KR100575463B1 - 1-substituted 4-carbamoyl-1,2,4-triazol-5-one derivatives and herbicide - Google Patents

Abstract

General formula (Ⅰ)

[Wherein, A is an unsubstituted or substituted phenyl group, 1-naphthyl group, 5,6,7,8-tetrahydronaphthyl group or an alalkyl group such as unsubstituted or benzyl group, R ₁ is lower alkyl or the like, and R ₂ is 1-phenyl or naphthyl or alalkyl-4- (N, N-disubstitutedcarbamoyl) -1,2,4-triazol-5-one as a novel compound do. This 1-substituted-4-carbamoyl-1,2,4-triazol-5-one is substantially innocuous to various crops and is useful as a selective herbicide.

Description

1-Substituted 4-carbamoyl-1,2,4-triazol-5-one derivatives and herbicides {1-SUBSTITUTED 4-CARBAMOYL-1,2,4-TRIAZOL-5-ONE DERIVATIVES AND HERBICIDE}

The present invention relates to novel 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivatives useful as herbicides and to herbicide compositions comprising the derivative as an active ingredient. . The invention is useful in the field of chemical industry and agriculture, in particular in the manufacture of pesticides.

Conventionally, it is already known that some kinds of 1,2,4-triazol-5-one derivatives and tetrazolinone derivatives have herbicidal or bactericidal activity as indicated below.

For example, the known 1,2,4-triazol-5-one derivatives include compounds described in the following documents.

(1) Japanese Patent Laid-Open No. 7-76578 discloses a compound represented by the following general formula (A).

General formula (A)

Wherein X represents an oxygen atom or a sulfur atom, R ₁ represents a haloalkyl group, R ₂ represents a cycloalkyl group, a cycloalkylalkyl group, R ₃ represents a hydrogen atom or a halogen atom, and R ₄ represents a nitrile group Or a nitro group, and R ₅ represents a halogen atom or a heterocyclic alkoxy group.

(2) Japanese Patent Application Laid-Open No. 3-106865 discloses a compound represented by the following general formula (B).

General formula (B)

Wherein R ₁ represents a cycloalkyl group, a phenylalkyl group, a halogen atom, an amino carbonyl group substituted with a substituted phenyl group, etc., R ₂ represents a hydrogen atom or a lower alkyl group, and R ₃ represents a halogen atom, an alkyl group, or the like. Represented compounds.

(3) Japanese Patent Application Laid-Open No. 64-29368 discloses a compound represented by the following general formula (C).

General formula (C)

(Wherein X and Y represent an oxygen atom or a sulfur atom, R ₁ represents a hydrogen atom, etc., R ₂ represents a phenyl group, an alalkyl group, etc. which may be substituted, R ₃ , R ₄ represents a hydrogen atom, an alkyl group or The aryl group etc. which may be substituted are represented).

(4) Japanese Patent Application Laid-Open No. 6-293744 discloses a compound represented by the following general formula (D).

General formula (D)

(R₆와 R₇은 알킬기, 알켄일기, 시클로알킬기, 아릴기 등을 나타낸다)을 나타내며, R₅는 아미노기 또는 히드록시 등을 나타낸다]으로 표시되는 화합물.[Wherein, R ₁ represents a hydrogen atom or the like, and R ₂ represents

(R <_6> and R <_7> represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, etc.), and R <_5> represents an amino group, hydroxy, etc.].

Some types of 1,2,4-triazol-5-one derivatives are described in the literature,

(5) Japanese Patent Application Laid-open No. 56-32403; (6) Japanese Patent Application Laid-Open No. 56-53663; (7) Japanese Patent Application Laid-Open No. 56-53662; (8) Japanese Patent Application Laid-Open No. 58-23680; (9) US Patent No. 4705557; (10) PCT International Publication WO 85/01637; (11) PCT International Publication WO 86/02642; (12) British Patent No. 2230261; (13) JP-A 3-106865; (14) German Patent No. 4437049; (15) German Patent No. 4435476; (16) German Patent No. 4431219; (17) US Pat. No. 50,5740; (18) Japanese Patent Application Laid-Open No. 3-181472; (19) German Patent No. 3920414; (20) Japanese Patent Application Laid-Open No. 3-17070; (21) South African Patent No. 8905308; (22) Japanese Patent Application Laid-Open No. 64-29368; (23) Japanese Patent Application Laid-Open No. 63-255271; (24) Japanese Patent Application Laid-Open No. 52-118471.

However, the documents (1) to (24) do not describe compounds having a carbamoyl group at the 4-position of the 1,2,4-triazol-5-one derivative.

Moreover, as a tetrazolinone derivative, the compound described in following documents (25)-(50) is known.

(25) Japanese Patent Application Laid-Open No. 62-12767 discloses a compound represented by the following general formula (E).

General formula (E)

(Wherein R represents a cycloalkyl group, a phenyl group, a naphthyl group, R ₁ , R ₂ are the same or different, and are C ₁ -C ₆ -alkyl groups, C ₅ -C ₆ -alkenyl groups, C ₅ -C ₆ A phenyl group which may represent a -cycloalkyl group, a C ₇ -C ₉ -alalkyl, or may be substituted with a halogen atom, a C ₁ -C ₆ -alkyl group or a C ₁ -C ₆ -haloalkyl group or a C ₁ -C ₆ -alkoxy group To represent a compound.

(26) Japanese Patent Application Laid-Open No. 60-146879; (27) Japanese Patent Application Laid-Open No. 5-331154; (28) Japanese Patent Application Laid-Open No. 5-339249; (29) Japanese Patent Application Laid-Open No. 5-331153; (30) Japanese Patent Application Laid-Open No. 6-306061; (31) Japanese Patent Application Laid-Open No. 6-199818; (32) Japanese Patent Application Laid-Open No. 7-258230; (33) Japanese Patent Application Laid-Open No. 8-81459; (34) Japanese Patent Application Laid-Open No. 8-99975; (35) Japanese Patent Application Laid-Open No. 8-119947; (36) Japanese Patent Application Laid-Open No. 8-119948; (37) Japanese Patent Application Laid-Open No. 8-119950; (38) Japanese Patent Application Laid-Open No. 8-119951; (39) Japanese Patent Application Laid-Open No. 8-225547; (40) Japanese Patent Application Laid-Open No. 8-311048; (41) Japanese Patent Application Laid-Open No. 8-259549; (42) US Pat. No. 4830661, Specificationshire; (43) US Patent No. 4956469; (44) US Patent No. 5003075; (45) US Patent No. 50952; (46) Patent specification No. 101563; (47) Japanese Patent Application Laid-Open No. 8-119949; (48) Japanese Patent Application Laid-Open No. 8-259548; (49) US Patent No. 5136868; (50) Tetrazononone derivatives as shown in PCT International Publication No. WO 85/01939.

In the development of herbicides, it is important to prepare new herbicidally active compounds having selective herbicidal activity on the basis of crops, ie, differences in susceptibility to herbicides between useful cultivars and weeds. Some types of herbicidally active compounds are not satisfactory as herbicides, even if they show high herbicidal effects and are harmful to crops. Therefore, the development of new herbicides without such drawbacks is required. In this regard, the above-mentioned known compounds 1,2,4-triazol-5-one derivatives and tetrazononone derivatives are not particularly satisfactory herbicides. Therefore, the object of the present invention is a novel 1-substituted-4-carbamoyl, which is safe for use as a herbicide, instead of such known herbicidal compounds, exhibiting extremely low phytotoxicity against crops requiring good herbicidal activity. To provide a -1,2,4-triazol-5-one derivative, or to provide a herbicide containing the same.

Disclosure of the Invention

MEANS TO SOLVE THE PROBLEM This inventor performed extensively in order to achieve the said objective. As a result, the synthesis of a number of novel 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivatives not known so far has been successful. In addition, their herbicidal activity and other usefulness were examined. As a result, the novel 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivatives represented by the following general formula (I) surprisingly show no harm to useful cultivated plants, i.e., crops. In addition, it was found that excellent herbicidal activity was obtained even when used in a low amount. Based on this knowledge, the present invention was completed.

Accordingly, according to the first aspect of the present invention, there is provided a 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative represented by the following general formula (I).

(단, X는 동일하거나 또는 서로 달라도 좋은 할로겐 원자, 저급 알킬기, 저급 할로알킬기, 저급 알콕시기, 저급 할로알콕시기, 시아노기, 니트로기, 메틸티오기, 메틸술핀일기, 메틸술폰일기, 펜옥시기, 아세틸아미노기 또는 트리플루오로아세틸아미노기 이고, n는 0 또는 1∼5의 정수이다)으로 표시되는 비치환 또는 치환 페닐기이거나, 또는 (ⅱ) A는 식

의 1-나프틸기 또는 식

의 5,6,7,8-테트라하이드로-1-나프틸기 이거나, 또는 (ⅲ) A는 식

(단, X와 n은 상기와 같은 의미를 갖고, R₃는 수소원자 또는 메틸기 이고, K는 1∼2의 정수를 나타낸다)으로 표시되는 비치화 또는 치환 벤질기 또는 펜에틸기 이고; 또한 R₁은 저급 알킬기, 저급 알켄일기, 저급 알킨일기 또는 저급 시클로알킬기 이고, R₂는 저급 알킬기, 저급 시클로알킬기, 식

(단, m은 0 또는 1∼5의 정수이고, Y는 동일하거나 또는 서로 달라도 좋은 할로겐 원자, 저급 알킬기, 저급 할로알킬기, 저급 알콕시기, 저급 할로알콕시기 또는 시아노기 이다)으로 표시되는 비치환 또는 치환 페닐기, 또는 벤질기가 벤젠환 상에서 할로겐 원자로 치환되어 있어도 좋은 벤질기 또는 식

(단, Z는 수소원자 또는 염소원자 이다)으로 표시되는 비치환 또는 치환 피리딜기이다]으로 표시되는 1-치환-4-카르바모일-1,2,4-트리아졸-5-온 유도체를 제공한다.[Wherein, (ⅰ) A is

(However, X is the same or different halogen atom, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, cyano group, nitro group, methylthio group, methylsulfinyl group, methylsulfonyl group, phenoxy group , An acetylamino group or a trifluoroacetylamino group, n is an unsubstituted or substituted phenyl group represented by 0 or an integer of 1 to 5), or (ii) A is a formula

1-naphthyl group or formula

Is a 5,6,7,8-tetrahydro-1-naphthyl group, or (iii) A is

Wherein X and n have the same meaning as described above, R ₃ is a hydrogen atom or a methyl group, and K represents an integer of 1 to 2; and is an unsubstituted or substituted benzyl group or a phenethyl group; R ₁ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, and R ₂ is a lower alkyl group, a lower cycloalkyl group, a formula

(Wherein m is an integer of 0 or 1 to 5 and Y is a halogen atom, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group or cyano group) which may be the same or different from each other Or a benzyl group or formula in which a substituted phenyl group or benzyl group may be substituted with a halogen atom on the benzene ring;

A 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative represented by (unsubstituted or substituted pyridyl group represented by Z is hydrogen or chlorine) to provide.

