JP2009298764A - Herbicide composition for paddy rice - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a herbicide composition for paddy rice having high safety, developing sure effect with a reduced application quantity, and comprising a 4-nitrobenzoyl derivative useful as an active component of herbicides for paddy rice or its salt in combination with other herbicidal components as active components. <P>SOLUTION: The herbicide composition for paddy field comprises one or more kinds of 4-nitrobenzoyl derivatives of formula (I) (in the formula, R1 is a halogen atom or the like; p is an integer of 0-3; R2 and R3 are each independently a 1-6C alkyl group or the like; and Q is 5-hydroxy-1-methylpyrazol-4-yl) or their salts and other herbicidal components as active components. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a herbicide composition for paddy rice containing a 4-nitrobenzoyl derivative or a salt thereof and other herbicidal active ingredients as active ingredients.

  In the cultivation of paddy rice, many herbicides have been used for weed control, which has required a great deal of labor. However, since it causes chemical damage to paddy rice, remains in the environment, or pollutes the environment, it is desired to develop a drug that can be used safely and at a lower dose.

  It is described in several patent documents that a benzoic acid derivative similar to the 4-nitrobenzoyl derivative used in the present invention has herbicidal activity.

  For example, Patent Document 1 describes that a benzoic acid derivative represented by the following formula is effective as an active ingredient of a herbicide. Moreover, it is described that the compound described in this document is useful as an active ingredient of a herbicide for paddy rice.

(In the formula, Y ′ represents a methyl group, Z represents a hydrogen atom, X ′ represents a fluorine atom, and R, R ′, R ″ each independently represents an alkyl group, etc.)
However, this document does not describe the 4-nitrobenzoyl derivative.

  Patent Document 2 describes that a benzoic acid derivative represented by the following formula is effective as an active ingredient of a herbicide and contains a compound having selectivity for rice.

(Wherein R1 'to R5' each independently represents a hydrogen atom or the like, and Q 'represents a group or the like represented by the following (Q'-1) to (Q'-3)).

However, what is actually synthesized in this document is only a compound in which the 4-position of the benzoyl group is a methylsulfonyl group (SO ₂ Me). Specific examples of 4-nitrobenzoyl derivatives used in the present invention and No examples are given.

WO98 / 42678 pamphlet WO04 / 052849 pamphlet

  An object of the present invention is to provide a herbicidal composition for paddy rice, which has a lower dose and a reliable and safe effect.

  The present inventors conducted further synthetic development of the compound described as a general formula in Patent Document 2 above. As a result, a 4-nitrobenzoyl derivative that is conceptually included in the compound described in Patent Document 2, but not specifically described in Patent Document 2, is useful as an active ingredient of a herbicide for paddy rice. As a result, a patent application has been filed first (PCT / JP2007 / 68283).

  The inventors of the present invention further studied diligently about a herbicide for paddy rice containing the 4-nitrobenzoyl derivative as an active ingredient. When the 4-nitrobenzoyl derivative and another herbicidal active ingredient are used in combination, the amount of the herbicide can be reduced. It has been found that safer and better herbicidal activity can be obtained, and the present invention has been completed.

  Thus, according to the present invention, the formula [I]

[Wherein, R 1 represents a halogen atom, a hydroxyl group, a mercapto group, an amino group that is unsubstituted or substituted, a nitro group, or an organic group.
p represents any integer of 0 to 3. When p is 2 or more, the plurality of R1s may be the same or different.
R2 and R3 are each independently an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, It represents an unsubstituted or substituted aryl group, or an unsubstituted or substituted heterocyclic group.
In addition, R2 and R3 are bonded together to form a 3- to 8-membered unsubstituted or substituted heterocyclic ring which may contain 1 to 4 nitrogen, oxygen or sulfur atoms. It may be formed.
Q represents a kind of group selected from groups represented by the following formulas Q1 to Q8.

(In the formula, * represents a binding site.
G represents an oxygen atom, an optionally oxidized sulfur atom, or a nitrogen atom that may have a substituent.
R4 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, or an unsubstituted or substituted amino group.
R5 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, unsubstituted or substituted A heteroaryl group having a group, an unsubstituted or substituted alkylcarbonyl group, an unsubstituted or substituted alkoxycarbonyl group, an unsubstituted or substituted benzoyl group, an unsubstituted or substituted aminocarbonyl group, It represents an unsubstituted or substituted alkylsulfonyl group, an unsubstituted or substituted arylsulfonyl group, or an unsubstituted or substituted aminosulfonyl group.

R6 represents a cyano group, an acetyl group, a group represented by the formula: C = NR7, or an unsubstituted or substituted tetrazolyl group.
R7 represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group.
R8 and R9 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group.

R10 and R11 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted cycloalkyl group.
X represents a group represented by the formula: C (R12) (R13) or a group represented by the formula NR12.
R12 and R13 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group.

