JPS62185063A - Urea derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 is alkyl or (substituted) 5- or 6-membered heterocyclic group or phenyl; R2 is methyl, difluoromethyl or ethyl; R3 is lower alkyl or lower alkoxy; X is O or S]. EXAMPLE:N'-(4-butoxy-3-methylphenyl)-N,N-dimethylurea. USE:A herbicide having high activity and broad heribicidal spectrum. PREPARATION:The compound of formula I can be produced by reacting the compound of formula II with the compound of formula III (Z is halogen) in a solvent such as benzene, water, etc., at 10-50 deg.C for 0.5-3hr. The reaction is carried out optionally in the presence of an acid acceptor (e.g. sodium bicarbonate). The molar ratio of the compound of formula III to the compound of formula II is 1:1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel urea derivatives useful as herbicides.

Prior Art Conventionally, for example, N'-(3,4-dichlorophenyl)-N
, N-dimethylurea (diuron) and N'-[4-(4
It is well known that urea derivatives such as -10lophenoxy)fenyl]-N,N-dimethylurea (chloroxuron) have herbicidal activity. Also, for example,
The herbicidal power of 4-alkoxyphenylurea derivatives has also been well studied, such as in No. 29755. However, all of these known urea compounds having herbicidal activity have the disadvantage that they require a large amount of drug in practice and are applicable to only a small number of types of weeds. In recent years, energy conservation, safety for humans, animals, and other living things,
Because of various problems such as residue in soil, it is desired that a herbicide with low toxicity, high activity, and a wide herbicidal spectrum be developed.

Problems to be Solved by the Invention As a result of intensive research from these viewpoints, the present inventors have found that the urea derivative [I] of the present invention or its salt, which is defined in detail below, has been disclosed in Japanese Patent Publication No. 46-29755, for example. It was found that this compound has significantly higher activity and a broader herbicidal spectrum than the known compounds described in Japanese Patent Application Publication No. 56-156253.

That is, the present invention provides a urea derivative or a salt thereof that is highly active and has a broad herbicidal spectrum.

Structure of the Invention The present invention is based on the general formula (wherein R4 is an alkyl group, a 5.6-membered heterocyclic group which may have a substituent, or a phenyl group, and R6 is a methyl group, a difluoromethyl group, or an ethyl group). , R8 represents a lower alkyl group or a lower alkoxy group, and X represents an oxygen atom or a sulfur atom) or a salt thereof.

In the formula, the alkyl group represented by RI is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 5e
An optionally branched alkyl group having 1 to 6 carbon atoms such as c-butyl, tert-butyl, pentyl, and hexyl is preferred, and R1 may further be a 5.6-membered heterocyclic group or a phenyl group. As the 5-, 6-membered heterocyclic group, 0. 5~ containing 1~4 heteroatoms selected from S or N
A 6-membered ring, such as pyridyl, N-oxytopyridyl, pyrimidyl, pyridazinyl, N-oxidopyridazinyl, pyrazolyl, thiazolyl, 1,2,3-thiadiazolyl.

1.2.4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, oxacylyl.

Isoxasilyl, benzoxasilyl, benzothiazolyl, chenyl, etc. are frequently used, and 2-pyridyl, 2-chenyl, etc. are most preferred. These 5.6-membered complexes,
The ring group and the phenyl group may further have a substituent, such as methyl, ethyl,
Lower alkyl groups such as n-propyl, isopropyl, n-butyl, 5ec-butyl, tert-butyl, such as methoxy, ethoxy, propoxy, isopropyl,
Examples include lower alkoxy groups such as butoxy, 5eC-butoxy, and tert-butoxy; for example, halogen atoms such as fluorine, chlorine, bromine, and iodine; these substituents may be located at any position on the ring; The number of substitutions is usually 1 to 3. R3 is a lower alkyl group such as methyl, ethyl, propyl, isopropyl, etc.
Indicates lower alkoxy groups such as methoxy, ethoxy, propoxy, and isopropoxy.

The metal compound of the present invention [1] is, for example, an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid, or p-)luenesulfonic acid.

Acid addition salts with organic acids such as formic acid, acetic acid, propionic acid, tartaric acid, malic acid, succinic acid, and fumaric acid may also be used. Such a salt is formed when the compound [I] has a basic group such as pyridyl in the group represented by R1.

Urea derivatives of the present invention [! ] or its salt is obtained by reacting a compound represented by (in the formula, the symbols are R, Rt and (2) General formula PCP' [IV] (wherein, P,
P' each represents a halogen atom or a nitrogen-containing aromatic 5-membered ring group. ) is reacted with a compound represented by the general formula [I [ ], R3 has the same meaning as above), or (3) a compound represented by the general formula Rr CHt CHt Q [■]
(In the formula, R3 has the same meaning as above. Q represents a halogen atom, an alkylsulfonyloxy group, or an arylsulfonyloxy group.) and a compound represented by the general formula and R has the same meaning as above. Manufactured by reaction.

In the above general formula [I[1], Z is, for example, fluorine.

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

In the above general formula [IV], P and P' are, for example, halogens such as chlorine, bromine, and iodine, and triazoles.