The novel 1,2,4-triazol-5-one derivatives of the general formula (I) according to the present invention are unsubstituted at the 1, 2,4-triazole-5-one ring or N at their 4 position. It has a characteristic chemical structure in that it is substituted by, N-disubstituted carbamoyl group.

In the derivative of general formula (I), "lower alkyl group" used in the definitions of R ₁ , R ₂ , X and Y is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, 2-methylbutyl, neopentyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 3,3- Dimethylbutyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 1-ethyl-2-methyl-propyl, 1-methyl-1-ethylpropyl, 1- C1-C6 linear or branched alkyl groups such as methyl-2-ethylpropyl, 2-methyl-1-ethylpropyl or 2-methyl-2-ethylpropyl group.

The term "lower alkenyl group" used in the definition of R ₁ shown in the general formula (I) is, for example, vinyl, 1-propenyl, 2-propenyl, 1-methyl-2-propenyl, 2-methyl 2-propenyl, 2-ethyl-2-propenyl, 2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-ethyl-2-butenyl, 3-part By C2-C6 straight or branched alkenyl groups such as tenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-hexenyl, 3-hexenyl or 4-hexenyl.

The term "lower alkynyl group" used in the definition of R ₁ shown in the general formula (I) is, for example, 2-propynyl, 1-methyl-2-propynyl, 2-butynyl, 1-methyl-2 -Butynyl, 1-ethyl-2-butynyl, 3-butynyl, 2-methyl-3-butynyl, 2-pentynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hex A straight or branched alkyl group of 3 to 6 carbon atoms, such as a sinyl or 5-hexynyl group.

Examples of the term "lower cycloalkyl group" used in the definitions of R ₁ and R ₂ shown in the general formula (I) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclopropyl, 2-methyl It means a C3-C7 cycloalkyl group which may have a branched chain, such as a cyclopentyl or 2-methylcyclohexyl group.

The halogen atom mentioned in the definitions of X and Y shown in the general formula (I) means chlorine, cancelled, fluorine or oxo atom.

Examples of the term "lower haloalkyl group" used in the definitions of X and Y shown in the general formula (I) include trifluoromethyl, chloromethyl, bromomethyl, dichloromethyl, difluoromethyl, trichloromethyl Chlorine, such as 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 3-chloropropyl or 3-iodinepropyl groups, cancellation, fluorine, oxo One or several halogen atoms such as represents a lower alkyl group bonded as a substituent.

Examples of the term "lower alkoxy group" used in the definitions of X and Y shown in the general formula (I) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy C1-C6 linear or branched alkoxy, such as t-butoxy, n-heptyloxy, isopentyloxy or n-hexyloxy group.

Examples of the term "lower haloalkoxy group" used in the definitions of X and Y shown in the general formula (I) include difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy It means a C1-C6 haloalkoxy group.

Examples of the benzyl group substituted with the halogen atom on the benzyl ring of the term “benzyl group” used in the definition of R ₂ in the general formula (I), for example, benzyl group or 2-chlorobenzyl group, 3-chlorobenzyl group, 4 A halobenzyl group such as a chlorobenzyl group, a 2-fluorobenzyl group, a 3-fluorobenzyl group or a 4-fluorobenzyl group.

For example, the term "unsubstituted or substituted pyridyl group" used in the definition of R ₂ in General Formula (I) means 2-pyridyl group, 4-pyridyl group, 5-chloro-2-pyridyl group and the like. .

In the 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative represented by the general formula (I), R ₁ is a lower alkyl group, and R ₂ is mono-halo substituted or di-halo. 1-substituted-4-carbamoyl-1,2,4-tria according to formula (I) wherein substituted phenyl group, X is a halogen atom, lower alkyl group or lower haloalkyl group, and n is 0 or an integer of 1 to 2 Preference is given to sol-5-one derivatives. In formula (I), R ₁ is a lower alkyl group, R ₂ is a lower cycloalkyl group, X is a halogen atom, a lower alkyl group, or a lower haloalkyl group, and n is an integer of 0 or 1 to 2, Preference is given to the 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivatives according to the invention.

In general formula (I), R ₁ is an isopropyl group, R ₂ is a mono-halo substituted or difluoro substituted phenyl group, X is a halogen atom or a lower alkyl group, and n is 0 or an integer of 1 to 2, Particular preference is given to 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivatives according to formula (I).

The 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative of the general formula (I) according to the second invention of the present invention has the following three kinds of derivatives, namely the general formula (Ia) , Derivatives of (Ib) and (Ic).

(1) General formula (Ia)

(단, m은 0 또는 1∼5의 정수, Y는 동일하거나 서로 다를 수 있는 할로겐 원자, 저급 알킬기, 저급 할로알킬기, 저급 알콕시기, 저급 할로알콕시기 또는 시아노기 이다)으로 표시되는 비치환 또는 치환 페닐기 또는 벤젠환이 할로겐 원자로 치환되어도 좋은 벤질기, 또는 식

(단, Z는 수소원자 또는 염소원자를 나타낸다)으로 표시되는 비치한 또는 치환 피리딜기 이다]으로 표시되는 1-페닐-4-(N,N-디치환 카르바모일)-1,2,4-트리아졸-5-온 유도체.[Wherein X has the same meaning as defined in the general formula (I), that is, X may be the same or different and may be a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a cyano group, Nitro group, methylthio group, methylsulfinyl group, methylsulfonyl group, phenoxy group, acetylamino group or trifluoroacetylamino group, n is 0 or an integer of 1 to 5, and R ₁ and R ₂ are represented by general formula (I Have the same meaning as defined in), that is, R ₁ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, and R ₂ is a lower alkyl group, a lower cycloalkyl group,

(Wherein m is an integer of 0 or 1 to 5, Y is a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a cyano group), which may be the same or different from each other, or Benzyl group which substituted phenyl group or benzene ring may substitute by halogen atom, or formula

(Wherein Z represents a hydrogen atom or a chlorine atom) or an unsubstituted or substituted pyridyl group] 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4 -Triazole-5-one derivative.

(2) General formula (Ib)

의 1-나프틸기 또는

의 5,6,7,8-테트라하이드로-1-나프틸기 이고, R₁과 R₂는 일반식(Ⅰ)에 정의된 것과 동일한 의미를 갖 고, 즉 R₁은 저급 알킬기, 저급 알켄일기, 저급 알킨일기 또는 저급 시클로알킬기 이고, 또한 R₂는 저급 알킬기, 저급 시클로 알킬기, 식

(단, m은 0 또는 1∼5의 정수, Y는 동일하거나 서로 다른 할로겐 원자, 저급 알킬기, 저급 할로알킬기, 저급 알콕시기, 저급 할로알콕시기 또는 시아노기 이다)으로 표시되는 비치환 또는 치환 페닐기 또는 벤질기가 벤젠환 상에서 할로겐 원자로 치환되어도 좋은 벤질기, 또는 식

(단, Z는 수소원자 또는 염소원자를 나타낸다)으로 표시되는 비치한 또는 치환 피리딜기 이다]으로 표시되는 1-나프틸-4-(N,N-디치환 카르바모일)-1,2,4-트리아졸-5-온 유도체.[Wherein ^{a a} is an expression

1-naphthyl group or

Is a 5,6,7,8-tetrahydro-1-naphthyl group, R ₁ and R ₂ have the same meaning as defined in formula (I), that is, R ₁ is a lower alkyl group, a lower alkenyl group, Lower alkynyl or lower cycloalkyl group, and R ₂ is a lower alkyl group, a lower cycloalkyl group,

An unsubstituted or substituted phenyl group represented by (wherein m is an integer of 0 or 1 to 5, Y is the same or different halogen atom, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group or cyano group) Or a benzyl group in which a benzyl group may be substituted with a halogen atom on a benzene ring, or a formula

(Wherein Z represents a hydrogen atom or a chlorine atom) or an unsubstituted or substituted pyridyl group] 1-naphthyl-4- (N, N-disubstituted carbamoyl) -1,2, 4-triazol-5-one derivative.

