JPH06104652B2 - Substituted aryloxyureas, their preparation and uses - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to novel substituted aryloxyureas, a process for producing the same, and herbicides containing the same as an active ingredient.

BACKGROUND ART Many herbicides have been used to ensure crop yields. Urea compounds, such as DCMU, which are widely used as herbicides in upland fields, have the disadvantage that they cannot be used in paddy fields because of 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 the 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 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, Cl, 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 C 1 to 3, or 1 when Y is alkyl or alkoxy; Z is a halogen atom of F, Cl, Br or I, or C ₁ 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, in the specification of U.S. Patent Application No. SN800,031 and the specification of European Patent Application No. EP-183174, which are prior applications of the present application, there is disclosed 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 be taken together with the nitrogen atom to which they are attached to form a _{3- to 8 -} membered ring (which may be a bicyclic 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 (I) are disclosed, and these compounds have herbicidal effects.

An object of the present invention is to provide novel substituted aryloxy ureas.

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

A further object of the present invention is to provide novel substituted 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 substituted 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 by providing a compound of formula (I): Here, Ar is represented by the formula (a) wherein X ¹ is a hydrogen atom, a lower alkyl, or a lower alkoxy; (b) Formula wherein ^X2 is a hydrogen atom or a halogen atom; (c) Formula where ^X3 is a halogen atom and l is 2 or 3.
(d) is an integer of wherein ^X4 is a fluorine atom, a bromine atom, or an iodine atom, and m is an integer of 1, 2, or 3; wherein ^X5 is a hydrogen atom, a halogen atom, a lower alkyl,
(f) a group of formula (I) which is lower alkoxy or trifluoromethyl; wherein ^X6 is a hydrogen atom or a halogen atom; (g) Formula wherein ^X7 is a hydrogen atom, a halogen atom, cyano, lower alkoxy, or trifluoromethyl; and n is 1 or 2.
(h) Formula wherein ^X8 is a hydrogen atom, a chlorine atom or a lower alkylthio, and p is an integer of 1 or 2; (i) Formula wherein X ⁹ and X ¹⁰ are the same or different and each represent a chlorine atom, a lower alkoxy, or a lower alkylthio; and (j) a group represented by the formula wherein ^X11 is a hydrogen atom or a chlorine atom, a group selected from the group consisting of aryl groups represented by: ^R1 is _C1 - _C6 alkyl, lower alkenyl, lower alkynyl, or _C3 - _C7 cycloalkyl; and ^R2 is a hydrogen atom or a _C1 - _C6 alkyl; ^R1 and ^R2 may together with the nitrogen atom to which they are attached 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 the substituted aryloxyureas and acid addition salts thereof are represented by:

In the above formula (I), Ar is any one of the groups represented by the above formulas (a) to (j). The groups represented by the formulas (a) to (j) are substituted phenyl ((a) to (f)), pyridyl (g), pyrimidinyl (h), triazinyl (i), and pyrazinyl (j), which are all aromatic groups and share the same orthogonality.

In the group of formula (a), X ¹ is a hydrogen atom, lower alkyl or lower alkoxy.

The lower alkyl is preferably a straight or branched alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n
Examples of the alkyl silyl include n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and t-butyl.

The lower alkoxy is preferably an alkoxy having a straight or branched alkyl moiety having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, t-butoxy, etc.

Examples of the group of formula (a) include 2-chlorophenyl,
2-chloro-5-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2-
Chloro-6-methylphenyl, 2-chloro-5-methoxyphenyl, 2-chloro-6-methoxyphenyl, 2-
Preferred examples include chloro-4-methoxyphenyl and 2-chloro-3-methoxyphenyl.

In formula (b), ^X2 is a hydrogen atom or a halogen atom.

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

Examples of the group of formula (b) include 4-chlorophenyl, 2,
Preferred examples include 4-dichlorophenyl, 2-bromo-4-chlorophenyl, and 4-chloro-2-fluorophenyl.

In formula (c), ^X3 is a halogen atom, and l
is an integer of 2 or 3.

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

Preferred examples of the group of formula (c) include 2,4,5-trichlorophenyl, 3,4,5-trichlorophenyl, 2,3,4-trichlorophenyl, 2,4,6-trichlorophenyl, and 2,3,4,5-tetrachlorophenyl.

In formula (d), X ⁴ is a fluorine atom, a bromine atom, or an iodine atom; and m is an integer of 1, 2, or 3.