Y represents an oxo group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxycarbonyl group.
m represents an integer of 0 to 4.
When m is 2 or more, a plurality of Y may be the same or different, and Y may be bonded to each other to form an unsubstituted or substituted alkylene group. Moreover, R12 of Y and X may be bonded to form an unsubstituted or substituted alkylene group. ]
A herbicide composition for paddy rice containing one or more of 4-nitrobenzoyl derivatives or salts thereof represented by the above and other herbicidal active ingredients as active ingredients is provided.

  In the composition of the present invention, the other herbicidal active ingredients are chloroacetanilide herbicide, aryloxyalkanoic acid herbicide, carbamate herbicide, thiocarbamate herbicide, diphenyl ether herbicide, sulfonylurea herbicide. , Pyrimidinyl carboxy herbicide, triazine herbicide, triazolopyrimidine herbicide, quinclolac, oxadiazone, oxadiargyl, piperophos, dimeron, bentazone, benfrate, naproanilide, mesotrione, tefriltrione, dithiopyr, pyrazoxifene, pyrazolate, benzobicyclo , Pentoxazone, Pyraclonil, Sinmethyline, Oxadiclomephone, Mefenacet, Fentrazamide, Indanophan, Cavenstrol, Pyributicarb, Pirimi At least one selected from the group consisting of ruphane, cumyluron, bromobutide, and 5,5-dimethyl-3- {2- [N- (isobutoxycarbonyl) -N- (trifluoromethanesulfonyl) amino] benzyl} -2-oxazolidinone Preferably it is a seed.

ADVANTAGE OF THE INVENTION According to this invention, the herbicide composition for paddy rice which has more herbicidal activity more safely with a smaller dosage is provided.
The composition of the present invention is a herbicidal composition for paddy rice, which has a certain effect at a lower dose and is highly safe.

  Hereinafter, the present invention will be described in detail.

  The herbicidal composition for paddy rice of the present invention contains one or more of 4-nitrobenzoyl derivatives represented by the formula (I) or salts thereof and other herbicidal active ingredients as active ingredients.

(1) A 4-nitrobenzoyl derivative having a sulfoxyimino group or a salt thereof The herbicide composition for paddy rice of the present invention has, as an active ingredient, a 4-nitrobenzoyl derivative having a sulfoxyimino group represented by the above formula (I) (hereinafter referred to as “active ingredient”). , Or “4-nitrobenzoyl form”) or a salt thereof.

In the formula (I), R 1 represents a halogen atom, a hydroxyl group, a mercapto group, an unsubstituted or substituted amino group, a nitro group, or an organic group.
Examples of the halogen atom for R1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  As an amino group having no substituent or a substituent, an amino group; methylamino group, ethylamino group, propylamino group, benzylamino group, phenylamino group, 4-chlorophenylamino group, acetylamino group, trifluoroacetylamino group , Monosubstituted amino groups such as benzoylamino group, methylsulfonylamino group, trifluoromethylsulfonylamino group, 4-methylphenylsulfonylamino group; dimethylamino group, diethylamino group, phenylmethylamino group, methylacetylamino group, methylbenzoyl group Examples thereof include disubstituted amino groups such as amino group, bis (methylsulfonyl) amino group, bis (trifluoromethylsulfonyl) amino group, and bis (phenylsulfonyl) amino group.

An organic group means all functional groups containing carbon atoms.
As the organic group, a cyano group, a formyl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted aryl group , Unsubstituted or substituted aryloxy group, alkylcarbonyl group, unsubstituted or substituted arylcarbonyl group, alkoxycarbonyl group, alkylthiocarbonyl group, alkylthio group, alkylsulfenyl group, alkyls, phonyl group, unsubstituted Alternatively, an arylthio group having a substituent, an arylsulfinyl group having no substituent or a substituent, an arylsulfonyl group having no substituent or a substituent, a sulfoximino group having a substituent, and the like can be given.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl group. (An alkyl group having 1 to 6 carbon atoms is preferable).

  Examples of the alkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, and 2-methyl-2-propenyl group. 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3 -Hexenyl group, 4-hexenyl group, 5-hexenyl group, etc. (an alkenyl group having 2 to 6 carbon atoms is preferred).

  The alkynyl group includes ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1-dimethyl- 2-butynyl group (C2-C6 alkynyl group is preferable).

  Alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, n-hexyl. And an oxy group (preferably an alkoxy group having 1 to 6 carbon atoms).

  Examples of the haloalkyl group include chloromethyl group, fluoromethyl group, bromomethyl group, dichloromethyl group, difluoromethyl group, dibromomethyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trichloroethyl group, 2,2 , 2-trifluoroethyl group, pentafluoroethyl group and the like (preferably a haloalkyl group having 1 to 6 carbon atoms).

  Examples of haloalkoxy groups include chloromethoxy, dichloromethoxy, trichloromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1-difluoroethoxy, 2,2,2-trifluoroethoxy. And the like (preferably a haloalkoxy group having 1 to 6 carbon atoms).