(1) General formula (Ic)

(단, m은 0 또는 1∼5의 정수, Y는 동일하거나 서로 다른 것으로 할로겐 원자, 저급 알킬기, 저급 할로알킬기, 저급 알콕시기, 저급 할로알콕시기 또는 시아노기 이다)으로 표시되는 비치환 또는 치환 페닐기 또는 벤질기가 벤젠환 상에서 할로겐 원자로 치환되어도 좋은 벤질기, 또는 식

(단, Z는 수소원자 또는 염소원자를 나타낸다)으로 표시되는 비치한 또는 치환 피리딜기 이고, R₃는 수소원자 또는 메틸기 이고, K는 1 또는 2의 정수이다]으로 표시되는 1-알알킬-4-(N,N-디치환 카르바모일)-1,2,4-트리아졸-5-온 유도체.[Wherein X has the same meaning as defined in formula (I), ie X is the same or different and is a halogen atom, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, cyano group, nitro Group, methylthio group, methylsulfinyl group, methylsulfonyl group, phenoxy group, acetylamino group or trifluoroacetylamino group, n is 0 or an integer of 1 to 5, R ₁ and R ₂ are represented by general formula (I) Has the same meaning as defined, ie, R ₁ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, and R ₂ is a lower alkyl group, a lower cycloalkyl group,

Unsubstituted or substituted represented by (wherein m is an integer of 0 or 1 to 5, Y is the same or different and is a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a cyano group) A benzyl group in which a phenyl group or a benzyl group may be substituted with a halogen atom on a benzene ring, or a formula

(Wherein Z represents a hydrogen atom or a chlorine atom), an unsubstituted or substituted pyridyl group, R ₃ is a hydrogen atom or a methyl group, and K is an integer of 1 or 2; 4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative.

The derivative of general formula (Ia) is represented by the following general formula (Ia-1)

[Wherein R _1a is a lower alkyl group, R _aa is a mono-halo substituted or di-halo substituted phenyl group, X ^a is a halogen atom, a lower alkyl group or a lower haloalkyl group, n is 0 or an integer of 1 to 2 It is preferably a 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative represented by].

In addition, the derivative of formula (Ia) is represented by the following formula (Ia-1-1)

[Wherein i-Pr is an isopropyl group, R _2a is a mono-halo substituted or di-halo substituted phenyl group, X ^a is a halogen atom, a lower alkyl group or a lower haloalkyl group, n is 0 or 1 to 2 Integer]] is preferably 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative.

In addition, the derivative of the general formula (Ia-1-1) is the following general formula (Ia-1-2)

[Wherein i-Pr is an isopropyl group, T is a hydrogen atom or a fluorine atom, X ^b is the same or different chlorine atom, cancel atom, fluorine atom, methyl group, ethyl group or trifluoromethyl group, n is 0, or an integer of 1 to 2], 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative.

1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2 of the general formula (Ia-1-2) contained in the derivative of general formula (Ia) according to the first invention Representative examples of 4-triazol-5-one derivatives are specifically compounds shown in Table 1A.

For example of some preferred compounds, there is a series of compounds listed below.

(1) 1-phenyl-4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazol-5-one (following) Compound No. 4 or 8 of Table 1a)

(2) 1- (2-chlorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazole- 5-one (Compound No. 38 or 35, in Table 1a, below)

(3) 1- (3-chlorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazole- 5-one (Compound No. 75 or 76 in Table 1a below)

(4) 1- (2-fluorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazole -5-one (Compound No. 165 or 166 in Table 1a below)

(5) 1- (2,4-difluorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4 -Triazol-5-one (compound No. 184 or 181 in Table 1a below)

(6) 1- (2-fluoro-4-chlorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2, 4-triazol-5-one (Compound No. 322 in Table 1a below)

(7) 1- (2-methylphenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazole-5 -One (compound No. 322 or 331 in Table 1a below)

(8) 1- (2,4-dimethylphenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-tria Zol-5-one (Compound No. 581 or 582 in Table 1a below)

(9) 1- (2-chloro-4-methylphenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4- Triazole-5-one (compound No. 634 or 633 in Table 1a below)

In addition, Compound No. 231; 234; 269; 270; 281; 284; 576; 577; 587; 591; 592; 596; 597; 635; 636; 637; 638; Compounds 639 and 640 are also preferred compounds.

In addition, the 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative of the general formula (Ia) is preferably the following general formula (Ia- 2)

1-phenyl-4- (N in which X and n have the same meanings as defined in general formula (I) or (Ia), R _1b is a lower alkyl group, and R _2b is a lower cycloalkyl group. , N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivatives.

In the derivative of general formula (Ia-2), X is a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a trifluoromethyl group or a trifluoromethyloxy group, n is an integer of 0 or 1 to 2, and R _1b is a methyl group , Ethyl group, n-propyl group or isopropyl group, 1-phenyl-4- (N, N-disubstituted carboxyl) of general formula (Ia-2) wherein R _2b is a cyclopropyl group, a cyclopentyl group or a cyclohexyl group Particularly preferred is bamoyl) -1,2,4-triazol-5-one.

In the 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative of the general formula (Ib), R ₁ is a lower alkyl group in the general formula (Ib) It is especially an isopropyl group, it is preferable that R <_2> is a mono-halo substituted or di-halo substituted phenyl group, especially 4-fluoro or 2,4-difluorophenyl group, and n is 0 or an integer of 1-2.

Representative examples of the derivative of formula (Ib) include Compound No. 649-652. In particular, 1- (5,6,7,8-carbamoyl) -1,2,4-triazol-5-one (Compound No. 650) is a preferred compound.

The 1-alalkyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative of the general formula (Ic) according to the first invention is preferably General Formula (Ic-1)

(Wherein R _1a is a lower alkyl group, R _2a is a mono-halo substituted or di-halo substituted phenyl group, X ^a is a halogen atom, a lower alkyl group or a lower haloalkyl group, n is 0 or an integer of 1 to 2, K is an integer of 1 or 2).

Derivatives of the general formula (Ic-1) is the following general formula (Ic-1-1)

[Wherein i-Pr is an isopropyl group, T is a hydrogen atom or a fluorine atom, X ^b is the same or different and is a chlorine atom, a cancel atom, a fluorine atom, a methyl group, an ethyl group or a trifluoromethyl group, n Is 0 or an integer of 1 to 2, R ₃ is a hydrogen atom or a methyl group, K is an integer of 1 or 2], and 1-alalkyl-4- (N, N-disubstituted carbamoyl)- Particular preference is given to 1,2,4-triazol-5-one derivatives.

Examples of representative compounds of the 1-alalkyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivatives of general formula (Ic) are given in Table 1c below. Displayed Compound No. 653-684 compound. Particularly preferred examples are 1- (2,3-dichlorobenzyl) -4- (N-isopropyl-N-2,4-difluorophenyl-carbamoyl) -1,2,4-triazol-5-one (Compound No. 662) and 1- (2-Chloro-α-methylbenzyl) -4- (N-isopropyl-N-2,4-difluorophenyl-carbamoyl) -1,2,4- Triazol-5-one (Compound No. 675).

In the second invention, the following general formula (I)

1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative represented by [wherein A, R ₁ and R ₂ have the same meanings as defined above] as an active ingredient A herbicidal composition is provided.

A second herbicide composition according to the present invention is a 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative of the general formula (Ia) as defined above. May be contained as an active ingredient. In addition, 1-naphthyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative of the general formula (Ib) as defined above may be contained as an active ingredient. have.

In addition, the second herbicidal composition of the present invention is 1-alalkyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazole-5- of formula (Ic) as defined above. On derivatives may be contained as an active ingredient.

Best mode for carrying out the invention

Representative examples of 1-phenyl-4-carbamoyl-1,2,4-triazol-5-one of general formula (Ia) according to the first invention are shown in Table 1A below. In addition, a representative example of 1-naphthyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one of formula (Ib) is shown in Table 1b below, Representative examples of 1-alalkyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one of formula (Ic) are shown in Table 1c below. In addition, the compound No. shown to Table 1a, Table 1b, and Table 1c was also referred to the following Example and the test example.

In Table 1a, the compound in which Xn is represented by H indicates that there is no substituent (X) on the phenyl group represented by formula (I), that is, n = 0. In addition, in 1a-Table 1c, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, and Bu represents a butyl group. For example, i-Pr represents an isopropyl group, n-Pr represents an n-propyl group, i-Bu represents an isobutyl group, n-Bu represents an n-butyl group, and sec-Bu represents a secondary butyl group.

A method for producing the 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative of the general formula (I) according to the first invention will be described.

In general, the compound of general formula (I) is reacted with carbamoyl chloride of general formula (III) of 1-substituted-1,2,4-triazol-5-one derivative of general formula (II) It can be produced by the method.

(여기서 X와 n은 상기와 동일한 의미를 갖는다)의 비치환 또는 치환 페닐기 또는 1-나프틸기 또는 5,6,7,8-테트라 히이드로-1-나프틸기 또는 식

(여기서 X, n, R₃와 K는 상기와 동일한 의미를 갖는다)의 알알킬기를 나타내고, 또한 R₁과 R₂는 상기에서 정의한 의미를 갖는다(이하, 동일하다).However, in the above reaction formula A is

(Where X and n have the same meaning as above) an unsubstituted or substituted phenyl group or 1-naphthyl group or 5,6,7,8-tetrahydro-1-naphthyl group or formula

(Where X, n, R ₃ and K have the same meaning as above), and R ₁ and R ₂ have the meanings defined above (the same applies hereinafter).

The reaction of this method is to contact the 1-substituted-1,2,4-triazol-5-one derivative of formula (II) in an organic solvent with carbamoyl chloride of formula (III) in the presence of a dechlorinating agent. Is achieved.

Examples of the dechlorination agent used in the reaction include bases, for example, organic tertiary amines such as triethylamine, tributylamine, diethylisopropylamine, 4-dimethylaminopyridine, pyridine or alkali metals such as sodium carbonate and potassium carbonate. Alkali metal hydroxides such as carbonate, sodium hydroxide, potassium hydroxide, and preferred bases are pyridine and potassium carbonate. The base is preferably used in an amount of about 1 equivalent when potassium carbonate is used, and an excess of pyridine is used because pyridine also acts as a solvent.

Examples of the organic solvent used in the reaction include aromatic hydrocarbons such as benzene, toluene and xylene, dichloroethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and halogenated hydrocarbons such as tetrachloroethane, acetonitrile and propionitrile. Nitriles such as nitrile, ethyl acetate, esters such as ethyl propionate, diethyl ether, ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, pyridine and the like can be used. Moreover, these mixed solvent can also be used. Preferably acetonitrile or pyridine.

