JPH06104653B2 - Aryloxyureas, their preparation and uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to novel aryloxyureas, a process for producing them, and herbicides containing them as active ingredients.

BACKGROUND ART Many herbicides have been used to ensure crop yields. Urea compounds, such as DCMU, which is widely used as a herbicide in upland fields, have the disadvantage that they cannot be used in paddy fields due to their strong phytotoxicity.

U.S. Pat. No. 3,332,975 discloses that m-chlorophenoxyureas, which have a different chemical structure from the compounds of the present invention, can be used as pharmaceuticals. However, as will be described later, these compounds do not exhibit herbicidal effects, or even if they do, the effects are very weak.

In Japanese Patent Publication No. 41-5254, the following formula wherein R ₁ is phenyl or halogen-substituted phenyl or a group of formula wherein _R5 and _R6 are the same alkyl or aralkyl, or _R5 and _R6 together with the nitrogen atom to which they are attached can form piperidino or morpholino; _R2 is a lower aliphatic hydrocarbon group or phenyl, or phenyl substituted with at least one of halogen, alkylmercapto, nitro, and alkoxy; _R3 and _R4 are
are the same alkyl or aralkyl, or _R3 and _R4 can also form piperidino or morpholino together with the nitrogen atom to which they are attached; and X is oxygen or sulfur, and these compounds are described as herbicides, although no biological data is disclosed.

In Japanese Patent Publication No. 46-6999, the following formula wherein R is _C1 - _C4 alkyl; Y is a halogen atom of F, C1, Br or I, _C1 - _C4 alkyl, or _C1 - _C4 alkoxy; n is 0 or 1 when Y is a halogen atom;
Z is an integer from C1 to 3 or 1 when Y is alkyl or alkoxy; Z is a halogen atom of F, C1, Br or I or an integer from C1 to ₃ ;
_C4 alkyl; a is 0 or 1 when Z is a halogen atom;
is an integer from 1 to 5, or when Z is alkyl,
It is disclosed that the compound: is a herbicide to be applied to plants or their growing parts.

Furthermore, the specification of U.S. Patent Application SN800031 and the specification of European Patent Application EP-183174, which are prior applications of the present application, disclose a compound represented by the following formula (I): wherein A is a halogen atom or trifluoromethyl; X, Y and Z are each a hydrogen atom, a halogen atom or trifluoromethyl; _R1 is _C1 - _C6 alkyl, lower alkoxy, lower alkoxy-substituted lower alkyl, cycloalkyl-substituted lower alkyl,
lower alkenyl, lower alkynyl, lower haloalkyl,
_{R1 and R2} may, together with the nitrogen atom to which they are attached, form a _{3- to 8 -} substituted (which may be a bicyclic ring) ring which may contain a double bond or an oxygen atom in the ring and which may have one or more branches, and the compounds represented by the formula:

An object of the present invention is to provide novel aryloxyureas.

Another object of the present invention is to provide novel aryloxyureas which exhibit excellent herbicidal activity.

A further object of the present invention is to provide novel aryloxyureas which exhibit excellent herbicidal effects against weeds when applied to weeds over a wide period from pre-emergence through the growing season.

A further object of the present invention is to provide novel aryloxyureas which exhibit herbicidal effects but are highly safe to crops or crop plants.

A further object of the present invention is to provide an industrially advantageous production of the compounds of the present invention having excellent herbicidal activity.

Further objects and advantages of the present invention will become apparent from the following description.

DISCLOSURE OF THE INVENTION According to the present invention, the above objects and advantages of the present invention are achieved in the first
to the following formula (I): wherein Ar is a group selected from the group consisting of phenyl, pyridyl, pyridazinyl, pyrimidinyl, and pyrazinyl; X and Y are the same or different and are a hydrogen atom, a halogen atom, cyano, trifluoromethyl, nitro, lower alkoxy, lower alkylthio, or lower alkoxycarbonyl; ^R1 is a hydrogen atom, lower alkyl, lower alkenyl, lower alkynyl, or _C3 - _C7 cycloalkyl; ^R2 is a hydrogen atom or lower alkyl; ^R1 and ^R2 may be joined together with the nitrogen atom to which they are attached to form a 4- to 8-membered heterocyclic group, which may contain an oxygen atom as a ring member and may be substituted with a lower alkyl group or a lower alkylene group; and ^R3 is a group represented by ^-COR4 , _-CH2OR5 , ^or a lower alkyl group; R wherein ^{R 4} is a hydrogen atom, lower alkyl, lower haloalkyl, lower alkoxymethyl or lower alkoxy, lower alkoxy-substituted lower alkoxy or halogen-substituted lower alkoxy; and R ⁵ is a hydrogen atom or lower alkyl, and the acid addition salts thereof.

is one of the groups

As Ar, phenyl, pyridyl and pyrazinyl are preferred, and phenyl and pyridyl are more preferred.

Pyridyls include pyridin-2-yl and pyridin-4-yl.
Among them, pyridin-2-yl is particularly preferred.

Pyridazinyl includes pyridazin-3-yl and pyridazin-4-yl.

Pyrimidinyl includes pyrimidin-2-yl and pyrimidin-4-yl.
4-yl is particularly preferred.

Pyrazinyl means pyrazin-2-yl.

In the above formula (I), X and Y are atoms or groups bonded to the ring carbon atoms of Ar, and are each a hydrogen atom, a halogen atom, cyano, trifluoromethyl, nitro, lower alkoxy, lower alkylthio, or lower alkoxycarbonyl.

Preferred examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

The lower alkoxy is preferably a straight or branched lower alkyl group having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, and the like.

The lower alkylthio is preferably a group having a straight or branched lower alkyl group having 1 to 4 carbon atoms, such as methylthio, ethylthio, n-propylthio, iso-
Propylthio, n-butylthio, sec-butylthio, iso
-butylthio and the like.

The lower alkoxycarbonyl is preferably one having a straight or branched lower alkyl group having 1 to 4 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl,
Examples include n-propoxycarbonyl and n-butoxycarbonyl.

X and Y are preferably a hydrogen atom, a halogen atom, particularly a chlorine atom and a bromine atom, trifluoromethyl, and nitro, with a hydrogen atom, a chlorine atom, and trifluoromethyl being particularly desirable.