  Examples of the cycloalkyl group of the unsubstituted or substituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group (preferably a cycloalkyl group having 3 to 8 carbon atoms).

In addition, examples of the substituent for the cycloalkyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group (preferably an alkyl group having 1 to 6 carbon atoms); a chloromethyl group, a fluoromethyl group, and a bromomethyl group. Group, dichloromethyl group, difluoromethyl group, dibromomethyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, etc. A haloalkyl group having 1 to 6 carbon atoms (preferably a haloalkyl group having 1 to 6 carbon atoms); an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group or an isopropoxy group (preferably an alkoxy having 1 to 6 carbon atoms) Group); hydroxy group; nitro group; cyano group; amino group; methoxycarbonyl group, ethoxycarbonyl group, n- Alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 6 carbon atoms) such as lopoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group; fluorine atom, chlorine atom, bromine atom, iodine A halogen atom such as an atom; an alkylsulfonyl group such as a methanesulfonyl group, an ethylsulfonyl group, or an n-propylsulfonyl group (preferably an alkylsulfonyl group having 1 to 6 carbon atoms);
Moreover, the cycloalkyl group may be the same or different and may have a plurality of substituents.

  Examples of the aryl group of the unsubstituted or substituted aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like (preferably an aryl group having 6 to 14 carbon atoms).

  Examples of the substituent for the aryl group include those exemplified as the substituent for the cycloalkyl group.

  Examples of the aryloxy group of the unsubstituted or substituted aryloxy group include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group (preferably an aryloxy group having 6 to 14 carbon atoms).

  Examples of the substituent for the aryloxy group include those exemplified as the substituent for the cycloalkyl group.

  Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a pivaloyl group (preferably an alkylacarbonyl group having 2 to 6 carbon atoms).

  Examples of the arylcarbonyl group of the unsubstituted or substituted arylcarbonyl group include a phenylcarbonyl group, a 1-naphthylcarbonyl group, a 2-naphthylcarbonyl group and the like (preferably an arylcarbonyl group having 7 to 15 carbon atoms).

  Examples of the substituent for the arylcarbonyl group include those exemplified as the substituent for the cycloalkyl group.

  Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, and n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, etc. (C2-C6 alkoxycarbonyl group is preferred).

  Examples of the alkylthiocarbonyl group include methylthiocarbonyl group, ethylthiocarbonyl group, n-propylthiocarbonyl group, i-propylthiocarbonyl group, n-butylthiocarbonyl group, i-butylthiocarbonyl group, s-butylthiocarbonyl group, and t-butylthiocarbonyl group, n-pentylthiocarbonyl group, n-hexylthiocarbonyl group and the like (C2-C6 alkylthiocarbonyl group is preferred).

  Examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group and the like (alkylthio group having 1 to 6 carbon atoms). Are preferred).

  Examples of the alkylsulfinyl group include methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, i-butylsulfinyl group, s-butylsulfinyl group, t-butylsulfinyl group and the like. (C1-C6 alkylsulfinyl group is preferable).

  Examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, s-butylsulfonyl group, t-butylsulfonyl group and the like. (C1-C6 alkylsulfonyl group is preferable).

  Examples of the arylthio group of the unsubstituted or substituted arylthio group include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group and the like (preferably an arylthio group having 6 to 14 carbon atoms).

  Examples of the substituent for the arylthio group include those exemplified as the substituent for the cycloalkyl group.

  Examples of the arylsulfinyl group of the unsubstituted or substituted arylsulfinyl group include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group and the like (preferably an arylsulfinyl group having 6 to 14 carbon atoms).

  Examples of the substituent for the arylsulfinyl group include those exemplified as the substituent for the cycloalkyl group.

  As the arylsulfonyl group of an unsubstituted or substituted arylsulfonyl group, the arylsulfonyl group includes a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group and the like (preferably an arylsulfonyl group having 6 to 14 carbon atoms). ).

  Examples of the substituent for the arylsulfonyl group include those exemplified as the substituent for the cycloalkyl group.

The sulfoximino group having a substituent is a group represented by the formula: —N═S (O) (r1) (r2).
Here, r1 and r2 are each independently the same as those exemplified as specific examples of R2 and R3 described later.
R1 and r2 may be bonded together to form a ring.
Specific examples of the sulfoximino group having a substituent include the following.

  Among these, as R1, as a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, and carbon At least one selected from the group consisting of cycloalkyl groups having 3 to 6 is preferable, and halogen atoms and haloalkyl groups having 1 to 6 carbon atoms are more preferable.

  R2 and R3 are each independently an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, It represents an unsubstituted or substituted aryl group, or an unsubstituted or substituted heterocyclic group.

  Preferred specific examples of alkyl group, cycloalkyl group, alkenyl group, alkynyl group and aryl group of R2 and R3, which are unsubstituted or have a substituent (alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group) Examples thereof include the same as those exemplified as the alkyl group, cycloalkyl group, alkenyl group, alkynyl group and aryl group of R1.