The reaction temperature is usually carried out at room temperature to 150 ° C, preferably at 20 to 80 ° C. The reaction time depends on the reaction temperature or the quality of the reactor, but is usually completed in 30 minutes to 24 hours.

The compound of the general formula (I), which is the desired reaction product, is collected by usual work-up from the obtained reaction solution. For example, water is added to the obtained reaction solution and washed with water, and then the solvent is distilled off. If desired, the desired product can be purified by an operation such as column chromatography or recrystallization.

The preparation of the compound of the present invention of general formula (I) by the above method is specifically the same as Examples 1 to 9 below.

In addition, the 1-substituted-1,2,4-triazol-5-one derivative of general formula (II) used as a starting material in the said method is a novel or known compound, For example, "SYNTHETIC COMMUNICATIONS" It synthesize | combined easily according to the method of the sixteenth volume (2), 166-167 page (1986), The manufacture is shown to following reference manufacture examples 1-4.

Carbamoyl chlorides of the general formula (III) used as the reactants in the above method are well known in the field of organic chemistry, for example, in the method described in "Chemische Berichte", Vol. 88, p. 301 (1955). Therefore, it is easily synthesized.

And the herbicide composition by a 2nd this invention is demonstrated concretely as follows.

The compound represented by the general formula (I) of the present invention is shown in the following test example, has excellent herbicidal activity, and can be used as a herbicide for removing weeds. The compound of the present invention can be used as a selective herbicide because it exhibits selective herbicidal activity between the following weeds and crops.

Flower and weeds include Alopecurus, Oven, Avro, Bromus, Cyperus, Digitaria, Echinochloa, Eleocharis, Eleusine, and Monochoria. ), Panicum, Paspalum, Phleum, Poa, Setaria, and Johnson Grass. As broadleaf weeds, Abutilon, Amaranthus, Ambrosia, Hairy Bidens, Ramsquates, Vine, Galium, Ipomoea, Common Star Spring (Lindernia), Persicaria, Common Purslane (Portulaca), Indian Tooth Cup (Rotala), Common Stellaria, Viola, and Burdock (Xanthium).

Useful cultivated plants, ie, crops, in the rice fields in which the compounds of the present invention can be used include barley (Hordeum), rice (Oryza), sugarcane (Saccharum), wheat (Triticum), and corn (Zea). The broad-leaf crops include peanuts (Arachis), beets (Beta), fluids (Brassica), soybeans (Glycine), cotton (Gossypium), tomato (Lycopersicon).

The use of the compound of the general formula (I) of the present invention as a herbicide is not limited only to the weeds and the paddy fields of the crops.

In the second herbicide composition according to the present invention, the 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative of general formula (I) according to the first invention is used as an active ingredient. In addition, the form of the composition blended with the carrier is also formulated.

When formulated as such a herbicide composition, a compound of the general formula (I) as its active ingredient is mixed with a carrier or diluent, and if desired, at least one additive and auxiliaries are mixed by a known method, and usually used as a pesticide. For example, it can be combined as a suitable form of granules, granules, hydrating agents, granulating hydrating agents, emulsions, water-soluble agents, floppy preparations, tablets, powders and the like.

The compounds of the present invention may also be used in combination with other pesticides, for example fungicides, insecticides, herbicides, mites, plant growth regulators or fertilizers, soil improvers and the like. In particular, by mixing with other herbicides, the amount of the compound of the present invention can be reduced or saved. A more powerful effect can be expected from the enlargement and synergy of the herbicidal spectrum caused by the co-action of two drugs. At this time, a combination with a plurality of known herbicides is possible at the same time.

As the carrier to be used in the formulation, any carrier, either solid or liquid, can be used as long as it is generally used for agrochemical formulations. The carrier is not limited to a specific one. For example, these solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, quartz, calcium carbonate, phosphate, slaked lime, silica sand, ammonium sulfate, urea, etc.) Material powder (soybean flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), high molecular compound (petroleum resin, polyvinyl chloride, ketone resin, etc.), alumina, silicate, sugar polymer, highly disperse silicic acid, wax Etc. can be mentioned.

Examples of the liquid carrier that can be used include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, ethylbenzene , Methylnaphthalene, etc.), halogen ring hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorofluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane , Tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorne, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (Dimethylformamide, dimethylacetamide, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), Alcohol esters (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbon rates (n-hexane, cyclohexane, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), Industrial gasoline (petroleum ether, solvent naphthane, etc.), petroleum oil (paraffins, kerosene, diesel, etc.) are mentioned.

In addition, when formulated with an emulsion, a hydrating agent, a flow agent, or the like, various surfactants are blended into the present composition for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, and diffusion. As such surfactant, nonionic surfactant (polyoxyethylene alkether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, etc.), anionic surfactant (alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl) Sulfates, polyoxyethylene alkyl sulfates, arylsulfonates, etc.), cationic surfactants [alkylamines (laurylamine, stearyltrimethylammonium chloride, etc.), polyoxyethylenealkylamines], amphoteric surfactants [carboxylic acids (Betaine type), sulfate ester salt, etc.], etc. are mentioned, It is not limited only to what was illustrated as such.

In addition, various auxiliaries such as other polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinylacetate, alkanoic acid, gelatin, casein and tragacanth rubber can be used.

In the herbicide composition of the second aspect of the present invention, when the above-mentioned various preparations are prepared, the compound of the present invention of the general formula (I) is 0.001% to 95% (wt%; the same or less), preferably 0.01% to 75% It can be formulated to contain in the range. For example, in the case of granulation, 0.01% to 10%, hydrating agent, follower, 1 to 75% for liquid and emulsion, powder, driftless powder, and 0.01% to 5% for fine powder It can contain a compound of this invention in the range.

In the case of granules and flowables, the preparations prepared in this way may be dispersed in an amount in the range of about 0.3 g to 300 g per 10 ar as a conversion amount of the active ingredient on its own soil surface, in the soil or in water. In the case of a hydrating agent, an oily agent, etc., it is good to dilute with water or a suitable solvent, and to make it spread in the quantity which consists of about 0.3 g-about 300 g per 10 ar as an active ingredient.

In addition, many specific examples of the compounds of the general formula (I) according to the first aspect of the present invention, even when used at a low usage amount in the range of 3 to 30 g per 10 ar, complete weeding of paddy field or field weed at 100% herbicidal rate. It was recognized that the herbicidal effect could be killed.

Examples and Reference Preparation Examples The preparation examples of the compound of the general formula (I) according to the present invention will be described in detail as follows.

Example 1

1- (2-Chlorophenyl) -4- (N-isopropyl-N-2,4-difluorophenyl-carbamoyl) -1,2,4-triazol-5-one (compounds in Table 1a) No. 35).

1.7 g of potassium carbonate is added to a 50 ml solution of 20 g of 1- (2-chlorophenyl) -1,2,4-triazol-5-one in acetonitrile. The resulting mixture was stirred at room temperature for 30 minutes, and then 3.0 g of N-isopropyl-N-2,4-difluorophenylcarbamoyl chloride was added and stirred at 80 ° C for 1 hour. Inorganic salt is filtered out from the reaction solution. The solvent is then removed from the filtrate under reduced pressure. The obtained residue is dissolved in 80 ml of toluene, the solution is washed with water, dried over anhydrous sodium sulfate and the solvent is removed. The obtained residue is purified by silica gel column chromatography to obtain 3.2 g (yield 80%) of the title compound as a title. Melting point 146-148 degreeC.

Example 2

1- (2-Chlorophenyl) -4- (N-isopropyl-N-4-fluorophenyl-carbamoyl) -1,2,4-triazol-5-one (Compound No. 38 in Table 1a) Manufacture).

2.6 g of N-isopropyl-N-4-fluorophenylcarbamoyl chloride is added to a 50 ml solution of 2.0 g of 1- (2-chlorophenyl) -1,2,4-triazol-5-one. . The resulting mixture is left at room temperature for 20 hours. The pyridine is removed from the reaction solution under reduced pressure. The obtained residue is dissolved in 80 ml of toluene, and the solution is washed with 1 N hydrochloric acid, then with water and dried over anhydrous sodium sulfate. After the solvent was removed from the dried solution, the obtained residue was purified by silica gel column chromatography to obtain 2.9 g (yield 77%) of the title compound. Melting point 118-120 degreeC.

Example 3

Preparation of 1-phenyl-4- (N-isopropyl-N-phenylcarbamoyl) -1,2,4-triazol-5-one (Compound No. 1 in Table 1a).

2.4 g of N-isopropyl-N-phenylcarbamoylchloride is added to a 50 ml solution of 1.6 g of 1-phenyl-1,2,4-triazol-5-one. The mixture is left at room temperature for 20 hours. Pyridine is removed from the reaction solution under reduced pressure. The obtained residue is dissolved in 80 ml of toluene, the solution is washed with 1 N hydrochloric acid, washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent, the obtained residue is purified by silica gel column chromatography to obtain 2.4 g (yield 75%) of the title compound. Melting point 144-145 degreeC.

Example 4

1- (2-Chlorophenyl) -4- (N-ethyl-N-2,4-difluorophenylcarbamoyl) -1,2,4-triazol-5-one (Compound No. 26).

2.8 g of N-ethyl-N-2,4-difluorophenylcarbamoyl chloride was added to a 50 ml solution of 2.0 g of 1- (2-chlorophenyl) -1,2,4-triazol-5-one. Add. The mixture is left at room temperature for 20 hours. Pyridine is removed from the reaction solution under reduced pressure. The obtained residue is dissolved in 80 ml of toluene, the solution is washed with 1 N hydrochloric acid, washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column chromatography to obtain 3.0 g (yield 79%) of the title compound of interest. Melting point 110-111 degreeC.

Example 5

Preparation of 1- (2-chlorophenyl) -4- (N-ethyl-N-cyclohexylcarbamoyl) -1,2,4-triazol-5-one (Compound No. 66 in Table 1a).