Examples of the group of formula (d) include 2-fluorophenyl,
3-fluorophenyl, 4-fluorophenyl, 2,5-
Difluorophenyl, 3,5-difluorophenyl, 2,4-
difluorophenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 2-iodophenyl,
Preferred examples include 4-iodophenyl.

In formula (e), X ⁵ is a hydrogen atom, a halogen atom, a lower alkyl, a lower alkoxy, or trifluoromethyl.

As the halogen atom, the same ones as those exemplified for ^X3 can be mentioned as preferred specific examples.

Preferred examples of lower alkyl and lower alkoxy include those exemplified for X ¹ .

Examples of the group of formula (e) include 2-nitrophenyl, 3 ...
-nitrophenyl, 4-nitrophenyl, 4-chloro-
2-nitrophenyl, 5-chloro-2-nitrophenyl, 5-chloro-2-nitrophenyl, 3-chloro-5
-nitrophenyl, 5-methyl-2-nitrophenyl,
4-methyl-2-nitrophenyl, 3-chloro-4-nitrophenyl, 2-chloro-4-nitrophenyl, 2-
Methyl-6-nitrophenyl, 3-methyl-4-nitrophenyl, 2-methyl-4-nitrophenyl, 2-methyl-5-nitrophenyl, 2-methoxy-5-nitrophenyl, 2-nitro-4-trifluoromethylphenyl, 3-nitro-5-trifluoromethylphenyl, 5
-nitro-2-trifluoromethyl and the like.

In formula (e), ^X6 is a hydrogen atom or a halogen atom.

Preferred examples of the halogen atom include those exemplified for ^X3 .

Examples of the group of formula (e) include 2-cyanophenyl, 3-
-cyanophenyl, 4-cyanophenyl, 3-chloro-
2-cyanophenyl, 4-chloro-2-cyanophenyl, 5-chloro-2-cyanophenyl, 6-chloro-2
-cyanophenyl, 2-chloro-3-cyanophenyl,
4-chloro-3-cyanophenyl, 3-chloro-5-cyanophenyl, 2-chloro-5-cyanophenyl, 3-
Preferred examples include chloro-4-cyanophenyl and 2-chloro-4-cyanophenyl.

In formula (g), X ⁷ is a hydrogen atom, a halogen atom, cyano, lower alkoxy, or trifluoromethyl.

Preferred examples of the halogen atom and lower alkoxy include those exemplified for ^X5 .

Examples of the group of formula (g) include 6-chloro-2-pyridyl, 5-chloro-2-pyridyl, 4-chloro-2-pyridyl, 3-chloro-2-pyridyl, 3,5-dichloro-2-pyridyl,
-pyridyl, 6-methoxy-2-pyridyl, 5-methoxy-2-pyridyl, 4-methoxy-2-pyridyl, 3-
Methoxy-2-pyridyl, 4-trifluoromethyl-2
-pyridyl, 5-trifluoromethyl-2-pyridyl,
6-trifluoromethyl-2-pyridyl, 3-chloro-
5-trifluoromethyl-2-pyridyl, etc. Among these, for example, 6-chloro-2-pyridyl and 6-trifluoromethyl-2-pyridyl are preferred.

In formula (h), X ⁸ is a hydrogen atom, a chlorine atom, or a lower alkylthio, and p is an integer of 1 or 2.

The lower alkylthio is preferably an alkylthio group having a straight or branched alkyl moiety having 1 to 4 carbon atoms, and preferred examples thereof include methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, iso-butylthio, sec-butylthio, and t-butylthio.

Examples of the group of formula (h) include 4-pyrimidinyl, 2-
Preferred examples include chloro-4-pyrimidinyl, 6-chloro-2-pyrimidinyl, 2,6-dichloro-4-pyrimidinyl, 6-chloro-2-methylthio-4-pyrimidinyl, and 2-methylthio-4-pyrimidinyl.

In formula (i), X ⁹ and X ¹⁰ are the same or different and each represents a chlorine atom, a lower alkoxy or a lower alkylthio.

Preferred examples of the lower alkoxy include those exemplified for X ¹ .

As the lower alkylthio, the same as those exemplified for ^X8 can be mentioned as preferred specific examples.

Examples of the group of formula (i) include 4-chloro-6-methoxy-2-triazinyl, 4,6-dimethoxy-2-triazinyl, 4-methoxy-6-methylthio-2-triazinyl, 4-chloro-6-methylthio-2-triazinyl, and 4,6-dimethylthio-2-triazinyl.