  Examples of the substituent for the alkyl group, alkenyl group and alkynyl group in R2 and R3 include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group; methylthio Group, an alkylthio group having 1 to 6 carbon atoms such as ethylthio group; an alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group and ethylsulfonyl group; phenylsulfonyl group, 4-methylphenylsulfonyl group, 2-chlorophenylsulfonyl group And a phenylsulfonyl group having an unsubstituted or substituted group; an aryl group having an unsubstituted or substituted group such as a phenyl group, a 4-methylphenyl group, a 1-naphthyl group and a 2-naphthyl group;

Moreover, the alkyl group, the alkenyl group, and the alkynyl group of R2 and R3 may have the same or different plural substituents.
Examples of the substituent of the cycloalkyl group and aryl group of R2 and R3 include the same as those exemplified as the substituent of the cycloalkyl group of R1.

  Examples of the heterocyclic group of R2 and R3 that are unsubstituted or have a substituent include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-oxazolyl group, and 2-oxazolinyl. Group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 3-isoxazolinyl group, 2-thiazolyl group, 2-thiazolinyl group, 3-isothiazolyl group, 3-isothiazolinyl group, 2-pyranyl group, 4-tetrahydropyranyl group, 1-azetidinyl group, 2-azetidinyl group, 3-azetidinyl group, 2-pyrrolyl group, 2-pyrrolidinyl group, 2-imidazolyl group, 3-pyrazolyl group, 2-imidazolinyl group, 2-pyridyl group Group, 3-pyridyl group, 4-pyridyl group, 2-piperidyl group, piperidino group, 2-morpholinyl group, morpholino , 2-piperazinyl group, 2-pyrimidinyl group, 3-pyridazinyl group, 2-pyrazinyl group and the like.

  Examples of the substituent of the heterocyclic group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group (preferably an alkyl group having 1 to 6 carbon atoms); a chloromethyl group, a fluoromethyl group, and a bromomethyl group. Haloalkyl such as dichloromethyl group, difluoromethyl group, dibromomethyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group Group (preferably haloalkyl group having 1 to 6 carbon atoms); alkoxy group such as methoxy group, ethoxy group, n-propoxy group and isopropoxy group (preferably alkoxy group having 1 to 6 carbon atoms); hydroxy group; nitro group Cyano group; amino group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, Alkoxycarbonyl groups such as propoxycarbonyl group, n-butoxycarbonyl group and t-butoxycarbonyl group (preferably alkoxycarbonyl groups having 2 to 6 carbon atoms); halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Alternatively, alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, and an n-propylsulfonyl group (preferably an alkylsulfonyl group having 1 to 6 carbon atoms);

  R2 and R3 are bonded together to form a 3- to 8-membered unsubstituted or substituted group which may contain 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms in addition to the sulfur atom. May form a heterocycle having

  Examples of the heterocyclic ring include a thiophene ring, a tetrahydrothiophene ring, a thiopyran ring, a tetrahydrothiopyran ring, a 4-oxathiane ring, a thiomorpholine ring, a 1,4-dithiane ring, and a tetrahydrothiopyran-4-one ring.

  Q represents a kind selected from groups represented by the following formulas Q1 to Q8.

In the above formulas (Q1 to Q8), * represents a binding site.
G represents an oxygen atom, a sulfur atom that may be oxidized, or a nitrogen atom that may have a substituent.
Examples of the sulfur atom that may be oxidized include —SO— and —SO ₂ —.

  Examples of the substituent of the nitrogen atom which may have a substituent include an alkyl group such as a methyl group and an ethyl group; an unsubstituted or substituted phenyl group such as a phenyl group and a 4-methylphenyl group; an acetyl group; An acyl group such as a benzoyl group;

  R4 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, or an unsubstituted or substituted amino group.

  The alkyl group having an unsubstituted or substituted group, the cycloalkyl group having an unsubstituted or substituted group, or the amino group having an unsubstituted or substituted group represented by R4 has an unsubstituted or substituted group represented by R1 or R2. Specific examples of alkyl groups, unsubstituted or substituted cycloalkyl groups, and unsubstituted or substituted amino groups are the same as those listed.

  R5 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, unsubstituted or substituted A heteroaryl group having a group, an unsubstituted or substituted alkylcarbonyl group, an unsubstituted or substituted alkoxycarbonyl group, an unsubstituted or substituted benzoyl group, an unsubstituted or substituted aminocarbonyl group, It represents an unsubstituted or substituted alkylsulfonyl group, an unsubstituted or substituted arylsulfonyl group, or an unsubstituted or substituted aminosulfonyl group.

  Examples of R5, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, and an unsubstituted or substituted aryl group include R1 to R3. Are the same as those listed as specific examples of the unsubstituted or substituted alkyl group, the unsubstituted or substituted alkenyl group, the unsubstituted or substituted alkynyl group, and the unsubstituted or substituted aryl group. Can be mentioned.

