CA1304382C - Substituted phenyl (or pyridyl) urea compound and herbicidal composition containing the same as active ingredient - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:
The present invention relates to a substituted phenyl(or pyridyl)urea compound and a herbicidal composition containing the substituted phenyl(or pyridyl)urea compound as an active ingredient. The compound of the present invention is of the formula:
(I) wherein A represents an alkylene group; B represents a nitrogen atom or CH; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; R1, R2, R3 and R4 independantly represent a hydrogen atom or a methyl group;
and n is 0 or 1.

Description

1.3t3~32 TITLE OF THE INVENTION:
SUBSTITUTED PHENYL(OR PYRIDYL)UREA COMPOUND
AND HERBICIDAL COMPOSITION CONTAINING THE
SAME AS ACTIVE INGREDIENT

BACKGROUND OF THE INVENTION:
The present invention relates to a substituted phenyl(or pyridyl)urea compound and a herbicidal composition containing the substituted phenyl(or pyridyl)urea compound as an active ingredient.

~.3~3~

It has already been known that a phenoxyphenylurea derivative has a herbicidal activity (Belgian Patent No.
593743), and that a benzyloxyphenylurea derivative has a herbicidal activity (Japanese Patent Application Laid-Open (XOKAI) No. 53-44544 (1978)). It is also known that a phenethyloxyphenylurea derivative has a herbicidal activity (Japanese Patent Application Laid-Open (KOKAI) No. 53-108947 (1978)), and that a benzyloxypyridylurea and a phenethyl-oxypyridylurea derivativa have a herbicidal activity (Japanese Patent Application Laid-Open (KOKAI) No. 55-122764 (1980)). Furthermore, it is known that a benzopyranyl-oxyphenylurea derivative has a herbicidal activity (PCT
Patent Application Laid-Open No. W087/00840). These compounds, however, are insufficient in the selectivity to crops or the strength of the herbicidal activity. Chemical substances (compounds) are very often changed in the presence or absence of the herbicidal activity, or the strength of the herbicidal activity, or in the selectivity of the herbicidal function by slightly chang~ng the structure thereof. It iq, therefore, difficult to forecast in advance the herbicidal activity or the selectivity of a new compound merely from the similarity of a chemical structure.
On the other hand, Japanese Patent Application Laid-Open (KOKAI) No. 57-158753 (1982) discloses compounds containing in the chemical structure a benzofuranyl-~.~fv~4 3 ~

oxyphenylurea component as a bicyclooxyphenylurea havingan insecticidal activity. These are, however, compounds having an insecticidal activity and no relationship to the above-described urea derivatives having a herbicidal activity is disclosed in Japanese Patent Application Laid-Open (KOKAI) No. 57-158753 (1982).
Accordingly, the development of a substituted phenyl(or pyridyl)urea derivative exhibiting a high herbicidal effect in upland field and paddy field and having an excellent selectivity so as to do no practical harm to the crops has been in strong demand.
As a result of studies of the present inventoxs it'has been found that a compound represented by the following general formula (I):

R (CH2~ A -- O ~NHCN <
R3 R4 (I) wherein A represents an alkylene group1 3 represents a nitrogen atom or CH; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; Rl, R2, R3 and R4 independantly represent a hydrogen atom or a methyl group;
and n is 0 or 1, is capable of controlling weeds in upland fields, such as lambsquarters (Chenopodium album), goosefoot (Chenopodium album var. centrorubrum), persicaria 3~32 blumei gross (Polygonum blumei), ladysthumb (Polygonum persicaria), livid amaranth (Amaranthus lividus), common purselane (Portulaca oleracea), common chickweed (Stellaria media), dead-nettle (Lamium amplexicaule), large crabgrass (Digitaria sanguinalis), goosegrass (Eleusine indica), green foxtail (Setaria viridis), water foxtail (Alopecurus aequalis) and flat-sedge (Cyperus microiria) and weeds in paddy fields, such as false pimpernel (Lindernia procumbens), toothcup (Rotala indica), abunome (Dopatrium junceum), american waterwort (Elatine triandra), narrowleaf waterplantain (~lisma canaliculatum), barnyardgrass (Echinochloa crus-galli L. Beauv. var. crus-galli), umbrella plant (Cyperus difformis) and duck-tongue weed (Monochloria vaginalis) by the preemergence treatment or by the treatment during the growing stage, and in addition, do no practical harm to crop plants such as rice (Oryæa sative), sunflower (Helianthus annuus), potato (Salanum tubero~um), wheat (Triticum aestivum), barley (Hordeum vulgare), sugar cane (Saccharum oficinarum), and corn (Zea mays). On the basis of this finding, the present invention has been attained.

SUMMARY OF THE INVENTION:
In a first aspect of the present invention there i9 provided a compound represented by the following general formula (I):

Rl 0 CH3 R ( C~} ~NHCN <

R3 R (I) wherein A represent~ an alkylene group; B represents a nitrogen atom or CH; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; Rl, R2, R3 and R4 independantly represent a hydrogen atom or a methyl group;
and n is 0 or 1.
In a second aspect of the present invention, there is provided a herbicidal composition comprising as an active ingredient a herbicidally effective amount of compound represented by the following general formula:

~ 3~343~Z

wherein A represents an alkylene group; B represents a nitrogen atom or CH; R represents a hydrogen atom, a lower-alkyl group or a lower alkoxy group; Rl, R2, R3 and R4 independantly represent a hydrogen atom or a methyl group; and n is O or 1, and a herbicidally acceptable carrier or adjuvant.

~ 3(;~ 2 DESCRIPTION OF THE PREFERRED EMBODIMENTS:
_ A substituted phenyl(or pyridyl)urea compound according to the present invention is a novel compound represented by the following general formula (I) Rl O /NH CH3 R (CH2 ~ A - O ~
R3 R (I) wherein A represents an alkylene group; B represents a nitrogen atom or CH; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; Rl, R , R3 and R4 independantly represent a hydrogen atom or a methyl group; and n is O or 1.
As compounds represented by the general formula (I), the following novel compounds represented by the general formula (II) to (V), respectively, may be exemplified.
(1) An N'-aryl-N-methylurea derivative represented by the following general formula (II):

A-O ~ NHCN ~R

..... (II) wherein A represents an alkylene group; and R represents 1.3~ 2 a hydrogen atom, a lower alkyl group or a lower alkoxy group.

(2) An N'-phenyl-N-methylurea derivative repre-sented by the following general formula (III):

Rl A-O ~ < R

wherein A represents an alkylene group; R represents a hydrogen atom, a lower alkyl group or a lowe~ alkoxy group;
and R1 represent5 a hydrogen atom or a methyl group.

(3) An N'-(S-pyridyl)-N-methylurea derivative represented by the following general formula (IV):

~ A-O ~ ¦¦ <CH3 wherein A repre~ents an alkylene groUp; and R reprecents a hydrogen atom, a lower alkyl group or a lower alkoxy group.

(4) An N'-phenyl-N-methylurea derivative represented by the following general formula (V):

NH~CN ~ 3 A-O ~ (V~

~.3(~4313~

wherein A represents an alkylene group; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group;
and Rl, R2, R3 and R4 independantly represent a hydrogen atom or a methyl group.
In the general formula (I), A represents an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. As an alkylene group, straight-chain or branched alkylene group such as, for example, CH2 ' -CH2CH2-, ,CIH3 , CH2CH2CH2 ' -CH--CH-CH2-, -cH2cH2cH2cH2-~ and -CH-CH2CH2- , preferably -CH2-, -CH2CH2-CIH3and CH-CH2-, may be exemplified.