2.0 g of N-ethyl-N-cyclohexylcarbamoylchloride is added to a 50 ml solution of 20 g of 1- (2-chlorophenyl) -1,2,4-triazol-5-one. The mixture is left at room temperature for 20 hours. Pyridine is removed from the reaction solution under reduced pressure. The obtained residue is dissolved in 80 ml of toluene, the solution is washed with 1 N hydrochloric acid, washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent, the obtained residue is purified by silica gel column chromatography to obtain 3.0 g (yield 84%) of the title compound of interest. Melting point 105-106 degreeC.

Example 6

1- (2-methylphenyl) -4- (N-isopropyl-N-2,4-difluorophenylcarbamoyl) -1,2,4-triazol-5-one (Compound No. 331).

3.0 g of N-isopropyl-N-2,4-difluorophenylcarbamoyl chloride was added to a 50 ml solution of 1.8 g of 1- (2-methylphenyl) -1,2,4-triazol-5-one. Add. The mixture is left at room temperature for 20 hours. Pyridine is removed from the reaction solution under reduced pressure. The obtained residue is dissolved in 80 ml of toluene, the solution is washed with 1 N hydrochloric acid, washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent, the obtained residue is purified by silica gel column chromatography to obtain 3.1 g (yield 81%) of the title compound of interest. Melting point 106-107 degreeC.

Example 7

1- (2,4-dichlorophenyl) -4- (N-isopropyl-N-2,4-difluorophenylcarbamoyl) -1,2,4-triazol-5-one (from Table 1a Preparation of Compound No. 231).

N-isopropyl-N-2,4-difluorophenylcarbamoylchloride in a 50 ml solution of 2.3 g of 1- (2,4-dichlorophenyl) -1,2,4-triazol-5-one Add 3.0 g. The mixture is left at room temperature for 20 hours. Pyridine is removed under reduced pressure. The obtained residue is dissolved in 80 ml of toluene, the solution is washed with 1 N hydrochloric acid, washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent, the obtained residue is purified by silica gel column chromatography to obtain 3.1 g (yield 71%) of the title compound of interest. Melting point 129-131 degreeC.

Example 8

1- (2-Chloro-α-methylbenzyl) -4- (N-isopropyl-N-2,4-difluorophenylcarbamoyl) -1,2,4-triazol-5-one (Table Preparation of Compound No. 675) of 1c.

0.8 g of potassium carbonate is added to a 30 ml solution of 1.0 g of 1- (2-chloro-α-methylbenzyl) -1,2,4-triazol-5-one in acetonitrile. The mixture was stirred at room temperature for 30 minutes, after which 1.3 g of N-isopropyl-N-2,4-difluorophenylcarbamoylchloride was added. The resulting mixture is stirred at 80 ° C. for 1 hour. After removing the inorganic salt from the reaction solution, the solvent is removed under reduced pressure. The obtained residue is dissolved in 50 ml of toluene, the solution is washed with water, dried over anhydrous sodium sulfate, and the solvent is removed from the solution under reduced pressure. The obtained residue is purified by silica gel column chromatography to obtain 1.3 g (yield 68%) of the title compound of interest. Melting point 160-161 degreeC.

Example 9

Preparation of 1-benzyl-4- (N-isopropyl-N-2,4-difluorophenylcarbamoyl) -1,2,4-triazol-5-one (Compound No. 656 in Table 1c) .

1.3 g of 1-benzyl-1,2,4-triazol-5-one and 2.3 g of N-isopropyl-N-2,4-difluorophenylcarbamoylchloride are added to 30 ml of pyridine. The mixture is stirred at room temperature for 1 hour and then left overnight. 150 ml of toluene and 150 ml of water are added from the reaction solution, and the mixture is separated. The obtained toluene layer was washed again with 1 N hydrochloric acid and saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed from the toluene solution under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 1.5 g (yield 54%) of the title compound. Melting point 109-111 degreeC.

Reference Manufacturing Example 1

Preparation of 1- (2-chlorophenyl) -1,2,4-triazol-5-one.

25 g of 2-chlorophenylhydradine hydrochloride are dissolved in 230 ml of water. 29 g of glyoxylic acid 40% aqueous solution was dripped at this solution under ice water cooling. The obtained mixture is stirred at 10 to 20 ° C. for 2 hours, and the precipitated powder is collected by suction filtration and washed with water. The powder thus obtained is dried under reduced pressure in a desiccator to give 27.2 g of brown powder. 27.2 g of this powder is suspended in 400 ml of toluene, and 14 g of triethylamine is added dropwise to the suspension, followed by 37.8 g of azylated diphenylphosphoryl.

The reaction mixture is heated and stirred at 70 to 80 ° C. for 4 hours and again at 100 ° C. for 2 hours. After cooling the obtained reaction solution, 760 ml of dibasic potassium hydroxide is added under ice water cooling, and extracted. 160 g of concentrated hydrochloric acid is added to the alkali aqueous layer obtained as an extract, and it is made acidic. The precipitated crystals are filtered off and washed with water. The obtained crystals are dissolved in a mixed solvent of toluene and ethanol, and azeotropically dehydrated in the solution under reduced pressure. When the obtained crystals were recrystallized from ethyl acetate, 19.1 g (yield 70%) of the title compound was obtained. Melting point 155-156 degreeC.

Reference Production Example 2

Preparation of 1-phenyl-1,2,4-triazol-5-one.

12 g of phenylhydradine hydrochloride are dissolved in 100 ml of water. 15.3 g of glyoxylic acid 40% aqueous solution was dripped at this solution under ice-water cooling. The obtained mixture is stirred at 10 to 20 ° C. for 2 hours, and the precipitated powder is suction filtered and washed with water. The powder thus obtained is dried under reduced pressure in a desiccator to obtain 12.9 g of a brown powder. 12.9 g of this powder is suspended in 250 ml of toluene, 7.9 g of triethylamine is added dropwise to the suspension, and then 21.7 g of azylated diphenylphosphoryl is added dropwise. The reaction mixture is heated and stirred at 70 to 80 ° C. for 2 hours and again at 100 ° C. for 1 hour. After cooling the obtained reaction solution, 400 ml of 2N sodium hydroxide is added and extracted under ice-water cooling. 90 g of concentrated hydrochloric acid is added to the alkali aqueous layer obtained as an extract, and it is made acidic. The precipitated crystals are filtered off and washed with water. The obtained crystals are dissolved in a mixed solvent of toluene and ethanol, and azeotropically dehydrated in the solution under reduced pressure. The obtained crystals were recrystallized from ethyl acetate to obtain 9.1 g (yield 68%) of the title compound. Melting point 182-183C.

Reference Production Example 3

Preparation of 1- (2-chloro-α-methylbenzyl) -1,2,4-triazol-5-one.

4.5 g of 2-chloro-α-methylbenzylhydradine hydrochloride are dissolved in 100 ml of water. To the solution, 4.1 g of a 40% aqueous solution of glyoxylic acid was added dropwise under ice water cooling. The obtained mixture is stirred at 10 to 20 ° C. for 2 hours, and the precipitated powder is suction filtered and washed with water. The powder thus obtained is dried under reduced pressure in a desiccator to obtain 4.7 g of brown powder. 4.7 g of this powder is suspended in 100 ml of toluene, 2.1 g of triethylamine is added dropwise thereto, and then 5.7 g of azide diphenylphosphoryl is added dropwise thereto. The reaction mixture is heated and stirred at 70 to 80 ° C. for 1 hour and again at 100 ° C. for 1 hour. After the reaction solution was cooled, 100 ml of 2N sodium hydroxide was added thereto under ice water cooling. 25 g of concentrated hydrochloric acid is added to this alkaline aqueous layer to make it acidic. The precipitated crystals are filtered off and washed with water. The obtained crystals are dissolved in a mixed solvent of toluene and ethanol, and azeotropically dehydrated in the solution under reduced pressure. When the obtained crystals were recrystallized from ethyl acetate, 3.0 g (yield 65%) of the title compound were obtained. Melting point 141-144 degreeC.

Reference Production Example 4

Preparation of 1-benzyl-1,2,4-triazol-5-one.

16.2 g of benzylhydradine dihydrochloride are dissolved in 300 ml of water. 15.4 g of glyoxylic acid 40% aqueous solution was dripped at this solution under ice-water cooling. The obtained mixture is stirred at 10 to 20 ° C for 1 hour, and the precipitated powder is filtered and washed with water. When the obtained powder is dried in a desiccator under reduced pressure, 9.9 g of brown powder is obtained. 9.0 g of this powder is suspended in 250 ml of toluene, and 5.1 g of triethylamine is added dropwise thereto, and then 13.9 g of azylated diphenylphosphoryl is added dropwise thereto. The reaction mixture is heated and stirred at 70 to 80 ° C. for 1 hour and again at 100 ° C. for 1 hour. After the reaction solution was cooled, 300 ml of 2N sodium hydroxide was added thereto under ice water cooling. 60 g of concentrated hydrochloric acid is added to the alkaline aqueous layer in small amounts to make acid, and extracted with 150 ml of ethyl acetate. The ethyl acetate layer (extract) is washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent is removed from the solution under reduced pressure. The obtained residue is purified by silica gel column chromatography to obtain 4.7 g (yield 53%) of the title compound of interest. Melting point 147-149 degreeC.

Representative specific examples of 1-substituted-1,2,4-triazol-5-ones prepared similarly to 1 to 4 and represented by the following general formulas (IIa), (IIb) or (IIc) The following Table 2-1, Table 2-2 and Table 2-3 are shown.                 

In addition, the above-mentioned method of formulating the compound of the present invention of general formula (I) into the herbicide composition will be specifically described with Examples 10 to 15 below. However, this invention is not limited only to these Examples, It can form and mix other types of additives other than what was illustrated by these Examples at arbitrary ratios, and can formulate. In addition, compound No. is shown to the said Table 1a, Table 1b, and Table 1c, and all the "part" in an Example shows a weight part.