Indicates a nitrogen-containing aromatic 5-membered ring group such as imidazole, benzotriazole, benzimidazole, pyrazole, etc., and a lower alkyl group such as phenyl or methyl, ethyl, n-propyl, etc. on the ring of the nitrogen-containing aromatic 5-membered ring group. Any number of groups may be substituted. Such compounds [
(1) Preferred specific examples of phosgene, 1.1
'-Carbonyldi(1,2,4-triazole);
1,1'-carbonyldiimidazole, 1.1'
-carbonyldibenzotriazole, 1.1'-carbonyldibenzimidazole, 1. l'-carbonylbis-(3,5-dimethylpyrazole), t, t
'-carbonylpyrazole, 1,1'-carbonylbis-(2-methylimidazole), l,bicarbonyldiindazole, 1,1'-carbonylbis-(2-phenylindazole), and the like.

In the above general formula (Vl), Q is, for example, chlorine, bromine,
1 halogen atom such as iodine, an alkylsulfonyloxy group such as methanesulfonyloxy, ethanesulfonyloxy, triple-olomethanesulfonyloquine, or an alkylsulfonyloxy group such as benzenesulfonyloxy, p-toluenesulfonyloxy, p-bromobenzenesulfonyloxy, mesitylene Indicates an alkylsulfonyloxy group such as rubonyloxy.

More specifically, the compound [1] of the present invention or a salt thereof is 2
For example, it is produced by reacting an aniline derivative represented by the general formula [I[] with an N,N-disubstituted carbamoyl halide represented by the general formula [I[]. This reaction is generally performed with any hydrocarbon such as benzene, toluene, xylene, ligroin, hexane, ether, isopropyl ether.

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

This may be carried out in a solvent such as ethyl acetate or water. These solvents can be used alone, or if necessary, two or more of them can be used in an appropriate ratio, for example, 1:1.
- You may mix in the ratio of 1:10. 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-methylpiperine, N,N-dimethylaniline, pyridine, picoline, lutidine, etc. can also be used. The organic base itself can also be used as a solvent.

Compound [[[] is usually 1
They are used at a molar ratio of 1, but in some cases one of the raw materials may 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 3 hours.

The compound [I] of the present invention or a salt thereof can also be produced by reacting the carbonyl compound [ff], the compound [ff], and the compound [Vl]. These compounds [IV
], [II] and [Vl may be reacted in any order, but usually compound [IV] and [111 are reacted first, and then compound [Vl] is reacted.

The reaction between carbonyl compound [IV], compound [11], and [Vl] can be performed using, for example, benzene, toluene, or xylene.

The reaction is carried out in an inert organic solvent such as chloroform, acetonitrile, methylene chloride, tetrahydrofuran, acetone, ethyl acetate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, hexamethylphosphoramide, etc. alone or in a mixture thereof. The reaction temperature is generally -20 to 40°C, but -10 to 30°C.
It is preferable to do so. The reaction usually proceeds quickly, approximately 0.5
Complete in ~3 hours. Typical reaction time is 1 to 2 hours.
It's time.

It is preferable to use approximately equivalent mole of compound [■] and compound [V] to carbonyl compound [IV], but 1.1 to 2
．． There is no problem even if it is used about 0 times. The reaction may also be carried out in the presence of a deoxidizing agent, such as triethylamine, tri-n-butylamine, N-methylpiperidine, N-methylmorpholine.

Organic bases such as N,N-dimethylaniline, pyridine, picoline, lutidine, collidine, etc., such as alkali metal bicarbonates (e.g., sodium bicarbonate, potassium bicarbonate), alkali metal carbonates (e.g., sodium carbonate, potassium carbonate), etc. Inorganic bases may also be used.

In addition, in this reaction, [11
and [IV] react to form a compound represented by the general formula [■] (the symbols in the formula have the same meanings as above) or/and a compound represented by the general formula [IX] (the symbols in the formula have the same meanings as above). The compound [■] and [IX] are then reacted with [V] to produce 'c[I], and [■] and [IX]
] may be performed in isolation.

Furthermore, the present compound [11 or a salt thereof is a compound [V
It can also be synthesized by reacting compound [I] with compound [■]. The reaction involves benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl.

Ether, methylene chloride, chloroform, carbon tetrachloride,
The reaction is carried out in an organic solvent such as ethyl acetate, methanol, ethanol, isopropanol, dimethyl sulfoxide, dimethyl formamide, acetonitrile, water, or a mixed solvent thereof. The reaction can be carried out in the presence of a deoxidizing agent.

Examples of deoxidizers include organic bases such as pyridine, collidine, triethylamine, N,N-dimethylaniline, 1,8-2 azabicyclo[5,4,01-7-undecene, and sodium hydroxide, potassium hydroxide, and carbonate. Inorganic bases such as sodium and potassium carbonate can also be used. The organic base itself can also be used as a solvent.

The ratio of compound [VI] and compound [■] is usually about 1:1.
It is used in a molar ratio of , but in some cases one is used in excess (
For example, 1:2 to 2:l) can also be used.

The reaction temperature is generally between 0°C and 200°C, preferably between 10 and 100°C.

The reaction time varies depending on the reaction temperature and the type of reagent used, but is in the range of several minutes to several tens of hours, preferably 0.5 to IO hours.

In addition to the above-described method, the compound [11 or a salt thereof of the present invention] can also be produced, for example, by the following method.