In the general formulae (II) to (V), R represents a hydrogen atom; a lower alkyl group, preferably (Cl - C4) alkyl group, more preferably methyl group; or a lower alkoxy group, preferably (Cl - C4) alkoxy group, more preferably methoxy group. Rl, R2, R3 and R4 respectively represent a hydrogen atom or methyl group.

_ g Preferred compounds of a substituted phenylurea compound represented by the general formula (II) are shown in Table 1. Further, compounds represented by the formula (II) wherein A represents a methylene group, an ethylene group or a propylene group; and R reprefients a methyl group or a methoxy group are preferable. Among these, compounds Nos. 3, 4, 8, 9, 20, 21, 26, 28 and 29 are more preferable.
Preferred compounds of a substituted phenylurea compound represented by the general formula (III) are shown in Tables 2 and 3. Further compounds represented by the formula (III) wherein A represents an ethylene group or a propylene group, R represents a methyl group or a methoxy group;
and R represents a methyl group are preferable. Among these, compounds Nos. 43, 44, 45, 49, 52 and 53 are more preferable.
Preferred compounds of a substituted pyridylurea derivative represented by the general formula tIV) are compounds Nos. 54 to 57. Fw~her, compounds represented by the formula (IV) wherein A represents a methyl group; R
represents a methyl group are preferable. Among these, compound No. 56 is more preferable.
preferred compounds of a substituted phenylurea derivative represented by the general formula (V) are shown in Tables 4 to 7. Further, compounds represented by the ,~

3~2 the formula (V) wherein A represents a ethylene group or a propylene group; R represents a methyl group or a methoxy group; Rl and R2 respectîvely represent a hydrogen atom or a methyl group; and R3 and R4 respectively represent a hydrogen atom are preferable. Among these, compound Nos. 61, 73, 85, 93, 101 and 102 are more preferable.
(l) A compound represented by the general formula (II) according to the present invention is a novel compound and can be produced from various materials, for example, in accordance With the following reaction schemes.

(i) A-0 ~ + ZCN <
(VI) base¦¦ CH3 ~ k~ ~ NHC ~

(II) (wherein A and R are as defined above, and Z repre5ents a halogen atom) The above-described reaction is carried out without any 901vent o~ in a solvent selected from the group consisting of: ketone9 such as acetone and ethylmethyl ketone; aromatic hydrocarbons suc,h as benzene and toluene;
ethers such as diethyl ether and tetrahydrofuran; and aprotic polar solvents such as acetonitrile, N,N-dimethyl-1.3~43~12 formamide, dimethyl sulfoxide and N-methylpyrrolidone at 0 to 150C, preferably 0 to 50C for 0.5 to 6 hours in the presence of an organic base such as triethylamine, pyridine and N,N-diethylanilinej or an inorganic ba~e such as sodium carbonate and sodium hydroxide.
(ii) k ~ A-O ~ +HN ~ 3 (VII) (wherein ~ and R are as defined above) The above-described reaction is carried out without any solvent or in a solvent selected from the group consisting of: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; acetate8 such as ethyl acetate and iso~utyl acetate; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; aprotic polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; ketones such as acetone and ethylmethyl ketone; alcohols such as methanol, ethanol and butanol; water; and a mixed solvent thereof at -50 to 100C, preferably 0 to 50C for 0.5 to 12 hours.

131D438~

An isocyanate (VII), which is the starting material for the above-described reaction can be produced from an aniline derivative (VI~, which is the starting material for the reaction represented by the reaction scheme (i) in accordance with the following reaction scheme:

NH

(VI) COCl2 NC0 - > ~ ~ A-0 (VII) (wherein A is as defined above) The above-described reaction is carried out in a solvent selected from the group consisting of: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; acetates such as ethyl acetate and isobutyl acetate; and ethers such as die~hyl ether, diisopropyl ether, tetrahydrofuran and dioxane at -20 to 18nC, preferably 0 to 120C for 2 to 15 hours in the presence or absence of an organic base such as triethylamine, pyridine, quinoline, N,N-diethylaniline.

~3~1438Z
(iii) o Il / CH3 NHCN
A-Y + H0 ~ \ R
(VIII) (IX) base 1¦ ~CH3 ~ A-0 ~ N(HII)N ~R
(wherein A and R are as defined above, and Y represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group~.
The above-described reaction is carried out without any solvent or in a solvent selected from the group consisting o~: ketones such as acetone and ethylmethyl ketone; aromatic hydrocarbons such as benzene and toluene;
ethers such as diethyl ether and tetrahydrofuran; and aprotic polar solvents such as acetonitrile, N,N-dimethyl-formamide, dimethyl sulfoxide and N-methylpyrrolidone at 0 to 150C, preferably 0 to 120C for 1 to 6 hours in the presence of an organic base such as triethylamine, pyridine and N,N-diethylaniline, an inorganic base such as sodium carbonate and sodium hydroxide, an alkali metal h~dride such as sodium hydride or an alkali metal such as metal sodium.
An aniline derivative (VI), which is a starting material for the reactions shown in (i) and (ii) can be produced in accordance with the following reaction scheme (a), (b) or (c).

~3C~3&2 a) NO

k~3A-oH + z ~

base N02 > >~A-O ~3/

reduction NH2 ~X~A O~/
(VI j (wherein A and Z are as defined above) (b) k ~A-Y + HO ~ NO~ b~se A-O ~

reduction NH2 A-O
(VI) (wherein A and Y are as defined above) ~3Q4382 (c) A-O ~ CH =C-CH2Cl base CH2-C-CH2O ~ A-O ~ 2 heating A-O ~ 2 reduction >

>~3 A- O ~J' (VI ) (wherein A and Z are as defined above) ~ 2) A compound represented by the formula (III) according to the present invention i8 a novel compound, and can be pxoduced from various materlals by a process shown in ~1).
For example, (i) ~ ~ A-O ~ + ZCN ~ 3 base O
3~1 NHIlN~ 3 0 - 150C ~ A- ~ R (III) 13~43&~

(wherein A, R and Rl are as defined above, and Z represents a halogen atom) (ii) .

H A-O ~ + HN~ 3 ~XI) 1 ll CH3 R ~ o ~ NHCN ~
-50 - 100C H ~ A-O ~ (III) (wherein A, R and Rl are as defined above) An isocyanate derivative (XI), which is the starting material for the above-described reaction can be produced from an aniline derivative (X), which i9 the starting material for the reaction represented in accordance with a process shown in (1):
For example, R

( X ) ~

H ~ A-O ~ NCO

(XI) 13~,~43~3Z

(wherein A and Rl are as defined above) (iii) Rl NHIlN~ CH3 H ~ + HO ~ R

(XII) (IX) base O

1 NHCN ~
0 - 150C ~ O ~ / R

H A-O ~ (III) ~wherein A, R and Rl are as defined above, and Y represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group) An aniline derivative (X), which is a starting material for the reactions represented by the reaction schemes (i) and (ii) can be produced by the following process (a) or (b):
(a) R A-OH base A-O ~ 2 reduction 13~43&;~

Rl H~A-o~3/ NH2 (X) (wherein A, R and R are as defined above) (b) Rl N02 Rl + HO ~ base ~ k ~ A-o ~ 2 reduction Hk ~
(X) (wherein A, R and Rl are as defined above) (3) A compound represented by the general formula (IV) according to the present invention is a novel compound and can be produced from various materials, for example, in accordance with the following reaction schemes.