Example 10 (granulation)

          Compound no. 1 Part 1

          Calcium lignin sulfonate 1 part

          Lauryl Sulfate Part 1

          Bentonite Part 30

          Talc 67

15 parts of water is added, the mixture is mixed in a mixer, and then granulated in an extrusion granulator. It is dried in a flow drier to obtain a granule containing 1% of the active ingredient.

Example 11 (flow enabled agent)

Compound no. 35 Part 20.0

2.0 parts of sulfosuccinic acid di-2-ethylhexyl ester sodium salt

2.0 parts of polyoxyethylene nonylphenyl ether

Propylene glycol 5.0 parts                 

Defoamer 0.5 parts

70.5 parts of water

The above components are mixed and ground uniformly in a wet ball mill to obtain a flow enabler containing 20% of the active ingredient.

Example 12 (Drying Flow Enabler)

   Compound no. 331 Part 75

   Isoban No. 1 [anionic surfactant:

     Nihon Claray Supren Chemical Co., Ltd.]

   Barnirex N [anionic surfactant:

      Sanyo Kokusaku Pulp Co., Ltd.]

   White Carbon Part 5

   Clay Part 5

The above components are uniformly mixed and pulverized to obtain a dry flow agent (granule hydrating agent) containing 75% of the active ingredient.

Example 13 (Hydrating)

              Compound no. 231 part 15

              White Carbon Part 15

              Calcium lignin sulfonate part 3

              2 parts of polyoxyethylene nonylphenyl ether

              Diatomaceous Earth Part 5                 

              60 parts of clay

The above components are uniformly mixed in a pulverizing mixer to obtain a hydrating agent containing 15% of the active ingredient.

Example 14 (emulsion)

  Compound no. 8 20

  Solpol 700H [Emulsifier: Japan Toyo Chemical Co., Ltd.] 20 parts

  Xylene 60

Example 15 (powder)

              Compound no. 4810.5Parts

              White Carbon Part 0.5

              Calcium Stearate0.5part

              50.0 parts of clay

              Talc 48.5

When the above components are mixed and ground uniformly, a powder containing 0.5% of the active ingredient is obtained.

In addition, according to the formulation example mentioned above, the herbicide composition containing the compound of general formula (I) which concerns on this invention can all be formulated as herbicide of various formulations, respectively.

Next, the herbicidal effect of the compound represented by the general formula (I) of the present invention will be described using test examples.                 

Test Example 1

Herbicide effect test on crude aquatic plants and pesticide test on rice

Fill the paddy soil with 1/5000 ar pot, add water and mix the fertilizer (N: P: K = 17:17:17) into the soil. The crude plants are sown 1 cm deep into the soil surface. Next, 2.5-leafed rice seedlings (breed: Nihon Bear) are transplanted and submerged to about 3 cm. Then, management is carried out in a glass greenhouse, and in accordance with Example 13, one day after rice transplantation, a predetermined amount of a water dilution liquid diluted with water is added dropwise to weed. After 28 days after treatment, herbicidal effects and rice weakness were investigated, and the herbicidal effect (%) was calculated by the following formula. The results are shown in Table 3.

Herbicidal effect (%) = [1- (a / b)] × 100

[Where a represents the dry weight of the weeds in the treatment zone (g), and b represents the dry weight of the weeds in the trade zone (g)]

In addition, the weakness of rice was investigated based on the evaluation index shown below.

Weakness Weakness

                   5 Test

                   4 weak

                   3 of the weak

                   2 weak cattle

                   1 weakness                 

                   0 no weakness

The following comparative compound A was used as a comparative agent, and a hydrating agent containing the same was prepared according to Example 13. A comparative test is carried out in the same manner as above. The results are shown in Table 3. Compound No is shown in the said Table 1a, Table 1b, Table 1c.

Test compound Active ingredient usage (g / 10 are) Herbicide effect (%) Weak One 15 100 0 4 4 100 0 8 4 100 0 25 4 100 0 26 4 100 0 27 4 100 0 28 4 100 0 29 4 100 0 30 4 100 0 31 4 100 0 32 4 100 0 33 4 100 0 34 4 100 0 35 One 100 0 38 One 100 0 42 4 100 0 65 15 100 0 66 4 100 0 72 15 100 0 73 15 100 0 74 15 100 0 75 15 100 0 76 15 100 0 85 2 100 0 88 4 100 0 135 15 100 0 165 4 100 0 166 One 100 0 169 15 100 0

Test compound Active ingredient usage (g / 10 are) Herbicide effect (%) Weak 170 4 100 0 181 2 100 0 184 4 100 0 200 2 100 0 221 One 100 0 222 One 100 0 231 2 100 0 234 2 100 0 269 2 100 0 270 2 100 0 281 2 100 0 284 2 100 0 318 4 100 0 320 15 100 0 322 2 100 0 324 2 100 0 331 One 100 0 334 2 100 0 381 4 100 0 384 4 100 0 431 2 100 0 434 2 100 0 481 One 100 0 484 One 100 0 518 2 100 0 520 15 100 0 521 4 100 0 522 4 100 0 531 4 100 0 534 4 100 0

Test compound Active ingredient usage (g / 10 are) Herbicide effect (%) Weak 576 2 100 0 577 2 100 0 581 4 100 0 582 4 100 0 586 4 100 0 587 4 100 0 591 2 100 0 592 2 100 0 596 One 100 0 597 One 100 0 631 2 100 0 632 2 100 0 633 15 100 0 634 15 100 0 635 4 100 0 636 4 100 0 637 15 100 0 638 15 100 0 639 2 100 0 640 4 100 0 650 4 100 0 656 15 100 0 658 15 100 0 662 4 100 0 665 4 100 0 666 4 100 0 675 4 100 0 678 15 100 0 Comparative Compound A 100 60 3

Comparative Compound A used in this Test Example is represented by the following formula

Tetrazolinone derivatives, i.e., 1-phenyl-4- (N-isopropyl-N-phenylcarbamoyl) -tetrazolin-5-one (described in Japanese Patent Application Laid-Open No. 62-12767). Compound A is also the same in the following Test Examples 2-4)

Test Example 2

Herbicide Effect Test on Crude Weeds (Weed Growth Treatment of Weeds)

Fill the paddy soil with water, add water, and mix the compound fertilizer (N: P: K = 17:17:17) into the soil. After alternation, the crude myelin sheaths are mixed to a depth of 1 cm of the soil surface and submerged to 3 cm. Subsequent management is carried out in a glass greenhouse, and at the time when the crude myelin reaches 1.5-leaf phase, according to Example 13 containing the compound of the present invention, a predetermined amount of a water dilution liquid diluted with water is added dropwise to weed. .

The herbicidal effect is examined 21 days after drug treatment, and the herbicidal effect is evaluated based on the same criteria as in Test Example 1. A hydrating agent containing Comparative Compound A was prepared as a comparative drug according to Example 11. A comparative test is carried out in the same manner as above. The results are shown in Table 4. Compound No. is shown to the said Table 1a-Table 1c.

Test compound Active ingredient usage (g / 10 are) Herbicide effect (%) One 30 100 4 8 100 8 8 100 25 8 100 26 8 100 27 8 100 28 8 100 29 8 100 30 8 100 31 8 100 32 8 100 33 8 100 34 8 100 35 2 100 38 2 100 42 8 100 65 30 100 66 8 100 72 30 100 73 30 100 74 30 100 75 30 100 76 30 100 85 4 100 88 4 100 135 30 100 165 8 100 166 2 100 169 30 100 170 8 100

Test compound Active ingredient usage (g / 10 are) Herbicide effect (%) 181 4 100 184 4 100 200 4 100 221 2 100 222 2 100 231 4 100 234 4 100 269 4 100 270 4 100 281 4 100 284 4 100 318 8 100 320 30 100 322 4 100 324 4 100 331 2 100 334 2 100 381 8 100 384 8 100 431 4 100 434 4 100 481 2 100 484 2 100 518 2 100 520 30 100 521 15 100 522 8 100 531 4 100 534 8 100 576 4 100

Test compound Active ingredient usage (g / 10 are) Herbicide effect (%) 577 8 100 581 15 100 582 8 100 586 8 100 587 15 100 591 8 100 592 8 100 596 4 100 597 4 100 631 8 100 632 8 100 633 30 100 634 30 100 635 15 100 636 15 100 637 30 100 638 30 100 639 8 100 640 30 100 650 30 100 656 30 100 658 30 100 662 30 100 665 15 100 666 15 100 675 15 100 678 30 100 Comparative Compound A 100 50

Test Example 3 Herbicidal effect test on paddyweed (usually starflower, hyacinth, Japanese mackerel)

Fill the paddy soil with water, add water, and mix the compound fertilizer (N: P: K = 17:17:17) into the soil. After alternation, the seeds of the spring primrose, water lily, and Japanese mackerel are sown each 30 seeds at a depth of 1-2 cm of soil surface. After sowing, it is soaked as it is to have a depth of 2 cm. After that, management is carried out in a glass greenhouse, and a certain amount of a water dilution liquid obtained by diluting the hydrating agent prepared according to Example 13 with water is added dropwise one day after sowing.

The herbicidal effect is investigated 21 days after drug treatment, and the herbicidal effect is evaluated on the same criteria as in Test Example 1. A hydrating agent containing Comparative Compound A as a comparative agent was prepared in accordance with Example 13. A comparative test is carried out in the same manner as above. The results are shown in Table 5. Compound No. is shown to the said Table 1a-Table 1c.