According to the definitions of Ar, X and Y above, the groups in formula (I) Examples of the phenyl group include phenyl and 2-chlorophenyl groups.
3-chlorophenyl group, 2,3-dichlorophenyl group, 3,5
-dichlorophenyl group, 2,5-dichlorophenyl group, 3
-trifluoromethylphenyl group, 3,5-di(trifluoromethyl)phenyl group, 2,5-di(trifluoromethyl)phenyl group, 2-chloro-5-trifluoromethylphenyl group, 5-chloro-2-trifluoromethylphenyl group, 3-chloro-5-trifluoromethylphenyl group, 2-bromophenyl group, 3-bromophenyl group, 2,
5-difluorophenyl group, 2-cyanophenyl group, 3
-cyanophenyl group, 4-cyanophenyl group, 2-chloro-4-cyanophenyl group, 3-chloro-2-cyanophenyl group, 3-nitrophenyl group, 5-chloro-2-nitrophenyl group, 2-chloro-5-nitrophenyl group,
2-nitro-4-trifluoromethylphenyl group, 6-
substituted or unsubstituted phenyl groups such as chloro-2-nitrophenyl; a 2-pyridyl group, a 3-chloro-2-pyridyl group, a 4-chloro-2-pyridyl group, a 5-chloro-2-pyridyl group, a 6-chloro-2-pyridyl group, a 3,5-dichloro-2-pyridyl group, a 6-methoxy-2-pyridyl group,
3-trifluoromethyl-2-pyridyl group, 5-trifluoromethyl-2-pyridyl group, 4-trifluoromethyl-2-pyridyl group, 6-trifluoromethyl-2-pyridyl group, 3-chloro-5-trifluoromethyl-2-
Pyridyl group, 5-chloro-3-trifluoromethyl-2
-pyridyl group, 6-chloro-4-trifluoromethyl-
2-pyridyl group, 3-chloro-6-trifluoromethyl-2-pyridyl group, 5-nitro-2-pyridyl group, 6-
a substituted or unsubstituted pyridyl group such as a chloro-3-nitro-2-pyridyl group or a 3-ethoxycarbonyl-2-pyridyl group; a substituted or unsubstituted pyridazinyl group such as a 3-pyridazinyl group, a 6-chloro-3-pyridazinyl group, a 4-pyridazinyl group or a 3,6-dichloro-4-pyridazinyl group; a 4-pyrimidinyl group or a 6-chloro-2-methylthio-4-pyridazinyl group;
substituted or unsubstituted pyrimidinyl groups such as a 2-pyrazinyl group and a 6-chloro-2-pyrazinyl group; and substituted or unsubstituted pyrazinyl groups such as a 2-pyrazinyl group and a 6-chloro-2-pyrazinyl group.

In the above formula (I), R ¹ is a hydrogen atom, lower alkyl, lower alkenyl, lower alkynyl or C ₃ -C ₇ cycloalkyl.

The lower alkyl is preferably a straight-chain or branched-chain lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-
butyl and tert-butyl.

The lower alkenyl has a longest carbon chain of 3 to 10 carbon atoms.
5 unsaturated hydrocarbon groups are preferred, such as allyl, 2-
Butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1,2-dimethyl-2
2-propenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, and the like can be mentioned.

The lower alkynyl group has a carbon number of 3 in the longest carbon chain.
Unsaturated hydrocarbon groups of from 1 to 5 are preferred, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-
propynyl, 1,1-dimethyl-2-propynyl, and the like.

_C3 - _C7 cycloalkyl includes, for example, cyclopropyl,
Mention may be made of cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

As ^R1 , lower alkyl and _C3 - _C7 cycloalkyl are particularly preferred.

In the above formula (I), ^R2 is a hydrogen atom or lower alkyl.

Examples of lower alkyl include the same as those mentioned above for ^R1 .

^R1 and ^R2 may be taken together to form a 4- to 8-membered, preferably 6- to 7-membered, alkyl group with the nitrogen atom to which they are attached.
The heterocyclic group of a ring may contain an oxygen atom as a ring member atom and may be substituted with a lower alkyl or lower alkylene. Examples of the lower alkyl as a substituent include the same as those mentioned above for ^R1 . The lower alkylene as a substituent is preferably an alkylene group having 2 to 4 carbon atoms, such as ethylene,
Mention may be made of trimethylene or tetramethylene.

Examples of such heterocyclic groups include the following groups.

4-membered ring group: 5-membered ring group: 6-membered ring group: 7-membered ring group: 8-membered ring group: Oxygen ring groups containing oxygen atoms: Heterocyclic groups (bicyclic groups) containing lower alkylene groups: In the above formula (I), ^R3 is a group represented by ^-COR4 , _-CH2OR5 or lower ^alkyl . ^R4 is a hydrogen atom, lower alkyl,
It is lower haloalkyl, lower alkoxymethyl, lower alkoxy, lower alkoxy-substituted lower alkoxy or halogen-substituted lower alkoxy.

The lower alkyl and lower alkoxy are each
Specific examples include the same groups as those mentioned above for R ¹ and X.

The halo of the lower haloalkyl may be, for example, fluorine, chlorine, bromine, or iodine. The lower haloalkyl is preferably a straight or branched chain haloalkyl having 1 to 4 carbon atoms, such as chloromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2,2,
Examples include 2-trifluoroethyl, 2,3,3,3-tetrafluoropropyl, and 4-chlorobutyl.

The lower alkoxy moiety of the lower alkoxymethyl is X
Preferred examples of lower alkoxymethyl include those mentioned above. Examples of lower alkoxymethyl include methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl, and the like.

Preferred examples of both lower alkoxy moieties of the lower alkoxy-substituted lower alkoxy include those mentioned above for X. Examples of the lower alkoxy-substituted lower alkoxy include 2-methoxyethoxy, 2-ethoxyethoxy, 3-methoxypropoxy, etc. Examples of the halogen of the halogen-substituted lower alkoxy include:
Examples include fluorine, chlorine, bromine, and iodine.
Preferred examples of the lower alkoxy moiety are the same as those mentioned above for X. Examples of the halogen-substituted lower alkoxy include 2-chloroethoxy, 2,2,2
-trichloroethoxy, 2-fluoroethoxy, etc.

From the above specific examples of ^R4 , it will be understood that the group represented by the formula ^-COR4 is therefore formyl ( ^R4 = H), alkylcarbonyl ( ^R4 = lower alkyl), haloalkylcarbonyl ( ^R4 = lower haloalkyl), alkoxymethylcarbonyl ( ^R4 = lower alkoxymethyl) and alkoxycarbonyl ( ^R4 = lower alkoxy), and specific examples of each will also be understood.

^R5 is a hydrogen atom or lower alkyl. Examples of lower alkyl include the same as those mentioned above for ^R1 .

_--CH.sub.2 ^OR.sub.5 is therefore hydroxymethyl ( ^R.sub.5 =H) or alkoxymethyl ( ^R.sub.5 =lower alkyl), examples of alkoxymethyl include methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl, and the like.

Preferred examples of the compounds of the present invention represented by the above formula (I) include the compounds shown in Table 1 below.