~.3Q~iZ

(i) o A-0 ~ NH2 + ZCN ~ H3 (XIII) base 0 > ~ A-0 ~ ~ R

. (IV) (wherein A and R are as defined above and Z represents a halogen atom) The above-described reaction is carried out without any solvent or in a solvent selected from the group consisting of: ketones such as acetone and ethylmethyl ketone; aromatic hydrocarbons such as benzene and toluene;
ethers such as diethyl ether and tetrahydrofuran; and aprotic polar solvents such as acetonitrile, N,N-dimethyl-formamide, dimethyl sulfoxide and N-methylpyrrolidone at 0 to 150C, preferably 0 to 50C for 0.5 to 6 hours in the presence of an organic base such as triethylamine, pyridine and N,N-diethylaniline, or an inorganic base such as sodium carbonate and sodium hydroxide.

1 3~3~

ii) ~ A-O - ~ NCO ~ HN ~ 3 XIV) o A-O ~ ~R

(IV) (wherein A and R are as defined above) The above-described reaction is carried out without any solvent or in a solvent ~elected from the group consisting of: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; acetates such as ethyl acetate and isobutyl acetate; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxanei aprotic polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; ketones such as acetone and ethylmethyl ketone; alcohols such as methanol, ethanol and butanol; water; and a mixed solvent thereof at -50 to 100C, preferably 0 to 50C for 0.5 to 12 hours.
An isocyanate derivative (xr~, which is a starting material for the above-described reaction can be produced from an aniline derivative (XIII), which is a starting material for the reaction represented by the reaction scheme (i) in accordance with the following reaction scheme:

~.3Q~

A-O - ~ NH2 (XIII) A-O ~ NCO
(XIV) (wherein A is as defined above) The above-described reaction is carried out in a solvent selected from the group consisting of: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene1 acetates such as ethyl acetate and isobutyl acetate; and ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane at -20 to 180C, preferably 0 to 120C for 2 to 15 hours in the presence or absence of an organic base such as triethylamine, pyridine, ~uinoline and N,N-diethylaniline.
An aniline derivative IXIII), which is a starting material for the reactions represented by the reaction schemes ~i) and (ii) can be produced by the following process:

X ~ A-OH + Z- ~ NO2 base 3~ ~A-O--~ N02 reduction '> k~A-O~NH2 (XIII) ~ 3~ 3~;~

(wherein A and Z are as defined above) (4) A compound represented by the formula (V) according to the present invention is a novel compound, and can be produced from various materials by a process shown in (1).
For example, (i) Rl NH2 O

R2 ~ A-O ~ XCN ~ R

R3 R4 (XV) Rl NH 1I N ~ 3 base ~ A-O ~ R

~wherein A, R, Rl, R2, R3 and R4 are as defined above, and X represents a halogen atom) (ii) Rl NCO

R2 ~ A-O ~ ~ HN~R

R3 R (XVI) o Rl NHCN ~CH3 ~ R ~ ~ A O ~ R
-50 - 100C ~ ~ (V) i A R Rl R2 R3 and R4 are as defined above) ~..3~ 2 An isocyanate derivative (XVI), which is a starting material for the above-described reaction can be produced from an aniline derivative (XV), which is a starting material for the reaction represented by the reaction scheme (V) in accordance with the following reaction scheme:

Rl NH

R2~A-O ~/ COC12 R R4 (XV) Rl NCO

R~A(-XoV~

(wherein A, Rl, R2, R3 and R4 are as defined above) (iii) O
Rl NH 1I N~ 3 R ~ A-Y ~ HO ~ R
R3 R4 (XVII) (IX) base Rl NHCN ~CH3 ~ R2 ~ ~ ~ (VL
(wherein A, R, Rl, R2, R3 and R4 are as defined above, and Y represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group) 1.3~ 3~Z

An aniline derivative (XV), which is a starting material for the reactions represented by the reaction schemes (i) and (ii) can be produced by the following process (a) or (b):

(a) Rl NO

R ~ A-OH + X ~ base Rl NO

R2 ~ A-O ~ reduction Rl NH
2 / ~ A-O ~ 2 3 4 (XV) R R
(wherein A, Rl, R2, R3, R4 and X are as defined a~ove) (b) R ~ N02 Rl / NO
R ~ A-O ~ 2 reduction Rl NH
R2 ~ A-O ~ 2 R3 R4 (XV) 13~g382 (wherein A, Rl, R2, R3, R4 and Y are as defined above) The thus-obtained compound according to the present invention can be used singly as a herbicide, but ordinarily, it is mixed with an inactive liquid or solid carrier and an appropriate surfactant or the like is added thereto so as to be used in the form of a composition such as emulsion, dust, granules and wettable powder.
As a liquid carrier, for example, toluene, xylene, methylnaphthalene, cyclohexane, butanol, glycol, dimethylsulfoxide, dimethylformamide, acetone, methyl-isobutyl ketone, animal and vegetable oils, fatty acids, fatty esters and water are usable. As a solid carrier, for example, clay, kaolin clay, talc, bentonite, diatomaceaous earth, silica, calcium carbonate, and vegetable flour such as soy bean flour and wheat flour are usable. Further, if necessary, the compound may be mixed before use with other active ingredients such as an agricultural germicide, insecticide and nematicide, or another herbicide, plant growth regulating agent, soil conditioner, and fertilizer.
The compound also may be appropriately mixed with an adjuvant such as a spreader, emulsifier, wetting agent and fixing agent.
The appropriate amount of herbicidal composition of the preRent invention for u~e is different depending upon the kind of the compound used, weeds being killed, treating season, treating method, and the nurture of the 13~43~

soil, but the appropriate range is generally 0.5 to 80 g/are, preferably 1 to 50 g/are as an active ingredient.
A compound of the present invention shows a high herbicidal activity in upland field and paddy field without doing no practical harm to crops. More specifically, the herbicidal compositions containing the compounds of the present invention as active ingredients are capable of controlling weeds in upland fields, such as lambsquarters (Chenopodium album), goosefoot (Chenopodium album var.
centrorubrum), persicaria blumei gross (Polygonum blumei), ladysthumb (Polygonum persicaria), livid amaranth (Amaranthus lividus), common purselane (Portulaca oleracea), common chickweed (Stellaria media), dead-nettle (Lamium amplexicaule), large crabgrass (Digitaria sanguinalis), goosegrass (Eleu-sine indica), green foxtail (Setaria viridis), water foxtail (Alopecurus aequalis) and flat-sedge (Cyperus microiria) and weeds in paddy fields, such as false pimpernel (Lindernia procumbens), toothcup (Rotala indica), abunome (Dopatrium junceum), american waterwort tElatine triandra), narrowleaf waterplantain (Alisma canaliculatum), barnyardgrass (Echinochloa crus-galli L. Beauv. var.
crus-galli), umbrella plant (Cyperus difformis) and duck-tongue weed (Monochloria vaginalis) by the preemergence treatment or by the treatment during the growing stage.
Further, the compounds of the present invention can be used as selective herbicides for the cultivation of crop plants such as rice (Oryza sative), sunflower (Helianthus annuus), potato (Salanum tuberosum), wheat (Triticum aestivum), barley (Hordeum vulgare), sugar cane (Saccharum officinarum), and corn (Zea mays).
As described above, the compound of the present invention is excellent in that it is capable of controlling a number of weeds without substantially adversely affecting the crop plants.
Furthermore, the compound of the present invention has been proved to have a high herbicidal activity against weeds which have hitherto been considered to be difficult to hardly control, namely, weeds in upland field such as velvetleaf (Abutilon theophrasti), purple-flowered thornapple (Datura tatula L.), wild mustard (Brassica kaber var. pinnatifida), bedstraw (Galium aparine), western violet (Viola sp.), and pineappleweed (Matricaria matricarioides). Thus, the compound of the present invention has a very wide herbicidal spectrum and at the same time a high level of safety.
The present invention i8 explained in more detail in the following Examples; however, it should be recognized that the scope of the present invention is not restricted to these Examples.