In formula (j), ^X11 is a hydrogen atom or a chlorine atom. Examples of the group of formula (j) include a 2-pyrazinyl group, a 3-chloro-2-pyrazinyl group, a 5-chloro-2-
Examples of Ar include a pyrazinyl group and a 6-chloro-2-pyrazinyl group.
Groups represented by (e), (g), (h) and (j) are preferred.

In the above formula (I), R ¹ is C ₁ to C ₆ alkyl, lower alkenyl, lower alkynyl or C ₃ to C ₇ cycloalkyl.
Of these, _C1 - _C6 alkyl and _C3 - _C7 cycloalkyl are preferred.

_C1 - _C6 alkyl may be linear or branched, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an isoamyl group, a sec-amyl group, an activated amyl group, a tert-amyl group,
1,2-dimethylpropyl group, 2,2-dimethylpropyl group,
1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3
-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1
Examples of the alkyl group include a 2-ethylpropyl group and a 2-ethylbutyl group.

The lower alkenyl group is preferably an unsaturated hydrocarbon group having a carbon number of 3 to 5 in the longest carbon chain portion, such as an allyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-butenyl group,
-propenyl group, 2-methyl-2-propenyl group, 1,2
dimethyl-2-propenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, and the like.

The lower alkenyl group is preferably an unsaturated hydrocarbon group having 3 to 5 carbon atoms in the longest carbon chain, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2 ...
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 a _C1 - _C6 alkyl, of which _C1 - _C6 alkyl is preferred.

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

^R1 and ^R2 may be taken together with the nitrogen atom to which they are attached to form a 4- to 8-membered, preferably 6- to 7-membered, alkyl group.
The heterocyclic group may contain an oxygen atom as a ring member and may be substituted with a lower alkyl or lower alkylene. Examples of the lower alkyl substituent include the same as those mentioned above for ^R1 . The lower alkylene 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: Heterocyclic groups containing oxygen atoms: Heterocyclic groups (bicyclic groups) containing lower alkylene groups: Preferred examples of the compounds of the above formula (I) of the present invention include the compounds shown in Table 1 below.

Among the compounds in Table 1 above, compound numbers 1 to 5, 7, 1
1, 16, 17, 21-26, 30, 31, 35-38, 41, 43-45, 4
8, 51, 53, 59-62, 64, 65, 67-72, 74, 76, 77, 7
Compounds 9, 81, 84, 86 to 91 and 93 are more preferred,
Among them, compounds Nos. 2, 3, 7, 11, 21, 22, 43, 44, 53,
60, 62, 64, 65, 68-70, 76, 77, 84, 86-88 and 93
The compound of formula (I) is particularly preferred.

The substance of the present invention may be in a free state or in the form of a salt, for example, an acid addition salt. Acids that form acid addition salts include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; acetic acid, chloroacetic acid, trichloroacetic acid, maleic acid,
An example is an organic acid such as 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, Ar' is (a) in the definition of Ar in formula (I) above.
the definition of ^R1 is the same as in the above formula (I), and ^R21 is a _C1 - _C6 alkyl, and ^R1 and ^R21 may form the same 4- to 8-membered heterocyclic group as the 4- to ₈ -membered heterocyclic group formed by ^R1 and ^R2 in the above formula (I), wherein R ¹ and R ²¹ are defined as in the above formula (I), with a carbamic acid chloride represented by the following formula: in the presence of a base.

In the above formula (II), Ar' is a group selected from the group consisting of aryl groups represented by formulas (a) to (g) in the definition of Ar in the above formula (I), and the definition of ^R21 is also the same as that of ^R2 in the above formula (I).
The only difference is that it does not contain hydrogen atoms.
The definition of ^R1 is the same as in the above formula (I). Therefore, specific examples of the compound of the above formula (II) will be apparent to those skilled in the art from specific examples of the compound represented by the above formula (I).

The compound of formula (II) can be prepared by the methods described in European Patent Application EP-183174, Japanese Patent Application Laid-Open No. 61-126065, Japanese Patent Application No. 60-257691 and Japanese Patent Application No. 61-119293, or essentially in accordance with these methods.

Specific examples of the compound represented by the above formula (III) will also be clear to those skilled in the art from the definitions of R ¹ and R ² in the above formula (I).