Among the compounds in Table 1 above, compound numbers 1 to 9 and 12 to 1
9, 21-25, 27, 33-35, 39-48, 50-62, 65-69, 7
2, 73, 78-80, 82, 84, 86, 88-90, 92-94, 113, 11
Compounds Nos. 6 and 119 are more preferred, and compound Nos. 1 and 2 are particularly preferred.
~3, 5, 6, 8, 12-15, 21-25, 33, 34, 39, 40,
42, 43, 45, 53, 54, 55, 56, 58, 62, 65, 67, 68, 7
8, 79, 80, 82, 84, 86, 89, 90, 92, 93, 94 and 119
Compound 1 is particularly preferred.

The substances of the present invention may be in a free state or in the form of a salt, for example, an acid addition salt.

Examples of acids that can form acid addition salts include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; and organic acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, maleic acid, and citric acid.

According to the present invention, among the compounds of the above formula (I) of the present invention, the compound of the following formula (I)-1 Here, the definitions of Ar, X, Y, ^R1 and ^R2 are as defined in the above formula (I).
and R ³¹ is a group represented by -COR ⁴¹ , -CH ₂ OR ⁵¹ or lower alkyl; R ⁴¹ is a lower alkyl group, lower haloalkyl, lower alkoxymethyl, lower alkoxy, lower alkoxy-substituted lower alkoxy or halogen-substituted lower alkoxy; and R ⁵¹ is lower alkyl, can be obtained by the aryloxyureas represented by the following formula (II): Here, the definitions of Ar, X, Y, ^R1 and ^R2 are as defined in the above formula (I).
The compound represented by the formula (I)-1 can be produced by reacting a compound represented by the formula (I)-1 with a compound represented by the formula (III) R ³¹ -Cl (III) in the presence of a base, wherein the definition of R ³¹ is the same as in the formula (I)-1.

In the formula (II), the definitions of Ar, X, Y, ^R1 and ^R2 are the same as those in the formula (I). Therefore, specific examples of the compound of the formula (II) will be obvious to those skilled in the art from the specific examples of the compound of the formula (I). The compound of the formula (II) can be prepared from the compounds described in European Patent Application EP-183174, Japanese Patent Laid-Open No. 61-126065,
It can be produced by the methods described in Japanese Patent Application Nos. 60-257691 and 61-119293 or essentially in accordance with these methods.

Furthermore, as is clear from the definition of ^R31 , the compound represented by the above formula (III) represents an acid chloride represented by the following formula ^R41 -COCl, where ^R41 is lower alkyl, lower haloalkyl, lower alkoxymethyl, lower alkoxy, lower alkoxy-substituted lower alkoxy, or halogen-substituted lower alkoxy, a chloroformate, or a lower alkoxymethyl chloride represented by the following formula ^R51 - _OCH2Cl , where ^R51 is lower alkyl.

In the above formula, examples of the lower alkyl represented by ^R41 and ^R51 include the same as those described above for ^R1 in formula (I). In addition, examples of the lower haloalkyl, lower alkoxymethyl, and lower alkoxy represented by ^R41 include the same as those described above for ^R4 in formula (I). Therefore, specific examples of the acid chloride, chloroformate, and lower alkoxymethyl chloride in the above formulas will also be clear from the specific examples of ^R41 and ^R51 , respectively.

The compound of formula (II) and the compound of formula (III) are reacted in the presence of a base.

The base may be either an organic base or an inorganic base. Examples of the organic base include pyridine bases such as pyridine, picoline, lutidine, and collidine; triethylamine; 1,8-diazabicyclo[5,4,0]
Tertiary amines such as undecene-7, N,N-dimethylaniline _, etc. are preferably used. Examples of inorganic bases include _NaHCO3 , _KHCO3 , _Na2CO3 , _{and K2CO3} .

In the reaction, 0.8 to 3 moles, preferably 1 to 3 moles of the compound of formula (III) are used per mole of the compound of formula (II).
The base is usually a compound represented by the above formula (II
The amount of the compound (I) is preferably 0.5 to 10 moles, more preferably 1 to 5 moles, per mole of the compound (I).

The reaction temperature is usually 0 to 100° C., preferably 0 to 60° C. The reaction time is usually 30 minutes to 30 hours. The reaction is preferably carried out with stirring.

A reaction solvent does not necessarily have to be used, but a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, or xylene; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, or dichlorobenzene; tetrahydrofuran, ethyl acetate, or dimethylformamide may be used.

After the reaction, the target product can be obtained from the reaction mixture by a conventional method as shown in the later examples.

Furthermore, according to the present invention, among the compounds of the above formula (I) of the present invention, the compound of the following formula (I)-2 Here, the definitions of Ar, X, Y, ^R1 and ^R2 are as defined in the above formula (I).
The aryloxyureas represented by the formula (I) are the same as
The compound represented by the ^formula (II) and the compound represented by the formula (IV) below can be used. wherein R ⁶ is lower alkyl, with a compound represented by the following formula:

In the above formula (IV), ^R6 is a lower alkyl group, and specific examples thereof are the same as those given for ^R1 in the above formula (I).

The compound represented by formula (IV) can be prepared by, for example, reacting formic acid with a compound represented by the general formula (R ⁶ C
The resulting reaction mixture can be optionally directly subjected to _the synthesis of compound (IV) without isolating it.
It can be used in the above method of the present invention.

In the reaction, 3 to 10 moles, preferably 3 to 7 moles, of the compound of formula (IV) are used per mole of the compound of formula (II).

The reaction temperature is usually 40 to 80° C. The reaction time is usually 1 to 10 hours. The reaction is preferably carried out under stirring.

The reaction can be carried out in the absence or presence of a solvent, and the solvent may be the same as that used in the process of the present invention using the compound of formula (III).

Furthermore, according to the present invention, among the compounds of the above formula (I) of the present invention, Here, the definitions of Ar, X, Y, ^R1 and ^R2 are as defined in the above formula (I).
The aryloxyureas represented by the formula (I) are the same as
^R3 is _-CH2OH ) corresponds to the compound of formula (II)
The compound can be produced by reacting a compound represented by the formula (I) with formaldehyde.

In the reaction, 1 to 5 moles of formaldehyde are usually used per mole of the compound of formula (II).

The reaction temperature is usually 0 to 50°C. The reaction time is usually 0.5 to 1
The reaction time is 0 hours. The reaction is preferably carried out under stirring.

As the formaldehyde source used in the reaction, commercially available formalin can be used as it is.