13 L;~ 2 Example 1 1-[4-(2,3-dihydro-2,2-dimethyl-5-benzofuranyl-methyloxy)phenyl]~3-methoxy-3-methylurea 6.9 g of 4-(2,3-dihydro-2,2-dime~hyl-5-benzo-furanylmethyloxy)aniline was dissolved into 30 ml of pyridine, and 3.8 g of N-methoxy-N-methylcarbamoyl chloride was slowly added dropwise thereto under cooling with ice.
After 2-hours' continuous stirring, pyridine was distilled off under a reduced pressure, and the residual oily matter was dissolved into 100 ml of toluene. After the solution was subsequently washed with water, diluted hydrochloric acid and saturated sodium chloride aqueous solution, toluene was distilled off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (1/3) as a developing solvent (developer) to obtain 7.6 g of Compound No. 2 shown in Table 1.

Example 2 1-[4-(2 ! 3-d ~ dro-2,2-dimet~1-6-benzofuranyl-methylox ~ henyl]-3-methoxy-3-methylurea 6.9 g of 4-(2,3-dihydro-2,2-dimethyl-6-benzofuranyl-methyloxy) aniline was dissolved into 70 ml of N,N-dimethyl-formamide, and 2.8 g of triethylamine was added thereto.
3.8 g of N-methoxy-N-methylcarbamoyl chloride was slowly added dropwise thereto. After the mixture was stirred at room temperature, the reaction mixture was poured into 1.3~ 3~2 water and extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off and the residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (1/2) as a developer to obtain 6.0 g of Compound No. 4 shown in Table 1.

Example 3 1-[4-(2,3-dihydro-2,2-dimethyl-4-benzofuranyl-methyloxy)phenyll-3-methoxy-3-methylurea 1.8 g of 4-(2,3-dihydro-2,2-dimethyl-4-benzofuranyl-methyloxy)phenyl isocyanate was dissolved into 20 ml of toluene, and 2.0 g of N,0-dimethylhydroxylamine dissolved in 5 ml of toluene was slowly added dropwise théreto at room temperature. After the mixture was stirred at room temperature for 2 hours, toluene was distilled off and the residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (1/4) as a developer to obtain 1.8 g of Compound No. 6 shown in Table 1.

Example 4 1-~4-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl-methyloxy)phenyl]-3,3-dimethylurea 3,0 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-methyl chloride and 3.0 g of 1-(4-hydroxyphenyl)-3,3-dimethylurea were dissolved into 20 ml of dried N,N-438~

dimethylformamide, and 2.5 g of anhydrous potassium carbonate was added thereto. After the mixture was stirred at 80C for 4 hours, the reaction mixture was poured into water and extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous magnesium sulfate and ethyl acetate was distilled off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (l/l) as a developer to obtain 4.0 g of Compound No. 7 shown in Table l.

Example S
l-t4-[2-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl) ethyloxy]phenyl]-3-methoxy-3-~ethylurea 2.6 g of l-(4-hydroxyphenyl)-3-methoxy-3-methylurea was dissolved into 20 ml of dried N,N-dimethylformamide, and 0.6 g of 60% sodium hydride was added thereto. After the mixture was stirred for 30 minutes, 1.7 g of 2-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl)ethyl chloride was added dropwise thereto under cooling with ice. After the mixture was stirred at room temperature for 5 hours, it was poured into water and extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous magnesium sulfate and ethyl acetate was distilled off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (l/l) as a developer to obtain 2.0 g of Compound No. 10 shown in Table 1.

13~43~Z

The compounds shown in Table 1 were produced in the same manner as in Examples 1 to 5. Table 1 also shows the melting point or the refractive index of each compound.

13(~38Z

Table 1 No Structural formula Melting Point or . Refractive Index 1 ~ 1I CH3 164-166C

CH2 ~NHCN<CH3 .

2 \ ¦¦ ~ CH3 132-133C

CH2 ~NHCN~OCH3 - ?' 3 CH2 - ~ -NHCN ~ CH 90-93C

. _ ~O ... _ 4 ~ O nD4 1.5559 . ~ ~ CH3 CH2 ~ NHCN ~ oCH3 _ O ~

5~ ¦¦ CH3 166-168C

CH2o--~3 NHCN<CH3, , ~ :

~3~ 4~

No Structural formula Melting Point or . Refractive Index . _ .. 1 ~

6 CH2 - ~ NHCN~ OCH 86-88C
_ 1~

7 ~ O 132-133C

_ CH 2--~3 NHCN< CH

8 CN2 - ~ NHCN <OCH 83-85C

, _ .

9 ~ 11 8 3 - 8 5 C
_ ~ .

10 OK2CH20 ~ NHCN< OCH n24 1.~550 ~f;P~3~

.
No. Structural formula Melting Point or Refractive Index 11 ~ X ~ CH3 89-900C
...

12 ~ 1~ CH3n23 1.5600 ._ 13 ~ ~ CH3 O 139~141C
___ 14 ~ \f 1l , CH3 129-130C
CHO _ ~ NHCN ~OCH3 .. ~ , CHO ~ ~ NHCN ~CH3 145-146C

1~43~2 No.Structural formula Melting Point or ~efract~ve Index l6~ CHO - ~ NHCN~ OCH 92-94C

NH N~ OCH 101-102C

_ _ .

18 ~ ~ NHCN ~ 3 126.5-127.5C

19 2 ~ 142-143C

- . _ ~

NHCN < 3 66-67C

13~43&;2 . .
No. Structural formula Melting Point or Refractive Index 21 ~ I 11 <CH3 120-121C

_ CH2CH20 ~
.

22 ~ NHCN < 124-125C

23 ~ NHCN < 106-107C

. _ _ 24 ~ 1¦ CH3 n24 1.5620 CH2CH2O ~ NHCN~ OCH3 _ ~2CH20 ~ NHcN ~ CH3 111-112C

~3~3~2 . .
No. Structural formula Melting Point or Refractive Index ~ CH3 ~ nD 1.5579 27 ~ ~ ~ ~ CH3 106-107C

. . ___ _. ___ 28 ~CH2O ~ NHCN < n24 1.5535 ... _ . _ 29 ~ ¦I CH3 89-90C
ÇHCH2O ~ C <CH

. ] ~ NHCN < n2 1.5647 Melting Point or No. Structural formula Refractive Index CH
31 ~ ~ NHCN < 3 120-120.5C

~ ~ NHCN < 3 _ ...__ .

. 33 O ~ ~ < CH3 113-115C

. ''''0-~- 0 34 ~ <OCH3 110.5-111.5C
C~I2CH20 _~
~ 9 / CH3 ...