The compound of formula (II) and the carbamate 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 and N,N-dimethylaniline are preferably used.

Examples of inorganic bases include NaHCO ₃ , KHCO ₃ , and Na ₂ C
Preferred examples include O ₃ and K ₂ CO ₃ .

In the reaction, 0.8 to 3 moles, preferably 1 to 2 moles of the carbamic acid chloride of the formula (III) is usually used per mole of the compound of the formula (II).
The amount of the hydroxybenzoate used is 1 to 10 moles, preferably 1 to 10 moles.

The reaction temperature is usually −20 to 100° C., preferably −10 to 60° C. The reaction time is usually 30 minutes to 30 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 from the reaction mixture by a conventional method as shown in the Examples below.

According to the present invention, among the compounds of the above formula (I),
The following formula (I)-2 wherein Ar′, R ¹ and R ² are defined as above, and the substituted aryloxyureas represented by the following formula (IV): wherein Ar' is defined as above, and A is a substituted or unsubstituted phenyl, and an aryloxycarbamic acid ester represented by the following formula (V): wherein R ¹ and R ² are defined as in the above formula (I), and the compound can be produced by reacting an amine represented by the formula:

In the above formula (IV), Ar' is defined as above, and A is a substituted or unsubstituted phenyl. Preferred examples of the substituted phenyl include halogenated phenyls such as chlorophenyl and lower alkyl-substituted phenyls such as tolyl.

The aryloxycarbamic acid ester of formula (IV) can be prepared by reacting, for example, the aryloxyamine of formula (II) with a compound of formula AOCOCl in the presence of a base and a solvent. The base and solvent may be the same as those exemplified in the method for preparing the compound of formula (I)-1.

In the above formula (V), the definitions of ^R1 and ^R2 are the same as in the above formula (I).

In the reaction, the amine of formula (V) is usually used in an amount of 0.8 to 1 mole per mole of the aryloxycarbamic acid ester of formula (IV).
5 moles, preferably 1 to 3 moles are used.

The reaction temperature is usually 0 to 100° C., preferably 0 to 80° C. The reaction time is usually 30 minutes to 5 hours. The reaction is preferably carried out under stirring.

The reaction is preferably carried out in a solvent.
The same amines as those exemplified in the above method for producing the compound of formula (I)-1 can be used. When using an amine of formula (V) in which ^R2 is _C1 - _C6 alkyl,
It is particularly desirable to use dimethylformamide as the reaction solvent.

Furthermore, according to the present invention, among the compounds of the above formula (I), the compound of the following formula (I)-3 wherein Ar" is a group selected from the group consisting of aryl groups represented by formulas (h), (i) and (j) in the definition of Ar in the above formula (I), and the definitions of ^R1 and ^R2 are the same as in the above formula (I). The substituted aryloxyureas represented by the following formula (VI): wherein ^X8 and p are defined as in the above formula (I), a chlorinated pyrimidine represented by the following formula (VII): wherein ^X9 and ^X10 are defined as in the above formula (I), and a triazine chloride represented by the following formula (VIII): wherein ^X11 is defined as in the above formula (I), and a chloride selected from the group consisting of chlorinated pyrazines represented by the following formula (IX): wherein R ¹ and R ² are defined as in the above formula (I), in the presence of a base.

In the above formula (VI), the definitions of ^X8 and p are the same as in the above formula (I), the definitions of ^X9 and ^X10 in the above formula (VII) are the same as in the above formula (I), and the definition of ^X11 in the above formula (VIII) is the same as in the above formula (I).

Therefore, the pyrimidine chlorides of the formula (VI), the formula (VII)
Specific examples of the chlorinated triazines of formula (VIII) and the chlorinated pyrazines of formula (VIII) will be apparent from the above specific examples of X ⁸ , p, X ⁹ and X ¹⁰ .

In the above formula (IX), the definitions of R ¹ and R ² are the same as in the above formula (I), and specific examples of the N-nitroxyureas of formula (IX) will therefore be clear from those specific examples.

The reaction involves the addition of chlorinated pyrimidines of formula (VI) and chlorinated pyrimidines of formula (VI)
Usually, 0.8 to 5 moles, preferably 1 to 2 moles of the N-hydroxyurea of formula (IX) are used per mole of the chloride selected from the triazine chlorides of I).

The reaction temperature is usually −50° C. to 50° C., preferably −30° C.
The reaction temperature is usually between 30 minutes and 10 hours.