Furthermore, according to the present invention, among the compounds of the above formula (I) of the present invention, the compound of the following formula (I)-4 wherein the definitions of Ar, X and Y are the same as in the above formula (I), R ¹¹ is lower alkyl, lower alkenyl, lower alkynyl or C ₃ to C ₇ cycloalkyl, R ²¹ is lower alkyl, R ¹¹ and R ²¹ may be taken together with the nitrogen atom to which they are bonded to form a 4 to 8 membered heterocyclic group, wherein the heterocyclic group may contain an oxygen atom as a ring member atom and may be substituted with a lower alkyl group or a lower alkylene group, and R ⁴² is lower alkoxy, lower alkoxy-substituted lower alkoxy or halogen-substituted lower alkoxy, and the aryloxy ureas represented by the following formula (V) wherein the definitions of Ar, X, and Y are the same as those in the above formula (I), and the definition of R ⁴² is the same as that in the above formula (I)-4, and a compound represented by the following formula (VI): wherein R ¹¹ and R ¹² are defined as in the above formula (I)-4, with a carbamoyl chloride represented by the following formula: in the presence of a base.

The base may be either an organic base or an inorganic base. Examples of the organic base include pyridine bases such as pyridine, picoline, lutidine, and collidine, triethylamine, and 1,8-diazabicyclo[5,4,0]
Tertiary amines such as undecene-7, N,N-dimethylaniline, etc. are preferably used. Examples of inorganic bases include NaHCO, KHCO ₃ , Na ₂ CO ₃ , and K ₂ CO ₃ .

In the reaction, the compound of the formula (VI) is usually used in an amount of 0.8 to 3 moles, preferably 1 mole, per mole of the compound of the formula (V).
The base is usually used in an amount of 0.5 to 20 moles, preferably 1 to 10 moles, per mole of the compound of formula (V). The reaction temperature is usually 0 to 100°C.
The reaction temperature is preferably 20 to 80° C. The reaction time is usually 1 to 100 hours. The reaction is preferably carried out under stirring.

A reaction solvent does not necessarily have to be used, but a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, or xylene; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, or dichlorobenzene; tetrahydrofuran, ethyl acetate, or dimethylformamide may be used.

After the reaction, the target product can be obtained by a conventional method as shown in the Examples below.

Furthermore, according to the present invention, among the compounds of the above formula (I) of the present invention, the compound of the following formula (I)-5 Here, the definitions of Ar, X, Y, ^R1 and ^R4 are as defined in the above formula (I).
The aryloxyureas represented by the following formula (VII) Here, the definitions of Ar, X, Y and ^R4 are the same as in formula (I) above, and the compound represented by the formula (VIII) can be produced by reacting the compound represented by the formula (VIII) with an isocyanate ester represented by the formula (VIII) below: O=C=N- ^R12 (VIII), where ^R12 is lower alkyl, lower alkenyl, lower alkynyl or _C3 - _C7 cycloalkyl.

In the reaction, 0.8 to 10 moles, preferably 1 to 5 moles, of the isocyanate ester of formula (VIII) are usually used per mole of the compound of formula (VII). The reaction temperature is usually 0 to 100°C, preferably 20 to 80°C. The reaction time is usually 1 to 100 hours. The reaction is preferably carried out under stirring.

A reaction solvent does not necessarily have to be used, but a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, or xylene, a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, or dichlorobenzene, tetrahydrofuran, ethyl acetate, or dimethylformamide, may be used.

In addition, a tertiary amine such as triethylamine may be added to the reaction in an amount of 0.1 to 30 mol % based on the compound of the formula (VIII).

Furthermore, according to the present invention, among the compounds of the above formula (I) of the present invention, the compound of the following formula (I)-6 wherein Ar' is a group selected from the group consisting of pyrimidinyl and pyridazinyl, R ³² is a lower alkyl group, and X, Y, R ¹ and R ² are defined as in the above formula (I), and the aryloxyureas represented by the following formula (IX): Here, the definition of Ar′ is the same as in formula (I)-6 above.
The definitions of X and Y are the same as in the above formula (I), and a compound represented by the following formula (X): Here, the definition of ^R is the same as that of formula (I)-6 above, and R
The definitions of ^R1 and ^R2 are the same as in formula (I) above, and the compound can be produced by reacting an N-hydroxyurea represented by the formula (I) in the presence of a base. Examples of the base include pyridine bases such as pyridine, picoline, lutidine, and collidine, tertiary amines such as triethylamine, 1,8-diazabicyclo[5.4.0]undecene-7, and N,N-dimethylaniline, inorganic bases such as _NaHCO3 , _KHCO3 , _Na2CO3 , _{and K2CO3 ,} as well as sodium ethoxide, potassium-
Alkali metal alkoxides such as t-butoxy can be used.

The amount of base used is 0.5 to 10 moles, preferably 1 to 5 moles, of N-hydroxyurea of formula (X) per mole of compound of formula (IX). The reaction temperature is usually -50 to +50°C, preferably -40 to +40°C. The reaction time is usually 0.5 to 10 hours. The reaction is preferably carried out under stirring. A reaction solvent may not be used, but a solvent inert to the reaction, such as aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethane,
Halogenated hydrocarbons such as benzene, tetrahydrofuran, ethyl acetate, dimethylformamide, etc. may also be used.

The aryloxyureas of the above formula (I) of the present invention and their acid addition salts exhibit the obtained and characteristic herbicidal efficiency.

Therefore, according to the present invention, there is also provided a herbicide containing the aryloxyurea or an acid addition salt thereof of the present invention as an active ingredient for herbicidal use.

When using the compound of the present invention as a herbicide, the compound of the present invention may be used as it is, or may be processed into any formulation such as granules, wettable powders, emulsifiable concentrates, dusts, and fine dusts. Better results can be obtained when used in a formulation. Herbicides having these formulations are prepared by mixing the compound of the present invention with a solid carrier such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, hydrated lime, silica sand, ammonium sulfate, and urea; a liquid carrier such as alcohol, dioxane, acetone, cyclohexanone, methylnaphthalene, dimethylformamide, and dimethyl sulfoxide; a salt of alkyl sulfate ester, an alkylaryl sulfonate, and the like.
They can be manufactured by appropriately using emulsifiers or dispersants such as polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan monoalkylates, etc., or various adjuvants such as carboxymethyl cellulose, gum arabic, etc. The proportion of the active ingredient can be adjusted as needed, but for dusts, 0.5 to 20% (by weight) is appropriate, and for emulsifiable concentrates or wettable powders, 5 to 70% (by weight) is appropriate.

The herbicide of the present invention is applied as is, or further diluted or suspended appropriately with water, etc., in an amount effective for controlling the weeds. The amount of the compound of the present invention to be used as a herbicide cannot be generally determined because it depends on the soil conditions, formulation, application time, application method, cultivated crop, type of target weed, etc., but it is effective to apply it so that it becomes 10 g to 5 kg per hectare.