That is, the method involves a methylation reaction of an N'-substituted phenyl-N-hydroxyurea derivative represented by the general formula [X] (wherein R+, R*, and X have the same meanings as above). Examples of methylating agents include methyl iodide, dimethyl sulfate, and para-toluenesulfonic acid methyl ester. The reaction is benzene, toluene, xylene, methanol,
The reaction can be carried out in an organic solvent such as ethanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, dimethyl formamide, dimethyl sulfoxide, dichloromethane, chloroform, water, or a mixed solvent thereof. Further, the reaction may be carried out in the presence of a deoxidizing agent, and the reaction is easily carried out using an organic base such as pyridine or an inorganic base such as potassium carbonate, sodium hydroxide, potassium hydroxide, etc. as the deoxidizing agent. It will be done.

The reaction is carried out under cooling, at room temperature, or by heating. The reaction time varies depending on the reaction temperature and the type of reagent used, but is approximately 0.5 to 10 hours.

When the urea derivative [1] thus obtained is a free compound, it can be converted into an acid addition salt, and when it is obtained as an acid addition salt, it can be converted into a free compound according to a conventional method.

Compound [1] or a salt thereof obtained in this manner can be obtained by known means such as concentration, vacuum concentration, one-fraction distillation, solvent extraction, liquid conversion, dissolution, and chromatography.

It can be isolated and purified by crystallization, recrystallization, etc.

Compound used as raw material for the method of the present invention [11]
All of these compounds are undocumented and can be produced by the following production method. A preferred raw material production method is summarized in the following reaction formula.

[■ Co and the general formula ['1
1] in the presence of a base. The compounds of general formula [XI[[] obtained here are all compounds that have not been described in any literature. In the above general formula [XII, Z' represents a halogen atom such as fluorine, chlorine, bromine, or iodine.

Examples of the base used include sodium hydroxide,
Alkali metal hydroxide such as potassium hydroxide 1 Alkali metal carbonate such as sodium carbonate, potassium carbonate, etc.
Inorganic bases such as sodium hydride are preferred. It may also be a mixed base such as soda lime.

This reaction is effective for example with benzene, toluene, and xylene.

Hydrocarbons such as hexane and ligroin, ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether, chloroform, and carbon tetrachloride.

The reaction may be carried out in a solvent such as a halogenated hydrocarbon such as methylene chloride, an amide such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, or acetonitrile. These solvents can be used alone, or two or more of them can be used as a mixture in an appropriate ratio, if necessary.

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.

The raw material compounds [XII and [Xl] are usually used in a molar ratio close to 1:1, but one may be used in large excess depending on the case.

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

In addition, compound [XII[] can be prepared by the general formula [■
It can also be synthesized by reacting a compound of formula [XIV] with a compound of formula [XIV].

The reaction is benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform,
Organic solvents such as carbon tetrachloride, ethyl acetate, methanol, ethanol, isopropanol, dimedyl sulfoxide, N-methylformamide, acetonitrile, or
The reaction can be carried out in water or a mixed solvent thereof, or in the presence of a deoxidizing agent such as pyridine, toluethylamine, sodium hydroxide, 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 between 0°5 and 10°C.
It takes about an hour.

Step C is carried out by reducing the compound [XII[] thus produced according to a method known per se.

For example, the nitro compound [X [[] is ethanol.

Iron is reduced using sodium sulfide, hydrazine, cyclohexene, etc. in an organic solvent such as ethyl acetate, water, or a mixed solvent thereof, or in the presence of an acid.

It can be obtained by reduction with tin or the like or by hydrogenation using a catalyst such as platinum dioxide or palladium. The reaction is carried out at 0°C to 150°C under normal pressure or increased pressure.

Further, the compound [■] can be directly obtained by reacting the compound [■] with the compound represented by the general formula [χ■] in step D.

The reaction is benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform,
Organic solvents such as carbon tetrachloride, ethyl acetate, methanol, ethanol, isopropanol, dimedyl sulfoxide, N-methylformamide, acetonitrile, or
The reaction can be carried out in water or a mixed solvent thereof, or in the presence of a deoxidizing agent such as pyridine, toluethylamine, sodium hydroxide, 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 is
, although it varies depending on the temperature and type of reagent used, 0°5
~10 hours.

Compound [■] is also used as a raw material compound in the method of the present invention. Compound [■] is a compound that has not been described in any literature, and can be produced by the following production method. A preferred manufacturing method is as follows.

(In the formula, Rs represents hydrogen or a protecting group that can be converted into hydrogen. The other symbols have the same meanings as above.) Step C and Step F are the synthesis of the present compound [11] from the aniline derivative [■]. You can proceed in the same way as . Here, R6 is a group that can be converted into any hydrogen, such as hydrogen or a known protecting group for phenol or thiophenol, such as methyl.

Methyl 4-rethiomethyl, 2-methoxyethoxymethyl.

Tetrahydropyranyl, tert-butyl, benzyl.

Substituted alkyl groups such as 4-picolyl, substituted silyl groups such as trimethylsilyl and lert-butyldimethylsilyl, acyl groups such as acetylpivaloyl and benzoyl,
methoxycarbonyl, tert-butoxycarbonyl,
Alkoxycarbonyl groups such as benzyloxycarbonyl, carbamoyl groups such as N-ethylcarbamoyl and N-methoxymethylcarbamoyl, methanesulfonyl, p
-Sulfonyl groups such as toluenesulfonyl, sulfo groups (
or esters and salts thereof), cyano groups, etc.

The compound [X■] obtained above was obtained by step C.
The compound of the general formula [■] can be prepared by a method known per se according to R6, such as acid hydrolysis, alkaline hydrolysis, neutral hydrolysis, various reductions, various oxidations, electrolysis, various catalysts, etc., or a combination thereof. can lead to compounds. R
When 6 is hydrogen, step C is not necessary.