35 ~ ~ \ CH3 75-80C

13~43~3Z

No. Structural formula Melting Point or Refractive Index <C~:3 -;

O~ . ...

~.

_ ~C32~20~ ~

~3~ 32 Example 6 1-[4-(2,3-dihydro-2-methyl-5-benzofuranyl-methyloxy)phenyl]-3-methoxy-3-methylurea 6.5 g of 4-(2,3-dihydro-2-methyl-5-benzofuranyl-methyloxy)aniline was dissolved into 30 ml of pyridine, and 3.8 g of N-methoxy-N-methylcarbamoyl chloride was slowly added dropwise thereto under cooling with ice. After 2-hours continuous stirring, pyridine was distilled off under a reduced pressure, and the residual oily matter was dissolved into 100 ml of toluene. After the reaction mixture was subse~uently washed with water, diluted hydrochloric acid and saturated sodium chloride aqueous solution, toluene was distilled off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (1/1) as a developer to obtain 7.3 g of Compound No. 40 shown in Table 2.

Example 7 1-[4-(2,3-dihydro-2-methyl-5-benzofuranyl-methyloxy)phenyl~-3,3-dimethylurea 6.5 g of 4-(2,3-dihydro-2-methyl-5-benzofuranyl-methyloxy)aniline was dissolved into 70 ml of N,N-dimethyl-formamide, and 2.8 g of triethylamine was added thereto.
3.8 g of N,N-dimethylcarbamoyl chloride was slowly added dropwise thereto. After the mixture was stirred at room temperature, the reaction mixture was poured into water and -- ~1 --~.3rD4~2 extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous magnesium sulfate and ethyl acetate was distilled off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (2/1) as a developer to obtain 5.8 g of Compound No. 41 shown in Table 2.

Example 8 1-{4-[2-(2,3-dihydro-2-methyl-5-benzofuranyl)-_thyloxy]phenyl}-3-methoxy-3-methylurea 1.8 g of 4-~2-(2,3-dihydro~2-methyl-5-benzofuranyl)-ethyloxy]phenyl isocyanate was dissolved into 20 ml of toluene, and 2.0 g of N,0-dimethylhydroxylamine dissolved in 5 ml of toluene was slowly added dropwise thereto at room temperature. After the mixture was stirred at room temperature for 2 hours, toluene was distilled off and the residue waC subjected to silica gel column chromatography using ethyl acetate/n-hexane (2/3) as a developer to obtain 1.8 g of Compound No. 42 shown in Table 2.

Example 9 1-[3-(2,3-dihydro-2-methyl-5-benzofuranyl-methyloxy)phenyl]-3-methoxy-3-methylurea 2.8 g of 2,3-dihydro-2-methyl-5-benzofuranylmethyl chloride and 3.0 g of 1-(3-hydroxyphenyl)-3-methoxy-3-methylurea were dissolved into 20 ml of dried N,N-dimethyl-130~3~;~

formamide, and 2.5 g of anhydrous potassium carbonate was added thereto. After the mixture was stirred at 80C for 4 hours, the reaction mixture was poured into water and extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous magnesium sulfate and ethyl acetate was dried off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (1/2) as a developer to obtain 3.7 g of Compound No. 46 shown in Table 2.

Example 10 1-{3-[2-(2,3-dihYdro-2-methyl-5-benzofuranyl~
ethyloxy]phe~l}-3-methoxy-3-methylurea 2.0 g of 1-(3-hydroxyphenyl)-3-methoxy-3-methylurea was dissolved into 20 ml of dried N,N-dimethylformamide, and 0.4 g of 60% sodium hydride was added thereto. After the mixture was stirred for 30 minutes, 3.3 g of 2-(2,3-dihydro-2-methyl-5-benzofuranyl)ethyl-p-toluene sulfonate was added dropwise thereto under cooling with ice. A~ter the mixture was stirred at room temperature for 5 hours, it was poured into water and extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous magnesium sulfate and ethyl acetate was distilled off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (1/2) as a developer to obtain 3.3 g of Compound No. 49 shown in Table 3.

~ ~3 -3~32 The compounds shown in Tables 2 and 3 were produced in the same manner as in Examples 6 to 10. Tables 2 and 3 also show the melting point or the refractive index of each compound.

~3~43&Z

Table 2 1 ~ <CH3 H ~ A-O ~

_ 1 Melting Point or No. R R A Refractive Index -OCH3 -CH3 -CH2- 10b-102C

44 -OCH3 -CH3-~HHCH2 n24 1.5652 -CH3 -CH3 CH3 13l-1~4-~

3'~382 Table 3 R~ ~ A-O ~ NHCN <

No R R1 AMelting Point or . Refractive Index 47 -CH3 -CH3 -CH2-133.5-134.5C

49 -OCH3 -CH3 CH2CH2nD 1.5645 -C2H5 -CH3 -CH2C~2n24 1.5648 52 -OCH3 -CH3 gHHCH2nD4 1.5655 53 -CH3 -CH3 CHHCH2nD4 1.5790 I

. ~

13~ 3~2 Example 11 1-[2-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl-methyloxy)-5-pyridyl]-3-methoxy-3-methylurea (Compound No. 54):

o ~ ~ NHCN~ 3 2.0 g of 2-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl-methyloxy)-5-aminopyridine was dissolved into 5 ml of pyridine, and 1.1 g of N-methoxy-N-methylcarbamoyl chloride was slowly added dropwise thereto under cooling with ice.
After 2-hours' continuous stirring, pyridine was distilled off under a reduced pressure, and the residual oily matter was dissolved into 30 ml of toluene. After the mixture was subsequently washed with water, diluted hydrochloric acid and saturated sodium chloride aqueous solution, toluene was distilled off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (1/1) as a developer to obtain 2.2 g of 1-12-(2,3-dlhydro-2,2-dimethyl-7-benzo~uranylmethyloxy)-5-pyridyl]-3~methoxy-3-methylurea.

Refractive index nD5 = 1.5634 13~438Z

Example 12 1-~2-[2-~2,3-dihydro-2,2-dimethyl-5-benzofuranyl)-ethyloxy]-5-pyridyl}-3-methoxy-3-methylurea tCompound ~o. 55):

o ¦¦ ~ CH3 2C 2 ~ NHCN~

2.2 g of 2-~2-(2,3-dihydro-2,2-dimethyl-5-benzo-furanyl)ethyloxy]-5-aminopyridine was dissolved into lOml of N,N-dimethylformamide, and 0.9 g of triethylamine was added thereto. 1.2 g of N-methoxy-N-methylcarbamoyl chloride was slowly added dropwise thereto. After the mixture was stirred at room temperature, the reaction mixture was poured into water and extracted with ethyl acetate.
After the organic layer was washed with water, it was dried over anhydrous magnesium sulfate and ethyl acetate was dried off. The residue was subjected to silica gel column chromatography using ethyl acetate/n-hexane (2/3) a~ a developer to obtain 2.1 g of 1-f2-~2-(2,3-dihydro-2,2-dimethyl-5-benzofuranyl)ethyloxy]-S-pyridyl}-3-methoxy-3-methylurea.
Melting point: 79 to 80C

13~43~

Example 13 1-[2-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl-methyloxy)-5-pyridyl]-3,3-dimethylurea (Compound No 56) o NHCN~ CH3 $ ~ CH20 ~ ~ CH3 Compound No. 56 was synthesized in the same manner as in Example 11.
Melting point: 127.5 to 128.5C