Test Compound No. Active ingredient usage (g / 10 are) Herbicide rate on weeds (%) Common star spring flower Water sleep Japanese big mackerel One 15 100 95 95 4 4 100 100 100 8 4 100 100 100 25 4 100 100 100 26 4 100 100 100 27 4 100 100 100 28 4 100 100 100 29 4 100 100 100 30 4 100 100 100 31 4 100 100 100 32 4 100 100 100 33 4 100 100 100 34 4 100 100 100 35 2 100 100 100 38 2 100 100 100 42 4 100 100 100 65 15 100 90 90 66 4 100 100 100 72 15 100 90 95 73 15 100 90 95 74 15 100 90 95 75 15 95 100 100 76 15 90 90 100 85 2 100 100 100 88 4 100 100 100 135 15 90 90 90 165 4 100 90 90 166 2 100 100 100 169 15 90 90 100 170 4 100 100 90

Test Compound No. Active ingredient usage (g / 10 are) Herbicide rate on weeds (%) Common star spring flower Water sleep Japanese big mackerel 181 2 100 100 100 184 4 100 100 100 200 2 100 100 100 221 2 100 95 100 222 2 100 100 100 231 2 100 100 100 234 2 100 100 100 269 4 100 100 100 270 4 100 100 100 281 2 100 100 100 284 2 100 100 100 318 4 95 90 100 320 15 100 90 95 322 2 100 100 100 324 2 100 100 100 331 2 100 100 100 334 2 100 100 100 381 4 100 100 100 384 4 100 100 100 431 4 100 100 100 434 4 100 100 100 481 2 100 100 100 484 2 100 100 100 518 4 100 100 100 520 15 90 95 90 521 4 100 95 100 522 4 100 100 95 531 4 100 100 100 534 4 100 100 100 576 4 100 100 100

Test Compound No. Active ingredient usage (g / 10 are) Herbicide rate on weeds (%) Common star spring flower Water sleep Japanese big mackerel 577 4 100 100 100 581 4 100 100 100 582 4 100 95 100 586 4 100 100 100 587 4 95 100 95 591 4 100 100 100 592 4 100 100 100 596 2 100 100 100 597 2 100 100 100 631 4 100 100 100 632 4 95 100 90 633 15 95 95 90 634 15 95 95 95 635 4 100 90 90 636 4 100 95 90 637 15 90 90 90 638 15 90 90 90 639 4 100 100 100 640 4 100 100 100 650 4 100 100 100 656 15 95 95 95 658 15 95 100 95 662 4 100 100 100 665 4 100 100 100 666 4 100 100 100 675 4 100 100 100 678 15 95 95 100 Comparative Compound A 100 70 70 40

Test Example 4

Herbicide Effect Test and Weakness Test on Field Crop Weeds

(1) Herbicide effect test on field crop weeds

Fill each biscuit pot with a size of 1/5000 are filled with alluvial soil, and evenly mix 50 grains of each of the weed seeds of the surface soil, southern barley, nectar, vervet leaf, indigo amaranth and bony grass. Press lightly. Two days after sowing, a water dilution solution diluted with water with an emulsion prepared in accordance with Example 14 is sprayed onto the soil surface at a rate of 100 liters per 10 liters. The amount of the active ingredient is equivalent to 50 g per 10 liters.

After 30 days of drug treatment, the herbicidal effect is evaluated based on the same criteria as in Test Example 1.                 

(2) Weakness test for crops

Fill a 10,000 to 10,000 biscuit pot with field soil (alluvial soil) and seed each crop (5 soybeans, 5 corn, 10 beets, 10 rapeseed, 5 cotton, 10 wheat, barley) 10 grains) are sown separately in pots, and the surface layer is lightly pressed. One day after sowing, a water dilution liquid diluted with water in accordance with Example 14 is sprayed onto the soil surface at a rate of 100 liters per 10 liters. The amount of active ingredient used corresponds to 50 g per 10 liters.

After 30 days of drug treatment, the degree of damage to each crop was examined based on the same criteria as in Test Example 1. The result is shown in Table 6, and compound No. is shown to the said Table 1a-Table 1c.

Also in the two tests (1) and (2), the test is conducted in the same manner as the compound of the present invention using a comparative oil prepared in accordance with Example 14 containing the comparative compound A.

Test Compound No. Herbicide rate on weeds (%) Weakness against crops Southern Winter Whack Burbi Reef Indigo rain knotgrass Big head corn Sugar beet Rapeseed cotton wheat barley One 90 100 90 90 90 0 0 0 0 0 0 0 4 100 100 90 90 95 One One 0 0 0 0 0 8 100 100 90 90 90 0 One 0 0 0 0 0 25 100 100 90 90 90 0 One One 0 0 0 0 26 100 100 90 90 90 One 0 0 0 0 0 0 27 100 100 90 90 90 0 0 0 0 0 0 0 28 100 100 90 90 90 0 0 0 0 0 0 0 29 100 100 90 90 90 0 0 One 0 0 0 0 30 100 100 95 95 90 0 One 0 0 0 0 0 31 100 100 95 90 90 0 One One 0 0 One 0 32 100 100 90 90 90 0 One One 0 0 0 One 33 100 100 95 90 90 0 One 0 0 0 0 0 34 100 100 95 90 90 0 One One 0 0 0 0 35 100 100 100 95 90 0 0 0 0 0 0 0 38 100 100 100 100 95 0 0 One 0 0 0 0 42 100 100 95 90 90 0 0 0 0 0 0 One 65 95 100 90 90 90 0 One One 0 0 0 0 66 100 100 90 90 90 0 One 0 One 0 0 0 72 90 95 90 90 90 One 0 One 0 0 0 0 73 95 100 90 90 90 One 0 0 0 One 0 0 74 95 100 90 90 90 0 0 One 0 0 0 0 75 95 100 90 90 95 0 0 One 0 0 0 0 76 95 95 100 100 95 0 0 0 One 0 One 0 85 100 100 95 90 90 0 0 0 0 0 0 0 88 100 100 95 90 90 0 0 One 0 0 0 0

Test Compound No. Herbicide rate on weeds (%) Weakness against crops Southern Winter Whack Bibit Leaf Indigo rain knotgrass Big head corn Sugar beet Rapeseed cotton wheat barley 135 95 95 95 100 90 0 0 0 0 One 0 0 165 100 100 100 95 90 0 One 0 0 One 0 0 166 100 100 90 90 95 0 One 0 0 One One 0 169 100 100 90 95 95 0 One 0 0 0 0 0 170 100 100 90 95 95 0 0 0 0 One One 0 181 100 100 95 90 90 0 0 0 0 0 0 0 184 100 100 100 90 90 0 One 0 0 0 0 0 200 100 100 100 95 90 0 One 0 One 0 One 0 221 100 100 100 90 90 0 One One 0 One One 0 222 100 100 100 95 95 0 One 0 0 One One 0 231 100 100 95 90 90 One 0 0 0 One 0 0 234 100 100 100 90 90 0 0 0 0 0 0 0 269 100 100 95 95 95 0 0 One 0 One One 0 270 100 100 95 90 90 0 0 One 0 0 One One 281 100 100 100 90 90 0 One 0 0 0 0 0 284 100 100 95 90 90 0 0 0 0 0 0 0 318 100 100 90 90 90 0 One 0 One 0 0 0 320 90 90 90 90 90 0 One 0 0 One One 0 322 100 100 100 90 90 One One 0 0 One 0 0 324 100 100 90 90 95 One One 0 0 One 0 0 331 100 100 95 90 90 0 0 One 0 0 0 0 334 100 100 95 90 90 0 One 0 One 0 0 0

Test Compound No. Herbicide rate on weeds (%) Weakness against crops Southern Winter Whack Vervet Leaf Indigo rain knotgrass Big head corn Sugar beet Rapeseed cotton wheat barley 381 100 100 95 90 90 0 0 0 0 0 0 0 384 100 100 95 90 90 0 One 0 One 0 0 0 431 100 100 90 90 90 0 0 One 0 0 0 0 434 100 100 95 90 90 0 0 0 0 One 0 0 481 100 100 95 90 90 0 One 0 One 0 0 0 484 100 100 100 95 90 One One 0 0 0 0 0 518 100 95 95 90 95 0 One One 0 One One 0 520 95 95 90 95 95 One One 0 0 One 0 One 521 100 100 100 100 100 0 One 0 One 0 One 0 522 100 100 95 95 95 0 One One 0 One One 0 531 100 100 90 90 90 0 0 0 0 0 0 0 534 100 100 90 90 90 0 0 0 0 0 0 0 576 100 100 95 90 90 0 0 0 One One 0 0 577 100 100 95 90 90 0 0 0 One One 0 0 581 100 100 90 90 90 0 0 0 One 0 One One 582 100 100 90 90 95 0 One One 0 One 0 0 586 100 100 90 90 100 0 One One 0 One 0 0 587 100 100 95 95 100 One 0 0 0 One 0 0 591 100 100 100 95 100 0 One 0 0 0 One 0 592 100 100 95 100 100 0 One 0 0 0 0 0 596 100 100 90 100 100 One 0 0 0 0 0 0 597 100 100 95 90 90 0 One 0 0 0 One 0 631 100 100 90 90 90 0 One 0 0 0 One 0 632 100 100 90 95 90 0 0 0 0 One One 0

Test Compound No. Herbicide rate on weeds (%) Weakness against crops Southern Winter Whack Vervet Leaf Indigo rain knotgrass Big head corn Sugar beet Rapeseed cotton wheat barley 633 100 90 90 90 100 One 0 0 0 One One One 634 100 100 90 90 95 0 One One 0 0 0 0 635 100 100 95 95 100 One 0 0 0 0 One 0 636 100 100 95 95 95 0 0 0 One One 0 0 637 100 90 90 90 90 0 One 0 0 One 0 0 638 100 95 90 90 90 0 One One 0 One 0 0 639 100 100 95 95 100 0 0 One One 0 0 0 640 100 100 95 95 100 0 0 One One 0 0 0 650 100 100 90 90 95 0 0 0 One 0 0 0 656 100 90 90 90 95 0 One One 0 One 0 0 658 100 95 90 90 90 0 0 One One 0 0 0 662 100 100 90 95 95 0 0 One 0 0 0 0 665 100 100 90 95 95 One 0 One 0 One 0 0 666 100 100 90 90 100 0 One One 0 One 0 0 675 100 100 95 95 100 0 0 0 One One One 0 678 100 95 90 95 100 0 0 0 0 One 0 0 Comparative Compound A 70 70 70 60 40 3 2 3 3 0 0 0

As described above, the novel herbicidal 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivatives of the present invention have herbicidal activity and can be used for various weeds in rice fields and fields. Weeds are consumed in low amounts and have good selectivity between weeds and crops. Thus, the novel compounds of the present invention are extremely useful as selective herbicides.