After completion of either reaction, the target compound is obtained from the reaction mixture according to a conventional method. In the above production method, formulas [■, [X], [XIII], [XV, etc.] may be acid addition salts of the compounds described in formula [I].

When the compound [1] of the present invention or a salt thereof is used as a herbicide, one or more of the compound [I] or a salt thereof is used in a suitable liquid carrier (for example, a solvent) depending on the purpose of use.
It is dissolved or dispersed in a suitable solid carrier (for example, a diluent/filling agent) or adsorbed thereon, and if necessary, an emulsifying agent, suspending agent, or spreading agent is added thereto.

Penetrating agents, wetting agents, mucilage agents, stabilizers, etc. are added, and oil agents,
It is used in dosage forms such as emulsions, wettable powders, powders (9 grains/1 tablet), sprays, and ointments. These formulations can be prepared by methods known per se.

The content ratio of the active ingredient in herbicides varies depending on the purpose of use, but for emulsions, wettable powders, etc., it is appropriate to range from 10 to 90%, and for oils, powders, etc., it is 0.1-10%.
Approximately 1% to 20% by weight is appropriate for granules.
These concentrations may be changed as appropriate depending on the purpose of use.

Note that emulsions, hydrating agents, and the like are preferably diluted with water or the like at the time of use (for example, 100 to 10,000 times) and then dispersed.

Liquid carriers (solvents) used in herbicides include, for example, water, alcohols (such as methyl alcohol, ethylene glycol, etc.), and ketones (
acetone, methyl ethyl ketone, etc.), ethers (e.g. dioxane, tetrahydrofuran, cellosolve, 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) , glycerin esters of fatty acids, etc.), nitriles (eg, acetonitrile, etc.), and one or a mixture of two or more of these are used. Solid support (dilution,
As fillers), vegetable powders (for example, soybean flour, tobacco flour) are used.

flour, wood flour, etc.), mineral powders (e.g. 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. Use a mixture.

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, sodium alginate.

Bentonite, higher alcohols, polyhydric alcohols such as glycerin, petrolatum, white petrolatum.

Liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, li! One or more of fossil oils, waxes, resins, etc., or mixtures thereof with various surfactants and the like can be appropriately selected.

In addition, as surfactants used as emulsifiers, spreading agents, penetrating agents and dispersants, soaps, polyoxyalkylaryl esters (e.g. nonal
(manufactured by Takemoto Yushi KK), alkyl sulfates (e.g. Emar 10.K-L 40O).

■ Manufactured by Kao Atlas KK), alkyl sulfonates (e.g., Neogen ■, Neogen T ■, manufactured by Daiichi Kogyo Seiyaku KK;
Neoperex ■, manufactured by Kao Atlas KK).

Polyethylene glycol ethers (e.g. Nonibo)
0 1/I/85, /Hubo J, lOO, /-Po/1
z160■, manufactured by Sanyo Kasei KK), polyhydric alcohol esters (eg, Tween 20■, Tween 800, manufactured by Kao Atlas KK), etc. are used.

When compound [1] or a salt thereof is used as a herbicide, the amount used is about 0.1 to 50 g, more preferably about 0.5 to 20 g per are. Compound [I] or a salt thereof is generally more effective when used as a post-emergence treatment agent.

Additionally, in addition to herbicides containing compound [1] or its salts, other types of herbicides, plant growth regulators, fungicides (e.g., organochlorine fungicides, organic sulfur fungicides, antibiotics, etc.), and insecticides ( Organophosphorus insecticides, natural insecticides, etc.) Other acaricides, nematicides, synergists, attractants, repellents, dyes, fertilizers, etc. can be mixed and used.

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 and Examples have the following meanings.

S, singlet; d, doublet; t, triplet; q, caltite; m, multiplet; Me, methyl; "Pr, n-propyl; 'Pr, isopropyl,
Ph, phenyl; Et, ethyl; OMe, 0C
Hs, Bu, n-butyl Reference example 1 n-butyl alcohol 2.20g, 2-fluoro-
Dissolve 4.7 g of 5-nitrotoluene and OJg of benzyltriethylammonium chloride in 50 ml of dichloromethane, and add 4.5 g of powdered sodium hydroxide in three portions every 30 minutes at 15-20°C while stirring. .

After further stirring at room temperature for 2 hours, the reaction solution was filtered.
Wash the filtrate with water. Dry over anhydrous magnesium sulfate, concentrate, and distill the resulting liquid under reduced pressure to obtain 2-butoxy-5-
5.5 g of nitrotoluene is obtained. boiling point 134-5℃10
．． 3nonl1g, NMR (CDC1,) δppm;
0.80-1.84 (7H, m, CH*CHzCH
t), 2°14 (3H, s, Ph-C1,), 3.
94 (2H, t, J=7.5Hz, CI], O), 6
゜64 (IH, m, Ph-H), 7.85 (2H, m
, Ph-H) Elemental analysis Calculated value (%) as C1, H4, NO5 C: 63.14 H near, 23
N: 6.69 Actual value (%) C: 63.36 i (near, OI) N: 6.62 The following compound was produced in the same manner as this reference example.

Table - RI R1X Physical constants Me Me O (liquid) (Note) "Pr
Me O74 points 155-160℃/2mdg'
Pr Me O boiling point 158℃/2 Dragon ■ gM
e.