Example 14 ~ [2-(2,3-dihydro-2,2-dimethyl-5-benzofuranyl)-ethyloxy]-5-pyridyl}-3,3-dimethylurea (Compound No. 57):

o ¦¦ ~ CH3 NHCN

CH2CH20 ~ ~ CH3 Compound No. 57 was synthesized in the same manner as in Example 11.
Melting point: 153 to 154C

131'~38Z

Example 15 1- {4-[(3,4-dihydro-2H-1-benzopyran-6-yl)methyloxy]-phe-yl--3-methoxy-3-methylurea 2.6 g of 4-[3,4-dihydro-2H-l-benzopyran-6-yl)-methyloxy]aniline was dissolved into 15 ml of pyridine, and l.S g of N-methoxy-N-methylcarbamoyl chloride was slowly added dropwise thereto under cooling with ice.
After 2-hours' stirring at room temperature, the reaction mixture was poured into iced water and extracted with ethyl acetate. After the organic layer was sub~equently washed with diluted hydrochloric acid and saturated sodium chloride aqueous solution, it was dried over anhydrous sodium sulfate.
Ethyl acetate was distilled off under a reduced pressure, and the residue was recrystallized from cyclo-hexane to obtain 2.9 g of Compound No. 58 shown in Table 4.

Example 16 1-{4-[(3,4-dihydro-2-methyl-2H-l-benzopyran-6-yl)-ethyloxy]phenyl}-3,3-dimethylurea 3.1 g of 4-[(3,4-dihydro-2-methyl-2H-l-benzopyran-6-yl)ethyloxy]phenyl isocyanate was dissolved into 30 ml of toluene, and 0.9 g of dimethylamine dissolved in 5 ml of toluene was slowly added dropwise thereto at room temperature. After the mixture was stirred at room temperature for 2 hours, toluene was distilled off under a ~3Q4~82 reduced pressure and the residue was recrystallized from ethyl acetate to obtain 2.7 g of Compound No. 67 showr. in Table 4.

Example 17 1-{3-[(3 ! 4-dihydro-2~2-dimethyl-2~-l-benzopyran-6-yl) methyloxy]phenyl~-3-methoxy-3-methylurea 2.0 g of 1-(3-hydroxyphenyl)-3-methoxy-3-methylurea was dissolved into 20 ml of dried N,N-dimethylformamide, and 0.4 g of 60% sodium hydride was added thereto. After the mixture was stirred for 15 minutes, 2.1 g of 3-[(3,4-dihydro-2,2-dimethyl-2H-l-benzopyran-6-yl)methyl]chloride was added dropwise thereto under cooling with ice. After the mixture was stirred at room temperature for 3 hours, it was poured into iced water and extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous sodium sulfate and ethyl acetate was distilled off under a reduced pressure. The residue was purified by silica gel column chromatography using ethyl acetate/n-hexane (3/1) as a developer to obtain 2.6 g of Compound No.
91 shown in Table 5.

~.3~38Z

Example 18 1- ~3-[ _,4-dihydro-2,2-dimethyl-2H-l-benzopyran-6-yl)-ethyloxy]phenyl}-3,3-dimethylurea 1.8 g of 1-(3-hydroxyphenyl)-3,3-dimethylurea was dissolved into 20 ml of dried N,N-dimethylformamide, and 0.4 g of 60% sodium hydride was added thereto. After the mixture was stirred for 15 minutes, 3.6 g of 3-[(3,4-dihydro-2,2-dimethyl-2H-l-benzopyran-6-yl)ethyl]-p-toluene sulfonate was added dropwise thereto under cooling with ice.
After the mixture was stirred at room temperature for 5 hours, it was poured into iced water and extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous sodium sulfate and ethyl acetate was distilled off. The residue was purified by silica gel column chromatography using n-hexane/ethyl acetate (1/1) as a developer to obtain 2.4 g of Compound No.94 shown in Table 5.
The compounds shown in Tables 4 to 9 were produced in the same manner as in Examples 15 to 18~ Tables 4 to 9 also show a physical property of each compound.

11.3~ 38~

Table 4 R O NHCN
R~ A-O ~

No. R1 R2 R3~R4 R ~ A Phys ' cal _ 58 H N H H -OCH3 -CH2- mp109-110C

59 N H H H CH3 -CH2- mp150-151C

H H H H -OCH3 CH2CH2 mp115-116C

61 H H H¦ H CH3 -CH2CH2- mp128-129C
. _ 62 H H H H -OCH3 -CcH3cH2- mp99-101C

63 H H H H CH3 -CH-CH2- mp134-135C
_ ... .... , _ 64 CH3 H H H-OCH3 -CH2- mp128-129C
__ . _ CH3 H H H CH3 -CH2- mp142-143C
. ._ 66 CH3 H H H-OCH3-CH2CH2- mp118-119C
.... _ 67 CH3 H H H CH3CH2CH2 mp136-137C

68 CH3 H H HCH 3-CH-3cH2 ~ mp136 -138 C

~3~3~3~32 Ro. Rl R R R R Physical .

69CH3 CH3 H H-OCR3 -CH2- mp 110-111C

70CH3 CH3 R H CH3 -CH2- mp 167-168C

71CH3 CH3 R H-OCH3 CH2CH2 mp 107.5-108.5 72CH3 CH3 H H CH3 CH2CH2 mp 123-124C

73CH3 CH3 H H-OCH3 CN1 mp 58-60C
. .... _ 74CH3 CH3 H H CH3 CH3 mp 152-153C

75CH3 CH3 H H-OCH3 -CH2CH2CH2- mp 105-106C

76CH3 CH3 H H CH3 -CH2CH2CH2- mp 163-164C

77 H H CH3 CH3 -OCH3 -CH2- mp 131-132C

78 H H CH3 CH3 CH3 -CH2- mp 111-112C

79 H H CH3 CH3 -OCH3 CH2CH2 Amorphous H H CH3 CH3 CH3 CH2CH2 mp 159-160C

1.3~

Table 5 R2~`

No. Rl R2 R3 R4 R A PhYopeCt _ 81 H H H H-OCH3 -CH2 mp 87-88C
. . _ 82 H H H HCH3 -CH2 mp 125-126C

83 H H H H-OCH3 CH2CH2 mp 89-90C

84 H H H HCH3 -CH2CH2- mp 99-100C
.
_ H H H-OCH3 -C,H-CH2- mp 96-98C

86 H H H HCH3 -CH-CH2- mp 126-127C

. .. , .. _ . .. _ , 87 CH3 H H H-OCH3 -CH2- mp 104-105C
_ 88 CH3 H H HCH3 -CH2- mp 163-164C
..
89 CH3 H H H-OCH3 -CH2CH2- mp 80-81C

CH3 H H HCH3 ~H2CH2 mp 134-135C

1.3~4~8~

.
No.Rl R2 R3R4 R _ Physical 91CH3 CH3 H H ~OCH3 -CH2- mp 137-138C

92CH3CEI3 ~ H CE13 -CH2- mp 147-147.5C
93CH3 CH3 H H -OCH3-CH2CH2- mp 64.5-65C

94CH3C113 H H CH3CH2CH2 mp 133-134C
95CH3 CH3 H H -OCH3 -CH-CH2- mp 96-97C

96CH3 CH3 11-- CH3~U CU2 mp 128 l29'C

97C}13C}13 }I H -OCH3 -CH2CH2CH2- mp 102-103C

98CH3 CH3 H H CH3 -CH;~CH2CH2- mp 130-131C
.
99 H H CH3CH3-OCH3 -CH2- nD5 1.5740 _ 100 H H CH3CH3 CH3 -CH2- mp 116-117C
_ 101 H H CH3 CH ¦ -OCH3 -CH2CH2- nD5 1.5700 102 H CH3 CH C83 CH2CH2 Amorphous 1.3~382 Table 6 ~3/ NHCN < 3 R R O R