The reaction is preferably carried out under stirring.

The base used in the reaction is the compound represented by the above formula (I)-
The same methods as those exemplified in the method for producing the compound represented by formula 1 can be used.
Preferably, alkali metal alkoxides such as sodium ethoxide and potassium t-butoxide can be used.

The base is used in an amount of usually 0.5 to 10 moles, preferably 1 to 5 moles, per mole of the chloride used.

The reaction can be carried out in the absence or presence of a solvent, and the same solvents as those exemplified in the production method of the compound of formula (I)-1 can be used.

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

Therefore, according to the present invention, there is also provided a herbicide containing the substituted 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. Even 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, when applied at the time of germination and the growing season, exhibits superior herbicidal effect to annual weeds such as barnyard grass, Cyperus galli, Monochoria vaginalis, Rottb. gracilis, Lindernia gracilis, and Ardisia gracilis that occur in paddy fields, as well as to perennial weeds such as Scirpus bulrush, Cyperus serotinus, and Ardisia gracilis, compared with commercially available herbicides. On the other hand, it has extremely high selectivity, causing no phytotoxicity even at high doses to effective crops, particularly paddy rice. The herbicide of the present invention can also be applied to various weeds that are problematic in upland fields, such as barnyard grass, Digitaria adscendens, Setaria viridis, Poa annua, and others.
The herbicide of the present invention is characterized by its high herbicidal effect against grass weeds such as alopecia, sedge weeds such as sedge, and broadleaf weeds such as pigweed and lamb's quarter weed, when applied to the soil or foliage, and is also highly safe for use on major crops such as rice, wheat, corn, soybean, cotton, etc. Furthermore, the herbicide of the present invention can also be used as a herbicide for orchards, pastures, lawns, and non-agricultural lands.

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

Examples Example 1A 1,1-hexamethylene-3-(3-nitrophenoxy)
Urea (Compound No. 1) 3.02 g (19.6 mmol) of 3-nitrophenoxyamine was dissolved in 7.9 ml of pyridine, and then 4.75 g (29.4 mmol) of N,N-hexamethylenecarbamoyl chloride was added. The mixture was stirred at 25°C for 10 hours and then at 35-40°C for 6.5 hours. 150 ml of saturated brine was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, and the ethyl acetate was removed under reduced pressure. The residue was recrystallized from toluene-hexane to obtain 3.92 g of the target product as yellow crystals (72% yield).

Melting point: 97-99°C Mass spectrum (FD method): m/z 279 (molecular ion peak) IR spectrum (KBr tablet method, cm ^-1 ): 3130, 1643, 530, 1474, 1347, 736 ^1H -NMR spectrum ( _CDCl3 solution, ppm) (a) 1.5-2.0 (8H, m) (b) 3.44 (4H, m) (c) 7.2-7.9 (4H, m) (d) 7.96 (1H, s) Example 2A 1-Cyclopentyl-3-(5-methyl-2-nitrophenoxy)urea (Compound No. 2) 3.86 g (13.4 mmol) of N-(5-methyl-2-nitrophenoxy)carbamic acid phenyl ester was dissolved in 60 ml of ethyl acetate.
After dissolving in 1 ml of water, 2.85 g of cyclopentylamine (33.5 mm
100 ml) was added and stirred at 60°C for 1.5 hours. After cooling to room temperature, the reaction mixture was washed with 3% aqueous sodium hydroxide solution and then saturated brine, and dried over anhydrous magnesium sulfate. After removing the ethyl acetate under reduced pressure, the residue was recrystallized from toluene-hexane to obtain 1.83 g of the target product as yellow crystals (yield 49%).