Et CHF, O boiling point 131-3℃/(j
, 35+aa+, Hg”Pr CHFz
O boiling point 135-8℃ 10.2+n+aHgMe
Me S boiling point 138℃ 10.9n+m
HgEt Me 3 boiling point 149°C
70.9mm 1g, melting point 45-7℃ (Note) NMR
(CC14) δppm: 1.01 (3H, t, J=
7Hz).

1.45-2.0 (2H, m), 2.12 (3H, s
), 3.84 (211, t.

J=611z), 6.45-6.83(II(,m)
, 7.6 (1 to 7.85 (2H, m) Reference Example 2, 7.6 g of n-propyl iodide, 5.0 g of 2-ethyl-4-ditrophenol, 6.2 g of anhydrous potassium carbonate, dimethylformamide Stir 40ml of the mixture at room temperature for 7 hours, then pour into 150ml of water.
Extract twice and wash the organic layer with water. After drying over anhydrous magnesium sulfate, concentrate and distill the residue under reduced pressure! -5.9 g of ethyl-2-propoxy-4-nitrobenzene are obtained.

Boiling point 123-5℃10.7II1mHgElemental analysis Ci
+ Calculated value as HIs N O3 (%') C:
63.14 H near, 23 N: 6.69 actual value (
%") C: 83.22 H: 6.98 N: 6
．． 55 Reference Example 3 In the same manner as Reference Example 2, 6.2 g of n-butyl bromide, 2-
From 5.0 g of ethyl-4-nitrophenol and 6.2 g of anhydrous potassium carbonate, 2-butoxy-1-ethyl-4-
Obtain 6.0 g of nitrobenzene. Boiling point 122-4℃70
゜mm1g Reference Example 4 In the same manner as Reference Example 2, n-pentyl bromide 5,... 5g
.

6.3 g of 1-ethyl-2-pentyloxy-4-nitrobenzene was obtained from 5.0 g of 2-ethyl-4-ditrophenol and 6.2 g of anhydrous potassium carbonate. boiling point 132-7
6C10,7mmHg Reference Example 5 A mixture of 2.7 g of 2-ethyl-4-nitrophenol, 2.4 g of anhydrous potassium carbonate, and 25 ml of dimethylformamide was heated to 70°C, and while stirring, 2-
A solution of 4.2 g of (6-methyl-2-pyridyl)ethyl p-toluenesulfonate dissolved in 15 ml of dimethylformamide is added dropwise over 1 hour.

After further stirring at 70°C for 1 hour, the mixture was poured into 40 h of water and the precipitate formed was collected by filtration. After air drying, 2-ethyl-1-
[2-(6-methyl-2-pyridyl)ethoxy]-4-
3.2 g of nitrobenzene are obtained. Melting point 71.5-72.
Elemental analysis CIeHteN at 5°C (recrystallized from hexane)
Calculated value as tOs (%) C: 67.12 H
:6J4 N :9.78 Actual value (%) C:66
．． 89 H: 6.22 N: 9.82 Reference Example 6 In the same manner as Reference Example 5, 2-ethyl-1-[2-(5-
Ethyl-2-pyrinol)ethoxy]-4-nitrobenzene is obtained. Melting point: 48°C (recrystallized from hexane) Reference Example 7 In the same manner as Reference Example 5, 2-ethyl-1-(p-phenethyloxy)-4-nitrobenzene was obtained.

NMR(CDC13)δI)Pm; 1.10
(38,t, J=7Hz), 2゜21(3H,s),
2.53 (211, qj=711z), 2.97 (
211,tj=711z), 4.06(2H,t,J
=7Hz), 6.5 to 6.7 (ill, m), 6°90 (4H, s), 7.65 to 7.90 (2H, m)
Reference Example 8 Dissolve 4.8 g of 2-butoxy-5-nitrotoluene in 50n+1 ethanol and add 0.5 g of 10% palladium on carbon.
(manufactured by Mitsuwa Chemicals) and hydrogenate at room temperature and pressure. After the reaction is completed, the catalyst is filtered off, the solvent is distilled off under reduced pressure, and the residue is distilled under reduced pressure to obtain 3.9 g of 4-butoxy-3-methylaniline. Boiling point 109-112℃ 10.71
11 mHg NMR (CD CIs) δppm; 0.7-1
．． 8 (7H, m), 2.03 (3H, s), 3.1
0 (211, wide s), 3.70 (2H, t, J=
611z), 6.1-6.55 (3H, m) Elemental analysis CIIHl? Calculated value as N O (%) C near 3.70 H: 9.56 N near, 81 Actual value (%) C near 3.68 H: 9.
61 N Near, 81 The following compound is obtained in the same manner as in this reference example.

Second Table Rt R1X Physical constant Me Me O boiling point 88-90℃10.2
mmHgnPr Me O boiling point 123℃1
0.6mm11g'Pr Me O boiling point 1
06℃10.4mmHgPh MeO melting point 32-3℃e Et CHP, O boiling point 111-3℃70.
3 cities HgnPr CHFz O boiling point 125-6
10.25mmml1gEt Et O Boiling point 100-110.4mmHgnPr Et
O boiling point 119-2110.9mmHgMebe>E
t OC liquid) (Note 2) Me EtQEt o <liquid) (Note 4) (Note 1) NMR (CDCIs) δl) I) m; 1.99
(38,s), 2゜17(3H,S), 2.38(
3H,s), 3.04(2H,s), 3.07(2
H, t), 4.04 (2H, t), 6.05-6.
8 (5H, m) (Note 2) NMR (CD CI3)
δppm; 1.03 (3H, t), 2°18 (3
H,s), 2.38(2H,Q), 2.84(2
+1. t), 3.00 (211, s), 3.86 (
21Lt), 5.9~6.5 (3H, m), 6°8
7(4H,s) (Note 3) NMR(CDCls)δppm;
1.05 (3H, t), 2゜25~2.7 (511,
n+), 3.15 (2H, t), 3.35 (2B,
s).