Claims (17)

General formula (Ⅰ)

[Wherein, (ⅰ) A is

Wherein X is the same or different halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, cyano group, nitro group, methyl thi Or an unsubstituted or substituted phenyl group represented by the following formula: n, methylsulfinyl group, methylsulfonyl group, phenoxy group, acetylamino group or trifluoroacetylamino group, and n is an integer of 0 or 1-5. expression

1-naphthyl group or formula

Is a 5,6,7,8-tetrahydro-1-naphthyl group, or (iii) A is

An unsubstituted or substituted benzyl group or a phenethyl group represented by (where X and n have the same meanings as described above, R ₃ is a hydrogen atom or a methyl group, and K represents an integer of 1 to 2); R ₁ is a C _1-6 alkyl group, C _1-6 alkenyl group, C _1-6 alkynyl group or C _1-6 cycloalkyl group, R ₂ is a C _1-6 alkyl group, C _1-6 cycloalkyl group, a formula

(Wherein m is 0 or an integer of 1 to 5, Y is the same or different halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 halo) Unsubstituted or substituted phenyl group represented by alkoxy group or cyano group), or benzyl group in which benzyl group is substituted with halogen atom on benzene ring or formula

1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative represented by (unsubstituted or substituted pyridyl group represented by Z is a hydrogen atom or a chlorine atom). A compound according to claim 1, wherein the derivative of general formula (I)

[Wherein, X has the same meaning as defined in claim ₁ , that is, X may be the same or different from each other, halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, cyano group, nitro group, methylthio group, methylsulfinyl group, methylsulfonyl group, phenoxy group, acetylamino group or trifluoroacetylamino group, n is 0 or an integer of 1 to 5, R ₁ and R ₂ have the same meaning as defined in claim 1, ie R ₁ is a C _1-6 alkyl group, C _1-6 alkenyl group, C _1-6 alkynyl group or C _1-6 cycloalkyl group, and R ₂ is a C _1-6 alkyl group, C _1-6 cycloalkyl group, formula

Where m is 0 or an integer from 1 to 5, Y is a halogen atom that may be the same or different, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy group, C _1-6 haloalkoxy Unsubstituted or substituted phenyl group, or benzyl group in which benzyl group is substituted with halogen atom on benzene ring or formula

1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4 represented by the above-mentioned substituted or unsubstituted pyridyl group represented by (where Z represents a hydrogen atom or a chlorine atom). Derivatives which are -triazol-5-one derivatives. 3. A derivative of formula (Ia) according to claim 2 wherein the derivative of formula (Ia)

[Wherein, R _1a is a C _1-6 alkyl group, R _2a is a mono-halo substituted or di-halo substituted phenyl group, X ^a is a halogen atom, a C _1-6 alkyl group or a C _1-6 haloalkyl group, n Is 0 or an integer of 1 to 2]. The derivative of 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative. The derivative of general formula (Ia) according to claim 2 or 3, wherein the derivative of general formula (Ia)

[Wherein i-Pr is an isopropyl group, R _2a is a mono-halo substituted or di-halo substituted phenyl group, X ^a is a halogen atom, a C _1-6 alkyl group or a C _1-6 haloalkyl group, n is Or a 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative represented by 0 or an integer of 1 to 2]. The derivative of general formula (Ia-1-1) according to claim 4, wherein the derivative of general formula (Ia-1-1)

[Wherein i-Pr is an isopropyl group, T is a hydrogen atom or a fluorine atom, X ^b is the same or different chlorine atom, a cancel atom, a fluorine atom, a methyl group, an ethyl group or a trifluoromethyl group, n is Or a 1-phenyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative represented by 0 or an integer of 1 to 2]. 6. A derivative according to claim 5 wherein the derivative of formula (Ia-1-2) 1-phenyl-4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazol-5-one; 1- (2-Chlorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazol-5-one ; 1- (3-chlorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazol-5-one ; 1- (2-fluorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazole-5- On; 1- (2,4-difluorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazole -5-one; 1- (2-fluoro-4-chlorophenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-tria Sol-5-one; 1- (2-methylphenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazol-5-one; 1- (2,3-dimethylphenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazole-5 -On or 1- (2-Chloro-4-methylphenyl) -4- (N-isopropyl-N-4-fluoro or 2,4-difluorophenyl-carbamoyl) -1,2,4-triazole- 5-one phosphorus derivatives. 3. A derivative of formula (Ia) according to claim 2 wherein the derivative of formula (Ia)

1-phenyl represented by [wherein X and n have the same meaning as defined in claim 1 or 2, R _1b is a C _1-6 alkyl group and R _2b is a C _1-6 cycloalkyl group] Derivatives which are 4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivatives. 8. In general formula (Ia-2), X is a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a trifluoromethyl group or a trifluoromethyloxy group, n is an integer of 0 or 1 to 2, R _1b is a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and 1-phenyl-4- (N, N) of general formula (Ia-2) wherein R _2b is a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group -Disubstituted carbamoyl) -1,2,4-triazol-5-one derivatives. The compound of formula (I) according to claim 1, wherein the derivative of formula (I)

[Wherein, A ^a is a formula

1-naphthyl group or

Is a 5,6,7,8-tetrahydro-1-naphthyl group, ie R ₁ and R ₂ have the same meaning as defined in _{claim 1} , ie R ₁ is a C _1-6 alkyl group, C _{1- 6} alkenyl group, C _1-6 alkynyl group or C _1-6 cycloalkyl group and R ₂ is C _1-6 alkyl group, C _1-6 cycloalkyl group,

Wherein m is 0 or an integer of 1 to 5, Y is the same or different halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group or Unsubstituted or substituted phenyl group, or a benzyl group, wherein the benzyl group may be substituted with a halogen atom on the benzene ring

(Wherein Z represents a hydrogen atom or a chlorine atom) or a substituted or unsubstituted pyridyl group] 1-naphthyl-4- (N, N-disubstituted carbamoyl) -1,2, Derivatives that are 4-triazol-5-one derivatives. 10. The compound according to claim 9, wherein in formula (lb) R ₁ is a C _1-6 alkyl group, in particular an isopropyl group, R ₂ is a mono-halo substituted or di-halo substituted phenyl group, in particular 4-fluoro or 2,4 A derivative that is a 1-naphthyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative represented by general formula (Ib) which is a difluorophenyl group. The compound of formula (I) according to claim 1, wherein the derivative of formula (I)

[Wherein, X has the same meaning as defined in claim 1, that is, X is the same or different, halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, cyano group, nitro group, methyloxy group, methylsulfinyl group, methylsulfonyl group, phenoxy group, acetylamino group or trifluoroacetylamino group, n is 0 or an integer of 1 to 5, R is ₁ and R ₂ have the same meaning as defined in claim 1, that is, R ₁ is a C _1-6 alkyl group, C _1-6 alkenyl group, C _1-6 alkynyl group or C _1-6 cycloalkyl group, and R is ₂ is a C _1-6 alkyl group, C _1-6 cycloalkyl group, formula

(Wherein m is an integer of 0 or 1 to 5, Y is the same or different, halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group Or a cyano group), or an unsubstituted or substituted phenyl group, or a benzyl group in which a benzyl group is substituted with a halogen atom on a benzene ring, or a formula

Is an unsubstituted or substituted pyridyl group represented by (wherein Z represents a hydrogen atom or a chlorine atom), R ₃ is a hydrogen atom or a methyl group, and K is an integer of 1 or 2; Derivatives which are 4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivatives. 12. The derivative of formula (Ic) according to claim 11, wherein the derivative of formula (Ic)

Wherein R _1a is a C _1-6 alkyl group, R _2a is a mono-halo substituted or di-halo substituted phenyl group, X ^a is a halogen atom, a C _1-6 alkyl group or a C _1-6 haloalkyl group, n Is 0 or an integer of 1 to 2, k is an integer of 1 or 2), and 1-alalkyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazole- Derivatives which are 5-one derivatives. 13. A derivative according to claim 12, wherein the derivative of formula (Ic-1) is

[Wherein i-Pr is isopropyl group, T is hydrogen atom or fluorine atom, X ^b is the same or different chlorine atom, cancel atom, fluorine atom, methyl group, ethyl group or trifluoromethyl group, n is 0 or an integer of 1 to 2, R ₃ is a hydrogen atom or a methyl group, k is an integer of 1 or 2], 1-alalkyl-4- (N, N-disubstituted carbamoyl) -1 Derivatives which are 2,4-triazol-5-one derivatives. General formula (Ⅰ)

A 1-substituted-4-carbamoyl-1,2,4-triazol-5-one derivative represented by [wherein A, R ₁ and R ₂ have the same meaning as defined in claim 1] Herbicide composition containing as an active ingredient. The 1-phenyl-4- (N, N-disubstitutedcarbamoyl) -1,2,4-triazol-5-one derivative of formula (Ia) as defined in claim 2, Herbicide composition containing as an active ingredient. The 1-naphthyl-4- (N, N-disubstituted carbamoyl) -1,2,4-triazol-5-one derivative of claim 14 as defined in claim 9. A herbicide composition containing as an active ingredient. The 1-alalkyl-4- (N, N-disubstitutedcarbamoyl) -1,2,4-triazol-5-one derivative of claim 14 as defined in claim 11. Herbicide composition containing as an active ingredient.