The herbicide of the present invention exerts superior herbicidal effects when applied to paddy fields at the time of germination and growth, compared with commercially available herbicides, not only against annual weeds such as barnyard grass, Cyperus sieboldii, Monochoria vaginalis, Turmeric, Lindernia gracilis, and Ardisia crassipes, but also against perennial weeds such as Scirpus bulrush, Cyperus serotinus, and Ardisia gracilis, even at high doses, showing excellent selectivity. Furthermore, the herbicide of the present invention exerts herbicidal effects against various weeds that are problematic in upland fields, such as gramineous weeds such as barnyard grass, Digitaria ciliaris, Setaria viridis, Poa annua, and Lamium gramineum, scyperus weeds such as Cyperus sieboldii, and broad-leaved weeds such as Lamium pigweed and Chenopodium album, when applied to soil or foliage. Furthermore, the herbicides of the present invention are effective against rice, wheat, corn, soybean, and other crops.
Furthermore, the herbicide of the present invention is characterized by its safety against major crops such as cotton.
It can also be used as a herbicide for lawns and non-crop land.

The herbicide of the present invention can also be used in combination with other agricultural chemicals, fertilizers, etc., if desired.

EXAMPLES Example 1A 1-t-butyl-3-(2,5-dichlorophenoxy)-
3-Formyl urea (Compound No. 1) A mixture of 1.53 g (33.3 mmol) of formic acid and 3.24 g (31.8 mmol) of acetic anhydride was stirred at 60°C for 2.5 hours, and then 1-t-butyl-3-
2.20 g (7.94 mmol) of (2,5-dichlorophenoxy)urea was added, and the mixture was stirred at 60° C. for 5 hours. After the reaction, the mixture was cooled to room temperature, and then 100 ml of ethyl acetate was added, followed by washing with saturated saline.
The residue obtained by distilling off the ethyl acetate under reduced pressure was purified by silica gel column chromatography (eluent: ethyl acetate-hexane) to obtain 1.48 g of the target product as colorless crystals (yield 61%).

Melting point: 101-102°C Mass spectrum (FD method): m/z 304 (molecular ion peak) IR spectrum (KBr pellet method, cm ^-1 ): 3400, 3380, 1730, 1705, 1572, 1503, 1464, 1389, 1268, 1195,
1092,910,815 ^1H -NMR spectrum ( _CDCl3 solution, ppm) (a) 1.39 (9H,s) (b) 6.24 (1H,br,s) (c) 7.0-7.4 (3H,m) (d) 9.22 (1H,s) Example 2A 3-acetyl-3-(3,5-dichlorophenoxy)-1,1
-Hexamethyleneurea (Compound No. 2) 2.0 g (6.6 mmol) of 3-(3,5-dichlorophenoxy)-1,1-hexamethyleneurea was dissolved in a mixed solution of 20 ml of tetrahydrofuran and 1.6 ml of pyridine, and then acetyl chloride was added.
A tetrahydrofuran solution (10 ml) of 1.0 g (13.2 mmol) of the compound was added, and the mixture was stirred at 25°C for 2 hours and then at 50°C for another 2 hours. After the reaction mixture was cooled to room temperature, 100 ml of water was added, and the mixture was extracted with ethyl acetate. The extract was washed with dilute sulfuric acid water and then saturated brine, and then dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate-hexane).
Further, recrystallization from toluene-hexane gave 1.72 g of the target product as colorless needles (yield 75%).

Melting point: 65-66°C Mass spectrum (FD method): m/z 344 (molecular ion peak) IR spectrum (KBr pellet, cm ^-1 ): 1720, 1685, 1580, 1430, 1375, 1270, 1205, 1100, 930, 845 ^1H -NMR spectrum (CDCl ₃ solution, ppm) (a) 1.4-2.0 (8H,m) (b) 2.27 (3H,s) (c) 3.53 (4H,m) (d) 7.01 (2H,d,J=1.8Hz) (e) 7.09 (1H,d,J=1.8Hz) Example 3A 3-(3,5-Dichlorophenoxy)-1-isopropyl-3-methoxycarbonyl-1-methylurea (Compound No. 3) 2.15g (7.76mmol) of 3-(3,5-dichlorophenoxy)-1-isopropyl-1-methylurea was dissolved in a mixed solution of 20ml of tetrahydrofuran and 1.9ml of pyridine, and
A solution (10 ml) of 1.47 g (15.5 mmol) of methyl chloroformate in tetrahydrofuran was added, and the mixture was stirred at 25°C for 2 hours. 100 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate-
The product was purified with hexane to give 1.14 g of the desired product as yellow crystals (yield 44%).

Melting point: 67-69°C Mass spectrum (FD method): m/z 334 (molecular ion peak) IR spectrum (KBr pellet, cm ^-1 ): 1742, 1708, 1581, 1432, 1280, 1095, 942, 840 ^1H -NMR spectrum (CDCl ₃ solution, ppm) (a) 1.21 (6H,d,J = 6.6 Hz) (b) 2.91 (3H,s) (c) 3.87 (3H,s) (d) 4.46 (1H,m) (e) 7.01 (2H,m) (f) 7.07 (1H,m) Example 4A 3-(2,5-Dichlorophenoxy)-3-hydroxymethyl-1-n-propylurea (Compound No. 4) 2.0 g (7.6 mmol) of 3-(2,5-dichlorophenoxy)-1-n-propylurea was dissolved in 10 ml of N,N-dimethylformamide.
After dissolving in 1.87 g (22.8 mmol) of 37% formalin solution,
The reaction mixture was added with 100 ml of water and stirred at 25°C for 3 hours.
The extract was washed with saturated saline and then dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure, and the resulting residue was recrystallized from ethyl acetate-toluene to obtain 1.4 g of the target product as colorless crystals (yield 63%).
%). Melting point: 119-121°C (decomposition) Mass spectrum (FD method) m/z 292 (molecular ion peak) IR spectrum (KBr pellet, cm ^-1 ) 3320, 1665, 1580, 1530, 1470, 1275, 1215, 1085, 1045, 955, 9
20,860,800 ^1H -NMR spectrum ( _CDCl3 solution, ppm) (a) 0.92 (3H,t,J = 7.2 Hz) (b) 1.3-1.8 (2H,m) (c) 3.1-3.4 (2H,m) (d) 3.90 (1H,t,J = 7.2 Hz) (e) 5.15 (2H,d,J = 7.2 Hz) (f) 5.8-6.1 (1H,m) (g) 7.05 (1H,dd,J = 9.0,1.8 Hz) (h) 7.35 (1H,d,J = 9.0 Hz) (i) 7.40 (1H,d,J = 1.8 Hz) Examples 5A-80A Compounds 5-80 were synthesized from the corresponding starting materials listed in Table 1 in a manner similar to that of Examples 1A-4A. The results are shown in Table 1A. In addition, manufacturing methods A, B,
C and D correspond to the production methods described in Examples 1A, 2A, 3A and 4A, respectively.