  Examples of the heteroaryl group of the unsubstituted or substituted heteroaryl group include thienyl group, furyl group, pyrazolyl group, imidazolyl group, 1,2,4-triazolyl group, thiazolyl group, isothiazolyl group, 1,3,4- Examples include thiadiazolyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, pyridyl group, pyrimidyl group, pyridazyl group, pyrazyl group, S-triazyl group, 1,2,4-triazyl group and the like.

  Examples of the substituent of the heteroaryl group include the same ones listed as specific examples of the substituent of the cycloalkyl group of R1.

  Examples of the unsubstituted or substituted alkylcarbonyl group include an acetyl group, a trifluoroacetyl group, and a pivaloyl group (preferably an alkylcarbonyl group having 2 to 6 carbon atoms).

  Examples of the unsubstituted or substituted alkoxycarbonyl group include a methoxycarbonyl group, a trifluoromethoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and the like (preferably an alkoxycarbonyl group having 2 to 6 carbon atoms). ).

  Examples of the unsubstituted or substituted benzoyl group include a benzoyl group, a 4-chlorobenzoyl group, a 4-methylbenzoyl group, a 3-methoxybenzoyl group, and a 2,4-difluorobenzoyl group.

  Examples of the unsubstituted or substituted aminocarbonyl group include an aminocarbonyl group, a methylaminocarbonyl group, an ethylaminocarbonyl group, a benzylaminocarbonyl group, a phenylaminocarbonyl group, a dimethylaminocarbonyl group, and a phenylmethylaminocarbonyl group. It is done.

  Examples of the unsubstituted or substituted alkylsulfonyl group include a methylsulfonyl group, a trifluoromethylsulfonyl group, an ethylsulfonyl group, and an n-propylsulfonyl group.

  Examples of the unsubstituted or substituted arylsulfonyl group include a phenylsulfonyl group, a 4-methylphenylsulfonyl group, a 1-naphthylsulfonyl group, and a 2-naphthylsulfonyl group.

  Examples of the unsubstituted or substituted aminosulfonyl group include an aminosulfonyl group, a methylaminosulfonyl group, an ethylaminosulfonyl group, a benzylaminosulfonyl group, a phenylaminosulfonyl group, a dimethylaminosulfonyl group, and a phenylmethylaminosulfonyl group. It is done.

  R6 represents a cyano group, an acetyl group, a group represented by the formula: C = NR7, or an unsubstituted or substituted tetrazolyl group.

R7 represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group.
Specific examples of the unsubstituted or substituted alkyl group of R7 and the unsubstituted or substituted alkoxy group include the unsubstituted or substituted alkyl group of R2 and R3, unsubstituted or substituted, and the like. Specific examples of the alkoxy group having the same are listed.

R8 and R9 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group.
Specific examples of the unsubstituted or substituted alkyl group for R8 and R9 include those listed as specific examples of the unsubstituted or substituted alkyl group for R1.

R10 and R11 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted cycloalkyl group.
Specific examples of the unsubstituted or substituted alkyl group and the unsubstituted or substituted cycloalkyl group of R10 and R11 include the unsubstituted or substituted alkyl group of R2 and R3, unsubstituted or Specific examples of the cycloalkyl group having a substituent are the same as those listed.

X represents a group represented by the formula: C (R12) (R13) or a group represented by the formula: NR12.
Here, R12 and R13 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group.
Specific examples of the unsubstituted or substituted alkyl group for R12 and R13 include those listed as specific examples of the unsubstituted or substituted alkyl group for R1.

  Y represents an oxo group (═O), an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxycarbonyl group.

  Specific examples of the unsubstituted or substituted alkyl group for Y include the same as those listed as specific examples of the unsubstituted or substituted alkyl group for R1. Specific examples of the unsubstituted or substituted alkoxycarbonyl group for Y include the same as those listed as specific examples of the unsubstituted or substituted alkoxycarbonyl group for R5.

m represents an integer of 0 to 4.
When m is 2 or more, a plurality of Y may be the same or different, and Y may be bonded to each other to form a hydrogen atom, an unsubstituted or substituted alkylene group. Moreover, R12 of Y and X may be bonded to form an unsubstituted or substituted alkylene group.

  As specific examples of the unsubstituted or substituted alkylene group, as shown below, a C 1-6 alkylene chain containing 0 to 3 nitrogen atoms, oxygen atoms, or sulfur atoms is formed. 3-8 membered spiro ring represented by (Q2-1), 3-8 membered condensed ring represented by (Q2-2) below, 3-8 membered bridged ring represented by (Q2-3) below, etc. Is mentioned.

(In the formula, G, R5, and X represent the same meaning as described above, and Z represents an alkylene chain having 1 to 6 carbon atoms including 0 to 3 nitrogen atoms, oxygen atoms, and / or sulfur atoms.)