Melting point: 131-132°C (decomposition) Mass spectrum (FD method): m/z 279 (molecular ion peak) IR spectrum (KBr tablet method, cm ^-1 ): 3390, 1660, 1605, 1590, 1340, 1310, 1260, 1240 ^1H -NMR spectrum ( _CDCl3 solution, ppm) (a) 1.4-2.2 (8H, m) (b) 2.44 (3H, s) (c) 4.16 (1H, m) (d) 6.74 (1H, d, J = 7.2 Hz) (e) 6.98 (1H, dd, J = 8.3, 1.3 Hz) (f) 7.48 (1H, d, J = 1.3 Hz) (g) 7.82 (1H, d, J = 8.3 Hz) (h) 8.7 (1H, br.s) Example 3A 3-(3-Cyanophenoxy)-1,1-hexamethyleneurea (Compound No. 3) 2.10 g (8.3 mmol) of N-(3-cyanophenoxy)carbamic acid phenyl ester was dissolved in N,N-dimethylformamide 2.
The resulting solution was dissolved in a mixed solvent of 0 ml of hexane and 20 ml of toluene, and then 1.64 g (16.5 mmol) of hexamethyleneimine was added and stirred at 60°C for 1 hour. After the reaction mixture was cooled to room temperature, 120 ml of water was added and the mixture was extracted with ethyl acetate. 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 purified by silica gel column chromatography (elution solvent: ethyl acetate-hexane).
Further recrystallization from toluene-hexane gave 2.05 g of the target product as pale yellow crystals (yield 91%).

Melting point: 77-79°C Mass spectrum (FD method) m/z 259 (molecular ion peak) IR spectrum (KBr pellet method, cm ^-1 ) 3285, 2230, 1656, 1575, 1482, 1405, 1241, 1205, 80
0,684 ^1H -NMR spectrum ( _CDCl3 solution, ppm) (a) 1.4-2.0 (8H, m) (b) 3.40 (4H, m) (c) 7.36 (4H, m) (d) 8.04 (1H, s) Example 4A 3-(2-chloro-4-pyrimidinyl)-1,1-pentamethyleneurea (Compound No. 4) 3.00 g (20.1 mmol) of 2,4-dichloropyrimidine and 3-
Hydroxy-1,1-pentamethylene urea 2.90 g (20.1 mmol)
l) was dissolved in 40 ml of N,N-dimethylformamide (DMF), cooled to -25°C, and then potassium t-butoxide was added.
A 20 ml DMF solution of 2.26 g (20.1 mmol) of the product was added dropwise over 25 minutes. After stirring at -25 to -10°C for 3 hours, 250 ml water was added and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, and then
The residue obtained by distilling off the ethyl acetate under reduced pressure was purified by silica gel column chromatography (eluent: ethyl acetate-hexane) and further recrystallized from toluene-hexane to obtain 0.78 g of the target product as colorless crystals (yield 15%).

Melting point: 136-138°C Mass spectrum (FD method) m/z 259 (molecular ion peak) IR spectrum (KBr pellet method, cm ^-1 ) 3200, 1660, 1555, 1510, 1408, 1347, 1294, 1265, 12
52, 1220, 1210, 1192, 1076, 1015, 978, 910, 862, 8
40, 765, 720 ^1H -NMR spectrum ( _CDCl3 solution, ppm) (a) 1.65 (6H, m) (b) 3.44 (4H, m) (c) 6.96 (1H, d, J = 5.7 Hz) (d) 8.42 (1H, d, J = 5.7 Hz) (e) 8.78 (1H, s) Examples 5A to 80A Target compounds 5 to 80 listed in Table 1 were synthesized from the corresponding starting materials in the same manner as in Examples 1A to 4A. The results are shown in Table 1A.
B, C, and D correspond to the preparation methods described in Examples 1A, 2A, 3A, and 4A, respectively.

The herbicides of the present invention will now be described with reference to formulation examples, in which "%" 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 14-32 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% Raymond Morillonite mixture are uniformly mixed and ground. 78 parts of this mixture are mixed with 22 parts water and kneaded, processed into 14-32 mesh powder 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% 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 cyclohexanenone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate, and methylnaphthalene
Dissolve 35% homogeneously to make 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 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 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 Formulation 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) 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 5C.

Test Example 5C (Herbicidal test by foliar application to field crops) 120 ^cm2 plastic pots were filled with field soil, and seeds of barnyard grass, crabgrass, red spider lily, and sedge were sown. The barnyard grass was then grown in a greenhouse until it reached the three-leaf stage. At the three-leaf stage, the test compound was made into a wettable powder according to Formulation Example 3B, diluted with water at an amount equivalent to 4 kg of active ingredient per hectare, and sprayed from above the foliage of the plants using a small sprayer at a spray rate of 1,000 liters per hectare. After spraying, the plants were grown in a greenhouse for 20 days, and their herbicidal activity was evaluated 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 (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 Formulation Example 3B, and the specified amount was diluted with water. The mixture was 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 11C.

Test Example 11C (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 m² of 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 12C.
As shown in the table.