Example 81A 3-(2,5-Dichlorophenoxy)-3-ethoxymethyl-1-n-propylurea (Compound No. 81) 2.63 g of 3-(2,5-dichlorophenoxy)-1-n-propylurea, 4.14 g (20 mmol) of water, potassium carbonate, and 1.42 g (15 mmol) of chloromethyl ethyl ether were added and stirred at 50° C. for 1 hour. The reaction mixture was cooled to room temperature, and then 300 ml of water was added.
The extract was washed with saturated saline and dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate-hexane) to obtain 0.44 g of the target product as a pale yellow oil (yield 14%).
%).

Mass spectrum (FD method) m/z 320 (molecular ion peak) IR spectrum (neat, cm ^-1 ) 3430, 1643, 1575, 1465, 1398, 1375, 1235, 1160, 1079, 975, 7
98 ¹ H-NMR spectrum (CDCl ₃ solution, ppm) (a) 0.95 (3H,t,J=7.2Hz) (b) 1.29 (3H,t,J=7.2Hz) (c) 1.58 (2H,m) (d) 3.21 (2H,m) (e) 3.80 (2H,q,J=7.2Hz) (f) 5.1 (1H,m) (h) 6.85 (1H, dd, J = 8.8, 2.2 Hz) (i) 7.22 (1H, d, J = 8.8 Hz) (j) 7.50 (1H, d, J = 2.2 Hz) Example 82A (Compound No. 82) 3-(3,5-Dichloro-2-pyridyloxy)-3-ethoxycarbonyl-1,1-pentamethyleneurea 2.20 g (8.76 mmol) of ethyl N-(3,5-dichloro-2-pyridyloxy)carbamate was dissolved in 3.5 ml of pyridine, and then 1.94 g (13.1 mmol) of 1-chloroformylpiperidine was added.
The mixture was stirred at 50°C for 20 hours. After the reaction mixture was cooled to room temperature, 250 ml of water was added and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate-hexane) to give 2.75 g of the target product as an orange liquid.
The product was obtained (yield 76%).

Mass spectrum (FD method) m/z 361 (molecular ion peak) IR spectrum (neat, cm ^-1 ) 1735, 1700, 1420, 1380, 1300, 1245, 1220, 1105 ¹ H-NMR spectrum (CDCl ₃ solution, ppm) (a) 1.30 (3H, t, J = 7.0 Hz) (d) 4.29 (2H, q, J = 7.0 Hz) (e) 7.73 (1H, d, J = 2.0 Hz) (f) 8.01 (1H, d, J = 2.0 Hz) Example 83A (Compound No. 83) 3-(3-trifluoromethyl-2-pyridyloxy)
-3-ethoxycarbonyl-1-n-propylurea N-(3-trifluoromethyl-2-pyridyloxy)
2.30 g (9.19 mmol) of ethyl carbamate in 50 ml of toluene
After dissolving it in 2.34 g of n-propyl isocyanate (2
0.2 g (7.6 mmol) of toluene and 0.2 g (2.0 mmol) of triethylamine were added, and the mixture was stirred at 45° C. for 40 hours. Toluene and excess n-propyl isocyanate were removed from the reaction mixture by distillation under reduced pressure.
The resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate-hexane) to obtain 2.61 g of the target product as a colorless liquid (yield 85%).

Mass spectrum (FD method) m/z 335 (molecular ion peak) IR spectrum (neat, cm ^-1 ) 3350, 1740, 1705, 1600, 1585, 1525, 1430, 1375, 13
20, 1220, 1150, 1070, 1035, 1005, 920 ^1H -NMR spectrum (CDCl ₃ solution, ppm) (a) 0.96 (3H, t, J = 7.0 Hz) (b) 1.20 (3H, t, J = 7.0 Hz) (c) 1.60 (2H, m) (d) 3.30 (2H, q, J = 7.0 Hz) (e) 4.24 (2H, q, J = 7.0 Hz) (f) 7.16 (1H, dd, J = 7.4, 5.3 Hz) (g) 7.9 (1H, br.s) (h) 7.98 (1H, d, J = 7.4 Hz) (i) 8.30 (1H, d, J = 5.3 Hz) Examples 84A-164A Compounds 84-164 listed in Table 1 were synthesized from the corresponding starting materials in a manner similar to that of Examples 82A and 83A. The results are shown in Table 2A. In addition, Production Methods E and F in Table 2A correspond to the production methods described in Examples 82A and 83A, respectively.

Example 165A (Compound No. 165) 3-(6-chloro-2-methylthio-4-pyrimidinyl)-1,1-pentamethyleneurea 4,6-dichloro-2-methylthiopyrimidine 4.98 g (25.5
4.85 g (30.7 mmol) of 3-hydroxy-3-methyl-1,1-pentamethyleneurea (4.85 mmol) were dissolved in 30 ml of N,N-dimethylformamide (DMF), and the solution was cooled to -30°C. Then, a DMF solution of 3.44 g (30.7 mmol) of potassium t-butoxide was added.
30 ml of the product was added dropwise over 15 minutes. The temperature was gradually raised from -30°C, and after reaching +20°C, the mixture was stirred for an additional 2 hours. 300 ml of water was added to the reaction mixture, which was then extracted with ethyl acetate. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. The ethyl acetate was removed under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate-hexane) to obtain 2.71 g of the desired product as a colorless liquid (yield: 34%).

Mass spectrum (FD method) m/z 316 (molecular ion peak) IR spectrum (neat, cm ^-1 ) 1680, 1550, 1525, 1425, 1385, 1310, 1275, 1215, 1130, 1100,
990,940 ^1H -NMR spectrum ( _CDCl3 solution, ppm) Example 166A The target compound 166 listed in Table 1 was synthesized from the corresponding starting material in the same manner as in Example 166A.

Yield: 83%, Liquid IR spectrum (neat, cm ^-1 ) 1675, 1562, 1545, 1410, 1345, 1225, 1130 Next, the herbicide of the present invention will be explained with reference to formulation examples.

In the formulation examples, "%" means percentage by weight.

Formulation Example 1B (Granules) 10% of the compound of the present invention, 2% of sodium lauryl alcohol sulfate, 5% of sodium lignosulfonate
%, 2% carboxymethyl cellulose and 81% clay are mixed and ground uniformly.

80 parts of this mixture is mixed with 20 parts of water, kneaded, processed into 14 to 32 mesh powder using an extrusion granulator, and then dried to form granules.