  The 4-nitrobenzoyl derivative of the present invention has the following formula (Ia) from the viewpoint of having excellent herbicidal activity.

(Wherein R1 to R3, p, and Q represent the same meaning as described above) are preferred, and the following formula (Ib)

(Wherein R1 to R3, and Q represent the same meaning as described above) are more preferable.
Further, the 4-nitrobenzoyl derivative of the present invention or a salt thereof is a compound in which R1 in the formula (Ib) is a group represented by a halogen atom, an unsubstituted or substituted alkyl group. Is more preferable.
In the 4-nitrobenzoyl derivative of the present invention or a salt thereof, R1 is more preferably a compound having a group represented by a chlorine atom, CH ₃ or CF ₃ in the formula (Ib).

  The 4-nitrobenzoyl derivative used for this invention can be manufactured by the manufacturing method described in PCT / JP2007 / 68283, for example.

  Examples of salts of 4-nitrobenzoyl derivatives used in the present invention include alkali metal salts such as lithium, sodium and potassium; alkaline earth metal salts such as calcium and magnesium; transition metal salts such as iron and copper; ammonia, And salts of organic bases such as triethylamine, tributylamine, pyridine, hydrazine, and the like.

  These salts can be produced by a conventionally known method.

  In any reaction, after completion of the reaction, if purification of the product is necessary after the usual post-treatment operation, it is purified by a known and conventional purification means such as distillation, recrystallization or column chromatography. The target product can be isolated.

  The structure of the obtained 4-nitrobenzoyl derivative can be determined by NMR spectrum, IR spectrum, MS spectrum and the like.

  The 4-nitrobenzoyl derivative used in the present invention may have optical isomers and may have a large number of tautomers. All such isomers are included within the scope of the present invention.

  Specific examples of 4-nitrobenzoyl derivatives used in the present invention are shown by combinations of Q shown in Table 1-1 to Table 1-6 and Table 1-7. The 4-nitrobenzoyl derivatives used in the present invention are those However, the present invention is not limited to these compounds.

In addition, the symbol in a table | surface represents the following meaning.
Me: methyl, Et: ethyl, Pr: propyl, Pen: pentyl, Bu: butyl, Hex: hexyl, Ph: phenyl, n: normal, i: iso, t: tertiary, c: cyclo, Tosyl: p-toluene Sulfonyl

  6-CH2-5 shares the 6- and 5-positions and forms a cyclopropane ring with a methylene group in between. 6-CH2CH2-4 shares the 6th and 4th positions, and shows that a cyclopentane ring is formed with an ethylene group interposed. Others are the same.

  A 4-nitrobenzoyl derivative and a salt thereof (hereinafter referred to as “4-nitrobenzoyl derivative”) can be used to cultivate rice, firefly, It shows high herbicidal activity against weeds such as oaks by either soil treatment or foliage treatment.

(2) Other Herbicidal Active Ingredients The herbicidal composition for paddy rice of the present invention contains other herbicidal active ingredients in addition to the 4-nitrobenzoyl compound and the like described above. By using a 4-nitrobenzoyl compound and other herbicidal active ingredients in combination, an excellent herbicidal activity (synergistic effect) higher than the total herbicidal activity obtained by using each single agent alone can be obtained.

  Other herbicidal active ingredients used in the present invention are not particularly limited as long as they are compounds having herbicidal activity. However, since the composition of the present invention is a herbicide for paddy rice, it has herbicidal activity against paddy weeds. Those are preferred.

Among them, chloroacetanilide-based herbicides such as butachlor, pretilachlor, and tenylchlor; aryloxyalkanoic acid-based herbicides such as 2,4-D, 2,4-DB, and MCPB; Carbamate herbicides such as esprocarb and molinate; thiocarbamate herbicides such as thiobencarb, dimethylpiperate, and EPTC; diphenyl ether herbicides such as bifenox; sulfonylurea herbicides such as bensulfuron-methyl, pyrazosulfuron-ethyl, imazosulfuron; Pyrimidinyl carboxy herbicides such as bispyribac and pyriminobac; triazine herbicides such as cimethrin and dimetamethrin; triazolopyrimidine herbicides such as penoxsulam; and quinclolac, oxadiazone, Xadialgyl, piperophos, dimron, bentazone, benfrate, naproanilide, mesotrione, tefriltrione, dithiopyr, pyrazoxifene, pyrazolate, benzobicyclone, pentoxazone, pyraclonyl, cinmethyline, oxadiclomephone, mefenacet, phentolazifol, tofenolpyrbutibol From the group consisting of: cumyluron, bromobutide, other herbicides such as 5,5-dimethyl-3- {2- [N- (isobutoxycarbonyl) -N- (trifluoromethanesulfonyl) amino] benzyl} -2-oxazolidinone; More preferably, at least one selected from the group consisting of pentoxazone, indanophan, oxadiclomephone, caventrol, dimetameth Emissions, daimuron, and 5,5-dimethyl -3- {2- [N- (isobutoxycarbonyl) -N- (trifluoromethanesulfonyl) amino] benzyl} -2-oxazolidinone more preferred.
In addition, 5,5-dimethyl-3- {2- [N- (isobutoxycarbonyl) -N- (trifluoromethanesulfonyl) amino] benzyl} -2-oxazolidinone is a compound described in the pamphlet of WO 2006/090792 (first Table, Compound No. 1-44).