───────────────────────────────────────────────────────── Continued from the front page (51) Int.Cl. ⁵ Identification symbol Internal reference number FI Technical marking location C07D 241/18 251/30 295/12 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 (8)

[Claims] Claim 1: A compound represented by the following formula (I): Here, Ar is represented by the formula (a) wherein X ¹ is a hydrogen atom, a lower alkyl, or a lower alkoxy; (b) Formula wherein ^X2 is a hydrogen atom or a halogen atom; (c) Formula where ^X3 is a halogen atom and l is 2 or 3.
(d) is an integer of wherein ^X4 is a fluorine atom, a bromine atom, or an iodine atom, and m is an integer of 1, 2, or 3; wherein ^X5 is a hydrogen atom, a halogen atom, a lower alkyl,
(f) a group of formula (I) which is lower alkoxy or trifluoromethyl; wherein ^X6 is a hydrogen atom or a halogen atom; (g) Formula wherein ^X7 is a hydrogen atom, a halogen atom, cyano, lower alkoxy, or trifluoromethyl; (h) Formula wherein ^X8 is a hydrogen atom, a chlorine atom or a lower alkylthio, and p is an integer of 1 or 2; (i) Formula wherein X ⁹ and X ¹⁰ are the same or different and each represent a chlorine atom, a lower alkoxy, or a lower alkylthio; and (j) a group represented by the formula wherein ^X11 is a hydrogen atom or a chlorine atom, a group selected from the group consisting of aryl groups represented by: ^R1 is _C1 - _C6 alkyl, lower alkenyl, lower alkynyl, or _C3 - _C7 cycloalkyl; and ^R2 is a hydrogen atom or a _C1 - _C6 alkyl; ^R1 and ^R2 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, and acid addition salts thereof. Claim 2: In the above formula (I), Ar is represented by formula (a):
(d), (e), (g), (h) and (j), wherein R ¹ is C ₁ -C ₆ alkyl or C ₃ -C ₇ cycloalkyl, and R ² is C ₁ -C ₆ alkyl, or R ¹ and R ² are selected from the group consisting of
together with the nitrogen atom to which they are attached,
2. The compound according to claim 1, which forms a 7- to 7-membered heterocyclic group. [Claim 3] A compound described in claim 1, wherein in the above formula (I), Ar is formula (g), and ^R1 and ^R2 together form a 6- to 7-membered heterobase together with the nitrogen atom to which they are attached. 4. In the above formula (I), Ar is 6-chloro-
2-pyridyl or 6-trifluoromethyl-2-pyridyl, and The compound according to claim 1, wherein Claim 5: A compound of the following formula (II): Ar'-ONH ₂ ... (II) wherein Ar' is (a) in the definition of Ar in the above formula (I).
The aryloxyamine represented by the formula (III) is a group selected from the group consisting of aryl groups represented by the formulas (I) to (G). wherein ^R1 is defined as in the above formula (I), ^R21 is a _C1 - _C6 alkyl, and ^R1 and ^R21 may form the same 4- to 8-membered heterocyclic group as the 4- to 8-membered heterocyclic group formed by ^R1 and ^R2 in the above formula (I), with a carbamic acid chloride represented by the following formula (I)-1, wherein Ar', ^R1 and ^R21 are defined as above. Claim 6: A compound represented by the following formula (IV): wherein Ar' is defined as in the above formula (II), and A is a substituted or unsubstituted phenyl, and an aryloxycarbamic acid ester represented by the following formula (V): wherein ^R1 and ^R2 are defined as in the above formula (I), wherein Ar', ^R1 and ^R2 are as defined above. Claim 7: A compound represented by the following formula (IV): wherein ^X8 and p are defined as in the above formula (I), wherein ^X9 and ^X10 are defined as in the above formula (I), and a triazine chloride represented by the following formula (VIII): wherein ^X11 is defined as in formula (I) above, and a chloride selected from the group consisting of: wherein ^R1 and ^R2 are defined as in the above formula (I), and an N-hydroxyurea represented by the following formula (I)-3 is reacted in the presence of a base. wherein Ar″ is a group selected from the group consisting of aryl groups represented by formulas (h), (i) and (j) in the definition of Ar in formula (I) above, and the definitions of ^R1 and ^R2 are the same as in formula (I) above. 8. A herbicide comprising the substituted aryloxyurea represented by the above formula (I) or an acid addition salt thereof as an active ingredient.