4.13 (2H, t), 6.2-7.05 (58, m
), 7.37 (11,t) (Note 4) NMR (CDC1
3) δppm; 0.9-1.4 (6H, i+).

2.2-2.8 (4H, +n), 3.12 (2H, t
), 3.66 (2H, s).

4.13 (2H, t), 6.15-6.65 (30,
+e), 6.9-7.4 (2H, m), 8.2-8
．． 3(LH,m) Reference Example 9 2-ethyl-4-nitro-1-propoxybenzene 5g
, 10g of cyclohexene, 2g of 10% palladium on carbon,
A mixture of 5 hl of ethanol is heated under reflux and stirred for 1 hour. After filtering off the catalyst and concentrating the solvent etc. under reduced pressure,
Distillation under reduced pressure yields 3.5 g of 3-ethyl-4-propoxyaniline. Boiling point: 102-3°C/1.0 mml (g Reference Example 10 0.2 g of hydrochloric acid was added dropwise to a mixture of 6.7 g of reducing iron powder (manufactured by Wako Pure Chemical Industries) and 40 ml of water, and heated and stirred at 50°C for 20 minutes. Add 4.2 g of 5-nitro-2-(propylthio)toluene to the reaction mixture, and raise the temperature to 90-10
The temperature was raised to 0°C, heated and stirred for 2 hours, then returned to room temperature, sodium hydrogen carbonate o and ag were added, and insoluble matter was filtered off. Insoluble matter is washed with chloroform, the filtrate and washing liquid are combined, and the organic layer is separated. Extract the aqueous layer with chloroform,
All organic layers are dried over anhydrous magnesium sulfate and then concentrated. The residue was distilled under reduced pressure to obtain a,og 3-methyl-4
-(Propylthio)aniline is obtained. boiling point 112℃10
．． 5 mmHgReference Example 11 4-(Butylthio)-3-methylaniline is obtained in the same manner as in Reference Example 1O. Boiling point: 117°C, 10.5 mmHg Reference Example 12: 5.6 g of 4-amino-2-methylthiophenol.

8.5 g of n-propyl iodide, 6.9 g of anhydrous potassium carbonate
g.

After stirring a mixture of 100 ml of acetonitrile at room temperature for 5 hours, the reaction solution was concentrated under reduced pressure and dichloromethane 100+
nl, 100 ml of water are added and the organic layer is separated. The organic layer is washed with water, dried over anhydrous magnesium sulfate, and concentrated. The residue was purified by column chromatography on silica gel (manufactured by Merck & Co., Kieselgel 60.70-230 mesh, developing solvent dichloromethane-ethyl acetate tO:1), and 6.7 g of 3-methyl-4-(propylthio)aniline was purified.
get. Boiling point 112℃ 10.5ea + Hg elemental analysis C
loH+sN Calculated value as S (%') C: 66.25 H: 8.34
N near, 73 actual value (%) C: 66.57 H: 8
．． 41 N Near, 86 Reference Example 13 In the same manner as Reference Example 12, 3.1 g of 4-amino-2-ethyldiophenol, 3.7 g of n-propyl iodide, 3.0 g of anhydrous potassium carbonate, and 50 m of dimethylformamide were prepared.
1, 3-ethyl-4-(propylthio)aniline 1
．． Obtain 2g.

NMR (CDC13) δppm: 0.7-1.85
(8H, m), 2.5-2.95 (41Lm):
(, 55 (211, wide s), 6.25-6.55
(211, m), 7.0 to 7.25 (LH, m) Reference Example 14 In the same manner as Reference Example 12, 3.1 g of 4-amino-2-ethylthiophenol, p-methylphenethyl p-)luene Sulfonate 6.4g, anhydrous potassium carbonate 3.0g
, 3-ethyl-4 from 50 ml of dimethylformamide
-[2-(p-tolyl)ethylthiocoaniline 2.6g
get.

NMR(CDCls)δI)pI; 1.15
(3H, t), 2.25 (3H.

s), 2.5-3.0 (6H, m), 3.43 (2
H, wide s), 6.3-6.55 (2H, m),
6.9-7.3 (5H, m) Reference Example 15 4-amino-2-methylphenyl thiocyanate 32
．． In a solution of 8g dissolved in 500ml dichloromethane,
While stirring at -tS to -7°C, add 39.0 g of 1,1'-carbonyldiimidazole over 10 minutes. After stirring this mixture at 25-30°C for 40 minutes,
Cool to 10-15°C, add 21.6 g of 50% dimethylamine aqueous solution over 5 minutes, and stir at 25-30°C for 2 hours. The reaction solution was washed with water, dried over anhydrous magnesium sulfate, and concentrated to dryness. The residue was recrystallized from ethyl acetate to obtain 38.5 g of N,N-dimethyl-N'-(3-methyl-4-thiocyanatophenyl)urea. Melting point 151
~2°C Reference Example 16 Same as Reference Example 15, 32.8 g of 4-amino-2-methylphenyl thiocyanate, 1. Becarbonyldiimidazole 39.0g, methoxymethylamine 1
From 4.7 g, N-methoxy-N-methyl-N'-(3-
Methyl-4-thiocyanatophenyl)urea 31.2g
get. Melting point: 83-4°C Reference Example 17 40.0 g of sodium sulfide nonahydrate is dissolved in 400 ml. This was treated with N at 10-15°C in a nitrogen stream.

