2 no.

Melting point 93-4'C N MR (CDC1a) δ 1.00-1.40 (6H, m, Cl0s) 2.6
0 (21+, Q, C112) 2.90 (all, s
.

C11a) 3.00-3.59 (411, m
.

Cll2CII2) 4.25 (211,t, C1h
) 6.19 (111, S, NIL) 6.63~7,
50 (611, m, Ar-II, Py-II) 8.
2y ~8.39 (111,+n, r'y-H) Elemental analysis value calculation value ((6):C69,70:T(7,70:N12
．． 83 actual value (%: C70, 04: H7, 51: N18
．． 01 Example 4 In the same manner as in Example 1, 4-[3-(4-methylthunyl)propyl]aniline 1,9-riyosu, N-ethyl-N
-Methyl-N'-[4-(8-(4-methylphenyl)
0.9 g of propyl]phenyl]urea (compound number 4) was obtained. Melting point 86~? "CNMR (CDC1g) 6: 1.07 (3H,t, J=6.91fz
, (Ila) 1.57-2.12 (2[I, m
) 2.24' (3H, s, Ar-C113)
2.38-2.75 (4'H, m) 2.85 (
3, H, s, C11a) 3.30 (2H, q, J=6
．． 9Hz, NCH2) 6.43 (III, br, s, j
'JI [) 6.72~7.37 (811, m, Ar
tl) Calculated elemental analysis value (a): C77,18, H8,44: ~9.
02 actual measurement value (g): (77,82・H8,58:~8.
85 Example 5 N-ethyl-N-methyl-N'-(8-fluoro-4-
Hydroxyphenyl)urea 1.3,4-methylphenethyl p-toluenesulfonate 1.87 was dissolved in dimethylformamide 5- and potassium carbonate 0.91 was added.
Add and stir at 25-30°C for 3 hours.

The reaction mixture was concentrated to dryness, dissolved in chloroform, and washed three times with water. The organic layer is dried over anhydrous magnesium sulfate, and the solvent is distilled off. The residue was recrystallized from isopropyl ether to give N-ethyl-N-methyl-N'-(3
-Fluoro-4-(2-(4-methylphenyl)ethoxy l phenyl l urea 0.47 (20,0%) (compound no. 5) is obtained.

Melting point 91~2"C Elemental analysis value calculated value (Working: C69,07: H7,02・~8.48 Actual value (%l: C69.10: l-l6.80: ~8
．． 44 Example 6 5 parts of compound number (1), 1 part of polyoxyethylene aryl ether surfactant, and 14 parts of talc were thoroughly ground and mixed to prepare a wettable powder. .

Example 7 Compound No. 100, 200 parts of polyethylene glycol surfactant, and 70 parts of cyclohexanone are combined to form an emulsion.

Example 8 Compound number (1) 5, bentonite 4, clay 5
0! Then, 5 parts of sodium ligninsulfonate are thoroughly ground, water is added and the mixture is thoroughly kneaded, then granulated and dried to form granules.

Test Example 1 Fill a sandy loam soil in a diameter 10 (Ml+) Sihui pot ■ and place it in a pot with sandy loam.

Seeds of white-spotted and soybean were sown separately, covered with soil to a thickness of 0.5 am, and then grown in a greenhouse for 2 to 30 minutes.
When the plants reached the two-leaf stage after 3 weeks of cultivation - Example 7
The chemical prepared according to the method was diluted 100 times with water and treated with a spray gun from above the plant body. 1, Chemical treatment 2
After a week, the phytotoxicity and herbicidal effects of each compound were evaluated according to the following criteria.

The herbicidal effect is expressed using the following index.

Phytotoxicity to crops is expressed using the following index.

(However, the indices O and 1 for crops mean that it is practical for crops.) The results are shown in Table 1.

Table 1 shows that the compounds of the present invention are superior to similar known compounds in herbicidal action and selectivity.

Test Example 2 Pigweed, wild mustard, chickweed, and wheat were each sown separately in a Sihui pot with a diameter of LO cm filled with sandy loam soil, covered with soil to a thickness of 0.5 am, and cultivated in a phylon house for 3 weeks until 2 plants were grown. When the period is reached, Example 7
A chemical solution obtained by diluting the emulsion 100 times with water is applied to the stem E! from the top of the plant using a spray gun. Processed. Three weeks after the chemical treatment, the phytotoxicity and herbicidal effects of each compound were evaluated on the same basis as Test Example 1.

The results are shown in Table 2.

Table 2 shows that the compounds of the present invention have better herbicidal activity and selectivity than similar known compounds.

The urea derivative [1] of the present invention and its salt have excellent herbicidal activity and high selectivity. The present inventors have extensively searched for the herbicidal activity and selectivity of compounds of the formula (wherein R, X and Y have the same meanings as above, and R' is alkyl).
Surprisingly, the compounds of the present invention [N and its salts] exhibited exceptional herbicidal effects and selectivity within the range of compounds of the above formula.

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R is phenyl or pyridyl which may be substituted with alkyl, X is an oxygen atom, sulfur atom or methylene, and Y is A compound represented by [representing a hydrogen atom or a fluorine atom] and its salt.