  In the herbicidal composition of the present invention, the blending ratio of the 4-nitrobenzoyl compound and other herbicidal active ingredients is not particularly limited, but the weight ratio of (4-nitrobenzoyl compound etc.): (other herbicidal active ingredients). And usually in the range of 1:10 to 10: 1, preferably 1: 5 to 5: 1.

  As a manufacturing method of the herbicide composition for paddy rice of the present invention, for example, (a) an agrochemical composition containing a 4-nitrobenzoyl compound and an agrochemical composition containing other herbicidal active ingredients in a predetermined ratio. Method to mix and make pesticide composition, (b) Method to mix 4-nitrobenzoyl body etc. with other herbicidal active ingredients at a predetermined ratio to make pesticide composition, (c) 4-nitrobenzoyl body etc. Examples include a method of diluting a predetermined amount of the agrochemical composition to be contained and a predetermined amount of the agrochemical composition containing other herbicidal active ingredients with water to obtain a water-diluted solution of the herbicide composition.

  The agrochemical composition containing 4-nitrobenzoyl compound and the like, the agrochemical composition containing other herbicidal active ingredients, and the methods (a) and (b) used in the methods (a) and (c) The pesticide composition obtained in step 1 can be used in the form of general pesticides for the purpose of use as a pesticide, that is, in the form of wettable powder, granule, powder, emulsion, aqueous solvent, suspension, flowable, etc. Can do.

  Additives and carriers, if solid dosage forms are intended, vegetable powders such as soybean flour, wheat flour, mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, benzoic Organic and inorganic compounds such as acid soda, urea and mirabilite are used.

  For liquid dosage forms, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water Etc. are used as solvents.

  In order to obtain a uniform and stable form in these preparations, a surfactant may be added if necessary. The surfactant is not particularly limited. For example, alkylphenyl ether added with polyoxyethylene, alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, sorbitan added with polyoxyethylene Higher fatty acid esters, nonionic surfactants such as tristyryl phenyl ether added with polyoxyethylene, sulfates of alkyl phenyl ether added with polyoxyethylene, alkylnaphthalene sulfonate, polycarboxylate, lignin sulfone Acid form, alkylnaphthalene sulfonate formaldehyde condensate, isobutylene-maleic anhydride copolymer, and the like.

  The active ingredient concentration (total amount of 4-nitrobenzoyl compound and other herbicidal active ingredients) in the herbicidal composition of the present invention varies to various concentrations depending on the form of the preparation described above. 5 to 90% by weight (hereinafter simply referred to as%), preferably 10 to 85% in emulsions, 3 to 70% in emulsions, preferably 5 to 60% in granules. In this case, a concentration of 0.01 to 50%, preferably 0.05 to 40% is used.

  The wettable powder and emulsion thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the granules are directly sprayed or mixed before or after germination of weeds. The When actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of active ingredient per hectare is applied.

  Additives such as rapeseed oil, soybean oil, sunflower oil, castor oil, pine oil, cottonseed oil, derivatives of these oils, and oil concentrates thereof are added to the herbicidal composition of the present invention. You can also.

  In addition, the herbicide composition of the present invention is used in combination with known fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, etc., thereby reducing the amount of drug used and saving labor. May be able to bring you.

EXAMPLES Next, although an Example and a reference example demonstrate this invention further in detail, this invention is not limited to the following Example.
Reference Example 1 1- {aza [2-chloro-3-[(5-hydroxy-1-methylpyrazol-4-yl) carbonyl] -6-nitrophenyl] methylene} thian-1-one (compound (1 ))Manufacturing of

  To a solution obtained by adding 320 ml of chloroform to 9.0 g of 3- [aza (oxothianylidene) methyl] -2-chloro-4-nitrobenzoic acid (a), 1,1′-carbonyldiimidazole 7 0.0 g was added at room temperature and stirred at room temperature for 1 hour. Thereto were added 3.2 g of N-methylpyrazolone and 3.3 g of triethylamine, and the whole was heated to reflux for 1.5 hours. The reaction solution was cooled and the solvent was concentrated. To the obtained residue, 180 ml of acetonitrile, 9.0 g of molecular sieve 3A, 0.7 g of acetone cyanohydrin, and 8.2 g of triethylamine were added, and the whole volume was stirred at room temperature for 3 days. Insoluble matters were filtered from the reaction mixture, and the filtrate was concentrated. The residue was dissolved in 600 ml of chloroform, and this solution was washed with 300 ml of 1N hydrochloric acid and then with water (500 ml), and then the organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to obtain 13.1 g of a crude product. Crystallize by adding 30 ml of methanol, filter, wash the crystals with 20 ml of methanol, and 1- {aza [2-chloro-3-[(5-hydroxy-1-methylpyrazol-4-yl) carbonyl] -6. 6.4 g of pale yellow crystals of -nitrophenyl] methylene} thian-1-one (1) were obtained. Yield 57%, melting point: 200-203 ° C.