A solution of 32.9 g of N-dimethyl-N'-(3-methyl-4-thiocyanatophenyl)urea in 250 ml of dimethylformamide is added dropwise over 1 hour with stirring. After stirring for another hour at 15-20°C, adjust the pl to 4 with concentrated hydrochloric acid, and add dichloromethane to 50
Add 0ml and filter off insoluble matter.

Separate the organic layer from the filtrate, extract the aqueous layer with dichloromethane, combine with the organic layer, and wash with water. After drying over anhydrous magnesium sulfate, it was concentrated to dryness to give N,N-dimethyl-N'
-(3-methyl-4-mercaptophenyl)urea 23
．． Obtain 9g. Melting point: 137-8°C Reference Example 18 In the same manner as Reference Example I7, N-methquin-N-methyl-N
'-(3-methyl-4-mercaptophenyl)urea is obtained. Melting point 59-60°C Example 1 2.0g of 1.1'-carbonyldiimidazole was added to 20m
The solution of 1 in dichloromethane is cooled to -10 to -5°C. To this, 4-butoxy-3-methylaniline 1
．． Add 8 g of dichloromethane (5 ml) dropwise over 10 minutes while stirring and maintaining the above temperature. After stirring at 15-20°C for 30 minutes, add 50% dimethylamine aqueous solution l at 10-15°C.

Drop 4g over 2 minutes. Thereafter, after stirring for 1 hour at 15-20°C, the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was reconstituted with isopropyl ether to obtain 2.2 g of ML, N'-(4-butoxy-3-methylphenyl)-N,N-dimethylurea (compound No. 6). Melting point 11G-
1'c Elemental analysis Calculated value (%) as Ct4Ht*f'LOt
C: 67.17 H: 8.86 N: 11.1
9 Actual measurement value (%) C: 67.17 H: 8.76
N: 11.16NMR (CDCl2) δppm:
0.8-1.9 (7H, m), 2.09 (3H, s)
, 2.86 (6H, s), 3.79 (2H, t, J
=6Hz), 6.25 (LH, wide s), 6.
4-6.65 (1B, m), 6.8-7.1 (2H,
m) Example 2 Same as Example 1, 2.0 g of 1,1'-carbonyldiimidazole and 1.8 g of 4-butoxy-3-methylaniline.
After reacting, methoxymethylamine hydrochloride 1.5
Add 1.5 g of triethylamine over 2 minutes while cooling to 10-15°C.
After further stirring at ℃ for 1 hour, the same post-treatment was carried out to obtain
N-methoxy-N-methylurea (compound No. 7
) 2.4g? I.

Elemental analysis Calculated value as CI4HttN to 3 (%
) C: 63.14 H: 8.33 N: 10.5
2 Actual measurement value (%) C: 63.06 H: 8.14
N: lO, 2ON M R (CD C13) δpp
m: 0.8-1.9 (711, m), 2.20 (
3Ls), 3.14 (311,s), 3.69 (3
11, s), 3.88 (211, t.

J=6Hz), 6.5-6.75 (LH, m), 7
．． 0-7.3 (2H, m).

7.44 (IH, wide S) The following compounds were produced in the same manner as in Example 2 above.

Third Table O Compound No., R+' Rt R3X
Melting point ('C)l Me Me Me 0 126
-72 Me Me OMe O61-23Me
Me Me S 98-94 Me Me 0
1le S 42-35 Me Me Et S
105-66 Et Me Me 0 110
-17 Et Me OMe
O syrup type (attached table) 8 Et Me
Me S 85-69 E
t Me OMe S Jiro, pu form (attached table) 10 Pr Me Me
O111-211nPr Me OMe
Ojiro 7-shaped (attached table) 12 iPr
Me Me O102-3-13Ph
Me Me O115-6A 15 Me Et Me
O13G-216Me Et OMe
O Jiro 7-shaped (attached table) 17 Me E
t Me S 125-618
Et Et Me O122-
3,519Pr Et Me O1
12-620”Pr Et OMe O Jiro 7-shaped (attached table) 21 Me()-Et M
e o ge-g22 Me-Q-
Et OMe o Jiro) (separate table)
23 Me()-EtMeS
109-1024 Me()-Et OM
e S 61-225 M, Cal Et
MeO102-3,526MeQEt
OMe o Syrup (attached table) tQ 29 Et OMe O syrup (attached table) 30 Et CHFg
translation 0 72.5-3.531
Et CHPz OMe O syrup (
Separate table) 32 nPr CHFt Me
O75-633”Pr CHFg OMe
O syrup form (attached table) Table Example 3 N,N-dimethyl-N'-(3-methyl-4-mercaptophenyl)urea 2.1 g, anhydrous potassium carbonate 1.5
1.8 g of n-aluminum bromide was added dropwise over 1 minute to a mixture of 30 ml of acetone and stirred, and the mixture was stirred at 15 to 20° C. for 6 hours. After removing insoluble matter by filtration, the filtrate was concentrated and dichloromethane (50ml) was added. Add 50 ml of water and separate the organic layer. The aqueous layer is extracted with dichloromethane, combined with the organic layer, and washed with water. After drying over anhydrous magnesium sulfate and concentrating, the residue was recrystallized from isopropyl ether to give N.