Formulation Example 2B (powder) 2% sodium salt of lauryl alcohol sulfate,
5% sodium lignosulfonate, 2% carboxymethylcellulose and 91% clay montmorillonite mixture
The mixture is uniformly mixed and pulverized. 22 parts of water is added to 78 parts of this mixture, kneaded, and processed into a powder of 14 to 32 mesh using an extrusion granulator, and then dried to prepare an adsorption base. 20 parts of a mixture of 20% of the compound of the present invention and 80% of polyethylene glycol are uniformly adsorbed into 80 parts of this base to form powder granules.

Formulation Example 3B (wettable powder) 10% of the compound of the present invention, 85% of diatomaceous earth, 2% of sodium dinaphthylmethanedisulfonate and 3% of sodium ligninsulfonate are uniformly mixed and pulverized to give a wettable powder.

Formulation Example 4B (emulsion) 30% of the compound of the present invention, 20% of cyclohexane, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate, and 35% of methylnaphthalene
are uniformly dissolved to form an emulsion.

Formulation Example 5B (Dust) 4% of the compound of the present invention, 5% of diatomaceous earth and 91% of clay are uniformly mixed and pulverized to give a dust.

Next, the effects of the herbicide of the present invention will be explained by way of test examples.

Test Example 1C (Herbicidal test by treatment with paddy field soil) Paddy field soil was filled into 10 cm diameter magnetic pots, and after plowing, seeds of barnyardgrass, Cyperus galloprovincialis, Monochoria vaginalis, and Scirpus juncoides were sown and flooded to a depth of 3 cm. The next day, a wettable powder prepared according to Formulation Example 3B was diluted with water and applied dropwise to the water surface (application rate: 4 kg of active ingredient per hectare). The plants were then grown in a greenhouse, and 30 days after treatment, the herbicidal activity was evaluated according to the criteria in Table 1C below. The results are shown in Table 2C.

Test Example 2C (Test on selective herbicidal activity between rice and barnyard grass) Paddy field soil was filled into a 1/5,000a Wagner pot, and after plowing, barnyard grass seeds were sown and grown in a greenhouse until the two-leaf stage.
The number of barnyardgrass plants at the two-leaf stage was adjusted to 15 per pot, and the test compound was made into a wettable powder according to Formulation Example 3B, and a predetermined amount of the diluted powder was applied dropwise to the water surface.
Two-leaf stage rice plants were transplanted into the 000a Wagner pots, and the test compounds were applied dropwise in the same manner as on the day after transplanting. After treatment, the plants were grown in a greenhouse for 30 days, and the herbicidal activity and phytotoxicity were evaluated according to the criteria in Table 1C. The results are shown in Table 3C.

Test Example 3C (Herbicidal Test by Treatment with Field Soil) Field soil was filled into 120 ^cm2 plastic pots, and seeds of barnyard grass, crabgrass, red spider lily, and sedge were sown and covered with soil. The test compound was made into a wettable powder according to Preparation Example 3B, and the specified amount was diluted with water. The mixture was sprayed evenly over the soil surface with a small sprayer at a rate of 1,000 liters per hectare (application rate: 4 kg of active ingredient per hectare). After treatment, the plants were grown in a greenhouse for 20 days, and the herbicidal effect and phytotoxicity were evaluated according to the criteria in Table 1C. The results are shown in Table 4C.

Test Example 4C (Test on herbicidal effect and phytotoxicity by treatment with field soil) Field soil was filled into a 600 ^cm2 plastic bat, and seeds of barnyard grass, crabgrass, green foxtail, red spider lily, sedge, rice, wheat, corn, soybean, cotton, and beet were sown and covered with soil. The test compound was made into a wettable powder in accordance with Formulation Example 3B, and the specified amount was diluted with water and applied per hectare.
The solution was sprayed evenly onto the soil surface using a small sprayer at a spray rate of 1000 liters. After treatment, the plants were grown in a greenhouse for 30 days, and the herbicidal effect and phytotoxicity were evaluated according to the criteria in Table 1C. The results are shown in Table 5C.

Test Example 5C (Weed control test by treatment of field crop foliage) Field soil was filled into a 120 ^cm2 plastic pot, and barnyard grass,
Sow seeds of crabgrass, red spider lily, and sedge.
The barnyard grass was grown in a greenhouse until it reached the three-leaf stage. The test compound was made into a wettable powder according to the barnyard grass three-leaf stage B, and diluted with water at an amount equivalent to 4 kg of active ingredient per hectare.
The herbicidal activity was investigated according to the criteria in Table 1C. The results are shown in Table 6C.

Test Example 6C (Herbicidal test by treatment with paddy field soil) Paddy field soil was filled into 10 cm diameter magnetic pots, and after plowing, seeds of barnyardgrass, Cyperus galloprovincialis, Monochoria vaginalis, and water sown. The soil was then flooded to a depth of 3 cm. The next day, a wettable powder prepared according to Formulation Example 3B was diluted with water and applied dropwise to the water surface (application rate: 4 kg of active ingredient per hectare). The plants were then grown in a greenhouse, and 30 days after treatment, the herbicidal activity was evaluated according to the criteria in Table 1C below. The results are shown in Table 7C.

Test Example 7C (Herbicide Test by Treatment with Field Soil) Field soil was filled into 120 ^cm2 plastic pots, and seeds of barnyard grass, crabgrass, red spider lily, and sedge were sown and covered with soil. The test compound was made into a wettable powder according to Formulation Example 3B, diluted in a specified amount with water, and sprayed uniformly over the soil surface with a small sprayer at a rate of 1,000 liters per hectare (application rate: 4 kg of active ingredient per hectare). After treatment, the plants were grown in a greenhouse for 20 days, and the herbicidal effect and phytotoxicity were evaluated according to the criteria in Table 1C. The results are shown in Table 8C.

Test Example 8C (Test on herbicidal effect and phytotoxicity by treatment with field soil) A 600 ^cm2 plastic bat was filled with field soil, and seeds of barnyard grass, crabgrass, green foxtail, red spider lily, sedge, rice, wheat, corn, soybean, cotton, and beet were sown and covered with soil. The test compound was made into a wettable powder in accordance with Formulation Example 3B, and the specified amount was diluted with water and applied to the 1000-gram per hectare.
The solution was sprayed evenly over the soil surface using a small sprayer at a spray rate of 1000 liters. After treatment, the plants were grown in a greenhouse for 30 days, and the herbicidal effect and phytotoxicity were investigated according to the criteria in Table 1C. The results are shown in Table 9C.