No.R1 R R R R A Property 103 _ CH3 H-OCH3 -CU~- nD51. 5692 104CH3 CH3 H H-OCH3 -CH2CH2- mp 93 - 94C

105C33 Cl!3 H HC~:3 -CH2CH2- mp 142-143C

-- 5i --~3~4~Z

Table 7 R ~ A-O ~ NHIlN <CH3 _ XO. R1 R~ R3 R4 R L~ PhYS1Ca1 106 CH3 CN3 H H_OCN3 _CH2_ n25 1. 5662 107 CN3 CN3 H HCN3 -CH2- mp 116-117C

108 CH3 CH3 H H-OCH3 -CH2CH2- mp 56-58C
, 109 CN3 CN3 H HCN3 CH2CH2 mp 146-147C

~.3~3~5~

Table 3 NHCN <

R43 ~ A-O R

R2 Rl No .Rl R R R4 R Physical _ 110 CH3 CH3 N H -OC~3CH2CH2n25 1.5608 111 CH3 CH3 H H CH3-CH2CH2-n25 1.5585 ~1 3~

Table 9 R3/~A-o J~NH ICIN< CRH3 O
R~ Rl No Rl R3 _ R A Property 112 3 H H ~ -OCH3-CH2- mp 105-106C

113CH3 ~ H ~ -OCH3-CH2CH2- n25 1. 5597 114C33 CH3 H H CH3CH2CH2 mp 102-104C

~ J~

Formulation Examples for preparing a herbicide from a compound according to the present invention are set forth below. "Part" and "%" hereinunder represent "part by weight" and "% by weight", respectively.

J

Formulation Example l (Wettable Powder) 40 parts of a compound of the present invention, 20 parts of Caprex #80~ (produced by Shionogi &
Co., Ltd.), 35 parts of N,N Kaolinclay (trade mark, produced by Tsuchiya Kaolin Co., Ltd.) and 5 parts of a higher alcohol sulfate surfactant Solbol 8070 (trade mark, produced by Toho Chemical Co., Ltd.) were uniformly mixeq and pulverized to obtain a wettable powder containing 40% of an active ingredient.

Formulation Example 2 (Granules) l part of a compound of the present invention, 43 parts of clay (produced by Nihon Talc Co., Ltd.), 55 parts of bentonite (produced by Hojun Yoko Co., Ltd.) and 1 part of a succinate surfactant Airol CT-1~ (produced by Toho Chemical Co., Ltd.) were mixed and pulverized. The resultant mixture was kneaded with 20 parts of water and extruded from the nozzles 0.6 mm in diameter of an extrusion pelletizer.
The extruded pieces were dried at 60C for 2 hours and were then cut into a length of l to 2 mm, thereby obtaining granules containing 1% of an active ingredient.

~ - 61 -.~ .
. ,9~ .

1.3~438;~

Formulation Example 3 (Emulsion) An emulsion containing 30% of an active ingredient was prepared by dissolving 30 parts of a compound of the present invention into a mixed solvent of 30 parts of xylene and 25 parts of dimethylformamide, and adding 15 parts of polyoxyethylene surfactant Solbol 3005X (trade mark, produced by Toho Chemical Co., Ltd.).

Formulation Example 4 (Flowable Agent) . . .
30 parts of a compound of the present invention was adequately mixed with and dispersed in a mixture of 8 parts of ethylene glycol, 5 parts of Solbol AC3032 (trade mark, Toho Chemical Co., ~td.), 0.1 part of xanthane gum and 56.9 parts of water. The thus-obtained mixture in the form of slurry was wet-pulverized by a Dino~ mill (produced by Symmal Enterprises Co.) to obtain a stable flowable agent containing 30% of an active ingredient.

Test Example 1 Treatment test on soil of flooded field A plastic vat having an area of 1/2500 are was charged with the alluvial clay loam of paddy field, and the soil was fertilized and plowed while adding an appro-priate amount of water thereto. On the thus-prepared soil, the seeds of barnyardyrass (Echinochloa crus-galli L. Beauv.
var. crus-galli), toothcup (Rotala indica) and duck-tongue ~t ...........

1.3~.~43~

weed (Monochloria vaginalis) were sown. The seeds were mixed well with the soil in the layer within 0.5 cm of the surface.
2- to 3-leaf stage seedlings of rice plants (species:
Akinishiki, quality of the seedlings: good) were trans-planted to the vat in a depth of about 1 cm (3 xoots per plant and 2 plants per vat). Thereafter, the water was maintained at a depth of 3.5 cm. 3 days after the trans-plantation, granules which contained a compound of the present invention as an active ingredient and which had been obtained in the same manner as in Formulation Example 2 were dropped to the flooded surfaces. For comparison, granules which contained a comparative compound as an active ingredient and which had been obtained in the same manner as in Formulation Example 2 were dropped to the flooded surfaces. The amounts of granules used were respectively so determined that the amounts of active ingredients contained were 10 g and 5 g, respectively, per are. After treating the soil with the granules, a leaching loss of water was adjusted at the rate of 3 cm/day for 2 days. Thereafter, the vats were kept in a greenhouse to allow growth of the plants under control. On the 21st day after the herbicidal treatment, the herbicidal effect and the phytotoxicity by the herbicide were examined.
The results are shown in Tables 10 to 12. The following equation was calculated and the evaluation of the ~.3~

herbicidal effect was represented by the herbicidal effect rate based on the following criteria:

' (SurVival terrestrial weeds) .
weight in treated area 1 ~ x 100 = Y (%) Survival terrestrial weeds weight in non-treated area Herbicidal effect rateY(%) O to 5 1 .6 to 30 2 31 to 50 3 51 to 70 4 71 to 90 91 to lOO

The phytotoxicity by the herbicide to the paddy-rice plants was evaluated by calculating the following formula and represented by the phytotoxicity rate based on the following criteria:

Survival terrestrial crop plant weight in treated area 1 - x 100 = Y' (%) Survival terrestrial crop plant - (weight in non-treated area 3~3Z

Phytotoxicity rate Y'(%) 0 0 to 5 1 6 ~o 10 2 11 to 20 3 21 to 40 4 41 to 60 61 to 100 ~t 3~ 2 Table 10 Com- Dose ~erbicidal effect rate Phytotoxicity rate pound g/are .
No. Barnyard Tooth Duck-grass cuptongue Rice 3 150 43 s5 . s5 0 4 10 4 5 5 0 .

5 10 ~ 4 5 0 .. __ . 6105 23 35 3 0 _ 710 3 S s5 0 - .. _ .__ ... ....

..