N-dimethyl-N'-[3-methyl-4-(pentylthio)phenyl]urea (compound No. 34) 1.4
get g. Melting point 86-7℃ ・Elemental analysis CIsHt4N As lOS ゛Calculated value (%) C: 64.25 H: 8.63 N
:9.99 Actual value (%) C:64.21 H:
8.66 N:lO, 16NMR (CDC13) δ
ppm: 0.63-1.02 (3H, m), 1°08-1.87 (61, m), 2.27 (3H, s)
, 2.72 (2+1.t), 2゜88 (6H,s)
, 6.38 (IIl, wide s), 7.0'O~7
．． 20 (3H.

m) The following compounds were produced in the same manner as in Example 3.

Fourth surface compound No., Rt Rt R3X
Melting point (°C) 35 CsH++ Me
MeS 84-536
CsH+t Me OMe S
Syrup (Note) 37Me()-Me OMe S
94-5 (Note) NMR (CD CI!l
) δI)I)m: 0r65-1.0L (3H.

m), 1.08-1.89 (6H, m), 2.
28 (3H, s), 2.71 (2H.

t), 3.05 (3H, s), 3.60 (3H,
s), 7.05 (3H, s), 7°46 (IH,
S) Example 4 25 g of Compound No. (2), 5 g of polyoxyethylene aryl ether surfactant, and 70 g of talc are thoroughly ground and mixed to prepare a wettable powder.

Example 5 Compound No. (2) log, 20 g of polyethylene glycol ether surfactant, and 70 g of ncrohexanone were mixed to form an emulsion.

Example 6 5 g of Compound No. (3), 40 g of bentonite, 50 g of clay, and 5 g of sodium ligninsulfonate were thoroughly ground and mixed, water was added, the mixture was thoroughly kneaded, and the mixture was granulated and dried to obtain granules.

Test Example 1 Fill a 10 cm diameter Shifuibot ■ with sandy loam soil, sow Aobiyu, Pigweed, Ichibi, Maruba morning glory, Japanese fir, and Shirobanachi morning glory separately, and spread them to a thickness of 0.5 cm in a greenhouse with a soil covering machine for 2 to 30 minutes. After cultivation for 3 weeks, when the plants reached the two-leaf stage, the chemicals prepared according to Example 4 or Example 5 were diluted as necessary and treated with a spray gun from above the plants. Two weeks after the chemical treatment, the herbicidal effect of each compound was evaluated according to the following criteria.

The herbicidal effect is expressed using the following index.

The results are shown in Table 5.

Table 5 Control Compound The above results show that the compound of the present invention has a superior effect to similar known compounds.

Test Example 2 Fill a 10cm diameter Jiffybo soil with sandy loam, sow pigweed, wild oak, and chickweed separately, cover with soil to a thickness of 0.5cm, and then place in a phylon house for 2 hours.
After cultivation for ~3 weeks, when the plants reached the two-leaf stage, the leaves were treated with a chemical solution containing a predetermined amount of the drug from above the plants using a spray gun in the same manner as in Test Example 1. Three weeks after the chemical treatment, the herbicidal effect of each compound was evaluated using the same criteria as Test Example 1.

The method for preparing the drug solution was the same as in Test Example 1. The results are shown in Table 6.

From the results shown in Table 6 and above, it is clear that the compounds of the present invention have superior effects to similar known compounds.

Effect of the invention The urea derivative or its salt of the present invention has high activity and can be used in a wide range of procedures.
Amendment (Own ship February 21, 1986 1, case description zo/-0) ro Flo Showa 6 Hayabusa 2, name of invention urea derivative 3, person making the amendment Relationship to the case Patent applicant address 2-27 Doshomachi, Higashi-ku, Osaka City Name (29
3) Takeda Pharmaceutical Co., Ltd. Representative: Iku Kurabayashi, Department 4, Agent address: 2-17-85 Jusohonmachi, Yodoyo-ku, Osaka City, Issue 6, Contents of amendment (1) Page 6 of the specification, 2 from the bottom Correct "symbols R2 and RsJ in lines 3 to "symbols R t , R * and X".

(2) “Imidazole, 1,l'-
" is corrected to [imidazole, 1.1'-J.

(3) "Pyrazole), 1.1'carbonylpyra" on page 7, line 16 of the same book is corrected to "pyrazole), 1.1'carbonyldipyra".

(4) In the same book, page 8, line 15, "hexane nido" is corrected to "hexane, etc."

(5) "Toruechi" on page 19, line 2 and page 20, line 9 of the same book is corrected to "Toriechi."

(6) "Acetyl pivaloyl" in the first line of page 22 of the same book is corrected to "acetyl, pivaloyl."

(7) “From 0.1 to 50g” on page 26, line 1θ of the same book
is corrected to [from 0.1-50g1].

(8) Line 11 of the table on page 34 of the same book correct.

(9) r40, page 39, line 12 of the same book. og 400m
Q J r40. Correct Og to 400m of water (!j.

(10) In the second line from the bottom of page 52 of the same book, “sterilization” is replaced with “weed killing”
Correct.

that's all

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼
represents a methyl group, difluoromethyl group or ethyl group, R
_3 represents a lower alkyl group or a lower alkoxy group, and X represents an oxygen atom or a sulfur atom. ) or a salt thereof.