Test Example 9C (Herbicidal test by treatment with paddy field soil) Paddy field soil was filled into 10 cm diameter magnetic pots, and after plowing, seeds of barnyardgrass, Cyperus galloprovincialis, Monochoria vaginalis, and water sown. The soil was then flooded to a depth of 3 cm. The next day, a wettable powder prepared according to Formulation Example 3B was diluted with water and applied dropwise to the water surface (application rate: 4 kg of active ingredient per hectare). The plants were then grown in a greenhouse, and 30 days after treatment, the herbicidal activity was evaluated according to the criteria in Table 1C below. The results are shown in Table 10C.

Test Example 10C (Weed Control Test by Treatment with Field Soil) Field soil was filled into 600 ^cm2 plastic pots, and seeds of barnyard grass, crabgrass, green foxtail, red spider lily, sedge, rice, wheat, corn, soybean, cotton, and beet were sown and covered with soil. The test compound was made into a wettable powder in accordance with Formulation Example 3B, and the specified amount was diluted with water and applied to the soil per hectare.
The herbicides were sprayed evenly onto the soil surface with a small sprayer at a spray rate of 1000 liters. After the treatment, the plants were grown in a greenhouse for 30 days, and the herbicidal effect and phytotoxicity were investigated according to the criteria in Table 1C. The results were reported in Table 11C.
As shown in the table.

─────────────────────────────────────────────────────── Continued from the front page (51) Int.Cl. ⁵ Identification symbol Internal reference number FI Technical marking location C07D 237/14 239/34 241/18 295/12 Z (72) Inventor Miyazawa Takeshige 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Inventor Nakamura Yasuo 1-14-15 Aobadai, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture

Claims (12)

[Claims] Claim 1: A compound represented by the following formula (I): wherein Ar is a group selected from the group consisting of phenyl, pyridyl, pyridazinyl, pyrimidinyl, and pyrazinyl; X and Y are the same or different and are a hydrogen atom, a halogen atom, cyano, trifluoromethyl, nitro, lower alkoxy, lower alkylthio, or lower alkoxycarbonyl; ^R1 is a hydrogen atom, lower alkyl, lower alkenyl, lower alkynyl, or _C3 - _C7 cycloalkyl; ^R2 is a hydrogen atom or lower alkyl; ^R1 and ^R2 may be joined together with the nitrogen atom to which they are attached to form a 4- to 8-membered heterocyclic group, which may contain an oxygen atom as a ring member and may be substituted with a lower alkyl group or a lower alkylene group; and ^R3 is a group represented by ^-COR4 , _-CH2OR5 , ^or a lower alkyl group; R ^{R 4} is a hydrogen atom, lower alkyl, lower haloalkyl, lower alkoxymethyl, lower alkoxy, lower alkoxy-substituted lower alkoxy, or halogen-substituted lower alkoxy; and R ⁵ is a hydrogen atom or lower alkyl, and an aryloxyurea compound represented by the formula (I) and an acid addition salt thereof. 2. The compound according to claim 1, wherein in the above formula (I), X and Y each independently represent a hydrogen atom, a chlorine atom, or trifluoromethyl. 3. The compound according to claim 1, wherein, in the above formula (I), Ar is phenyl or pyridyl. 4. The compound according to claim 1, wherein in the above formula (I), R ¹ and R ² together form a 6- to 7-membered heterocyclic group together with the nitrogen atom to which they are attached. Claim 5: In the above formula (I), is 3,5-dichlorophenyl or 3-chloro-5-trifluoromethyl-2-pyridyl, 2. The compound of claim 1, wherein R ³ is ethoxycarbonyl, n-propoxycarbonyl, or iso-propoxycarbonyl. Claim 6: A compound represented by the following formula (II): wherein the definitions of Ar, X, Y, ^R1 and ^R2 are the same as in the above formula (I), and a compound represented by the following formula (III) ^{: R31-Cl (III) wherein R31 is a group represented by -COR41 or -CH2OR51 ; R41 is a} _lower ^alkyl group, a lower haloalkyl group, a lower alkoxymethyl group, a lower alkoxy group, a lower alkoxy-substituted lower alkoxy group, or a halogen-substituted lower alkoxy group; and R51 is a lower alkyl group, Here, the definitions of Ar, X, Y, ^R1 and ^R2 are as defined in the above formula (I).
wherein R ³¹ is the same as in formula (III) above. Claim 7: A compound represented by the following formula (II): wherein Ar, X, Y, ^R1 and ^R2 are defined as in the above formula (I), and a compound represented by the following formula (IV): wherein ^R6 is lower alkyl, Here, the definitions of Ar, X, Y, ^R1 and ^R2 are as defined in the above formula (I).
The method for producing an aryloxyurea compound represented by the formula: Claim 8: A compound represented by the following formula (II): wherein the definitions of Ar, X, Y, ^R1 and ^R2 are the same as in the above formula (I), and a compound represented by the following formula (I3) is reacted with formaldehyde: wherein Ar, X, Y, ^R1 and ^R2 are defined as in formula (I) above. Claim 9: A compound represented by the following formula (V): Here, the definitions of Ar, X, and Y are the same as those in the above formula (I), and R ⁴² is lower alkoxy, lower alkoxy-substituted lower alkoxy, or halogen-substituted lower alkoxy. wherein R ¹¹ is lower alkyl, lower alkenyl, lower alkynyl or C ₃ -C ₇ cycloalkyl, R ²¹ is lower alkyl, and R ¹¹ and R ²¹ may together form a 4- to 8-membered heterocyclic group together with the nitrogen atom to which they are bonded, wherein the heterocyclic group may contain an oxygen atom as a ring member atom and may be substituted with a lower alkyl group or a lower alkylene group; wherein the definitions of Ar, X, and Y are the same as in the above formula (I), the definitions of ^R11 and ^R12 are the same as in the above formula (VI), and the definition of ^R42 is the same as in the above formula (V). Claim 10: A compound represented by the following formula (VII): Here, the definitions of Ar, X, Y, and ^R4 are the same as in the above formula (I). A compound represented by the following formula (I)-5 is reacted with an isocyanate ester represented by the following formula (VIII): O=C=N- ^R12 (VIII), where ^R12 is lower alkyl, lower alkenyl, lower alkynyl, or _C3 to _C7 cycloalkyl. Here, the definitions of Ar, X, Y, ^R1 and ^R4 are as defined in the above formula (I).
The same applies to the above. A method for producing an aryloxyurea represented by the following formula: Claim 11: A compound represented by the following formula (IX): wherein Ar' is a group selected from the group consisting of pyrimidinyl and pyridazinyl, and R ³² is a lower alkyl group. Here, the definitions of ^R1 and ^R2 are the same as in the above formula (I), and the definition of ^R32 is the same as in the above formula (X). A method for producing aryloxyureas represented by the formula: 12. A herbicide characterized by containing an aryloxyurea represented by the above formula (I) or an acid addition salt thereof as an active ingredient.