.. _ . _ _ S 2 4 4 ___ ~.~f~3&2 Com- Dose Herbicidal effect rate Phytotoxicity rate pound g/are . _ _ _ No. Barnyard Tooth Duck-grass cupweonegue Rice 7 10 _ _ S S 0 19 10 2 4 ~44 0 _ ~ 4 S 0 21 10 ~ 5 5 0 . 22 10 43 s4 s5 0 24 105 54 s5 55 . . __ ~.3~ 3&Z

, Com- Dose Herbicidal effect rate Phytotoxicity rate pound g/are No. Barnyard Tooth Duck-grass cup weendUe Rice 27 10 ~ _ 5 5 O

. 30 10 ~ 5 5 O

~ _~ ~
_ _ 2 5 5 ___ 36 15 ~ 5 4 O

1.3~3&;~

Com- Dose Herbicidal effect rate Phytotoxicity rate pound g/are .
No. Barnyard Tooth Duck-grass cuptongue Rice 38 10 5~ _ 5 39 10 1 4 5 O .
Cotmpia- 103 1 3 3 com- 5 2 O 2 O
pound _ (Note) Comparative compound: 1-(4-chlorophenoxy)phenyl-3,3-dimethylurea 1 3~9t38Z

Table 11 Com- Dose Herbicidal effect rate Phyto~oxicity rate pound g/are No. Barnyard Tooth Duck-grass cup wenedgU~ Rice ~ 4 S O

43 10_ _ _ 5 4 , 48 10 ~ - 4- S O

49 10 ~ S- 5- ol ~ _ . .. __ _ _ _n~_._ Compa-rative10 1 4 4 2 pomund 5 _ _ (Note) Comparative compound: 1-4-[2-(4-methylphenyl)ethylaxy]phen 3-methoxy-3-methylurea - 70 ~

J.3~ 2 Table 12 Com- Dose Herbicidal effect rate Phytotoxicity rate pound g/are No. Barnyard Tooth Duck-grass cuptongue Rice weed 61 10 ~ S S O

4 5 .5 __ _ . 69 10 S S S 1 . 81 10 4 5 5 O

_ .

~.3Q~2 Com- Dose Herbicidal effect rate Phytotoxicity rate pound g/are .
No. Barnyard Tooth Duck-grass cuptenedgUe Rice 104 10 ~ S 4 0 . _ 108 10 5 5 5 1 .

. Compa- _ .
Coam-Ve 10 1 4 4 2 pound (Note) Comparative compound: 1-4-[2-(4-methylphenyl)~
ethyloxy]phenyl-3-methoxy-3-methylurea ~1 3~ 3&2 Test Example 2 Treatment test on foliage A small-sized polyethylene pot having an area of 1/8850 are was charged with black volcano ash soil. After the soil was fertilized, the seeds of persicaria blumei gross (Polygonum blumei), lambsquarters (chenopodium album), velvetleaf (Abutilon theophtasti),dead-nettle (Laminum amplexicaule), bed straw (Galium spurium), corn (Zea mays) and barley (Hordeum wlgare) were sown in the respective pots.
The pots were left in a greenhouse to allow growth of the plants under control. Wettable powders containing as an active ingredient a compound of the present invention and a comparative compound, obtained in the same way as in Formulation Example 1 were diluted with water so as to have a predetermined amount of active ingredient. When the test plants of persicaria blumei gross reached 2-leaf stage, lambsquarters reached 3-leaf stage, velvetleaf reached 2-leaf stage, dead-nettle reached 2-leaf stage, bedstraw reached 1.5-leaf stage, corn reached 3-leaf stage and barley reached 2-leaf stage, respectively, the wettable powders were sprayed by a small-sized power pressurized sprayer at a dosage of 10 litter per 1 are. Thereafter, the plants were observed in the greenhouse, and 15 days after the treatment, the herbicidal 1.3(~4382 effect and the phytotoxicity of the crops from the compounds were examined. The results are shown in Table 13 to 16. The evaluation of the herbicidal effect and the phytotoxicity were based on the same criteria as in Test Example 1.

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~.3~43~

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Claims (18)

1. A compound represented by the following general formula (I):
(I) wherein A represents an alkylene group; 3 represents a nitrogen atom or CH; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; R1, R2, R3 and R4 independantly represent a hydrogen atom or a methyl group;
and n is 0 or 1.

2. A compound according to claim 1, wherein said compound is an N'-aryl-N-methylurea derivative represented by the following general formula (II):
(II) wherein A represents an alkylene group; and R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group.

3. A compound according to claim 1, wherein said compound is an N'-phenyl-N-methylurea derivative represented by the following general formula (III):
(III) wherein A represents an alkylene group; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; and R1 represents a hydrogen atom or a methyl group.

4. A compound according to claim 1, wherein said compound is an N'-(5-pyridyl)-N-methylurea derivative represented by the following general formula (IV):
(IV) wherein A represents an alkylene group; and R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group.

5. A compound according to claim 1, wherein said compound is an N'-phenyl-N-methylurea derivative represented by the following general formula (V):

(V) wherein A represents an alkylene group; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group;
and R1, R2, R3 and R4 independantly represent a hydrogen atom or a methyl group.

6. A compound according to claim 2, wherein A
represents a methylene group, an ethylene group or a propylene group; and R represents a methyl group or a methoxy group.

7. A compound according to claim 3, wherein A
represents an ethylene group or a propylene group; R
represents a methyl group or a methoxy group; and R1 represents a methyl group.

8. A compound according to claim 4, wherein A
represents a methylene group; R represents a methyl group.

9. A compound according to claim 5, wherein A
represents an ethylene group or a propylene group; R
represents a methyl group or a methoxy group; R1 and R2 respectively represent a hydrogen atom or a methyl group;
and R3 and R4 respectively represent a hydrogen atom.

10. A herbicidal composition comprising as an active ingredient a herbicidally effective amount of compound represented by the following general formula:
(I) wherein A represents an alkylene group; B represents a nitrogen atom or CH; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; R1, R2, R3 and R4 independantly represent a hydrogen atom or a methyl group;
and n is 0 or 1, and a herbicidally acceptable carrier or adjuvant.

11. A herbicidal composition according to claim 10, wherein said compound is an N'-aryl-N-methylurea derivative represented by the following general formula (II):

(II) wherein A represents an alkylene group; and R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group.

12. A herbicidal composition according to claim 10, wherein said compound is an N'-phenyl-N-methylurea deri-vative represented by the following general formula (III):
(III) wherein A represents an alkylene group; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group;
and R1 represents a hydrogen atom or a methyl group.

13. A herbicidal composition according to claim 10, wherein said compound is an N'-(5-pyridyl)-N-methylurea derivative represented by the following general formula (IV):
(IV) wherein A represents an alkylene group; and R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group.

14. A herbicidal composition according to claim 10, wherein said compound is an N'-phenyl-N-methylurea deriva-tive represented by the following general formula (V):
(V) wherein A represents an alkylene group; R represents a hydrogen atom, a lower alkyl group or a lower alkoxy group and R1, R2, R3 and R4, independantly represent a hydrogen atom or a methyl group.

15. A herbicidal composition according to claim 11, wherein A represents a methylene group, an ethylene group or a propylene group; and R represents a methyl group or a methoxy group.

16. A herbicidal composition according to claim 12, wherein A represents an ethylene group or a propylene group; R represents a methyl group or a methoxy group; and R1 represents a methyl group.

17. A herbicidal composition according to claim 13, wherein A represents a methylene group; R
represents a methyl group.

18. A herbicidal composition according to claim 14, wherein A represents an ethylene group or a propylene group; R represents a methyl group or a methoxy group; R1 and R2 respectively represent a hydrogen atom or a methyl group; and R3 and R4 respectively represent a hydrogen atom.