  The raw material compound represented by the formula (a) was synthesized according to the method described in the pamphlet of WO04 / 052849.

(Examples 1-43) Manufacture of a herbicide composition for paddy rice (1) 4-nitrobenzoyl body, etc. As an agrochemical composition containing 4-nitrobenzoyl body, 4-nitrobenzoyl body, etc. An emulsion (EC) containing was prepared.
5 parts by weight of the compound (1) obtained in Reference Example 1, 90 parts by weight of a solvent such as dimethylformamide, and 5 parts by weight of a surfactant were mixed and dissolved to prepare an emulsion (EC) containing 5% by weight of the active ingredient.

(2) Agrochemical composition containing other herbicidal active ingredients (a) Flowable formulation (SC) containing pentoxazone as an active ingredient
A commercially available flowable preparation (SC) (available from Kaken Pharmaceutical Co., Ltd.) containing pentoxazone as an active ingredient was used.
(B) Preparation of emulsion (EC) 5 parts by weight of other herbicidal active ingredients shown in Table 2, 90 parts by weight of a solvent such as dimethylformamide, and 5 parts by weight of a surfactant were mixed and dissolved to obtain 5% by weight of an active ingredient. An emulsion (EC) was prepared.

  As other herbicidal active ingredients, indanophan and dimetamethrin, commercially available products (manufactured by Kanto Chemical Reagent Co., Ltd.) were used. In addition, oxadichromephone, caffeentrol, dimrone, and 5,5-dimethyl-3- {2- [N- (isobutoxycarbonyl) -N- (trifluoromethanesulfonyl) amino] benzyl} -2-oxazolidinone are prepared by methods described in the literature. The one synthesized according to the above was used. For convenience, 5,5-dimethyl-3- {2- [N- (isobutoxycarbonyl) -N- (trifluoromethanesulfonyl) amino] benzyl} -2-oxazolidinone is described as “oxazolidinone Y” in the table. did.

(3) Manufacture of herbicide composition for paddy rice The emulsion containing the compound (1) obtained in (1) and the agent containing other herbicidal active ingredients in (2) are in the proportions shown in Table 2. The paddy rice herbicide composition of Examples 1-43 was manufactured by tank mixing.

(Paddy field soil test)
Filled with 100cm ² plastic pot with paddy paddy soil, seeded with the seeds of weeds shown in Table 2 below, transplanted rice, brought to 3cm submerged condition and grown in greenhouse did.

  The herbicidal composition for paddy rice of Examples 1-43 at the time shown in Table 2 below (for example, +11 indicates that the growth period of rice until drug treatment after sowing is 11 days), the above compound Each of the emulsion of (1) and the other herbicidal active ingredient agents used were treated dropwise on the water surface using a pipette. Herbicidal activity was observed on the survey date shown in Table 2 below (for example, “after 22 days indicates that the survey was conducted on the day 22 days after the drug treatment date”). Herbicidal activity was objectively investigated on a scale of 0% to 100% compared to the untreated control. 0% means no herbicidal activity, 100% means that the plant is completely dead. The observation results are summarized in Table 2 below. Moreover, the leaf stage of the weeds on the survey date is also shown in Table 2 (L indicates the leaf stage, for example, 3L is the three-leaf stage).

(Calculation of expected value E)
Expected value E (expected value of additive effect of compound (1) used and other herbicidal active ingredients) R. According to the method described in Colby, Calculating synergistic and antagonistic responses of herbicide combinations, Weeds, 15, 20 pp (1967), calculation was performed using the following Colby equation.

Expected value (E) = X + Y− (XY / 100)
(In the above formula, X (single-use section) represents the rate (%) of herbicidal action at the application rate (a) of compound (1), etc., and Y (single-use section) is the application of other herbicidal active ingredients. The rate (%) of herbicidal action at the dose (b) is shown, and the expected value (E) is expected at the application rate (a) of the compound (1) etc. and the application rate (b) of other herbicidal active ingredients (Shows herbicidal action (%).)

  From Table 2, the value observed when using the herbicidal composition for paddy rice of Examples 1 to 43 (mixed section (%)) exceeds the expected value E calculated according to the above Colby equation, A synergistic effect was observed.

Claims (2)

Formula [I]

[Wherein, R 1 represents a halogen atom, a hydroxyl group, a mercapto group, an amino group that is unsubstituted or substituted, a nitro group, or an organic group.
p represents any integer of 0 to 3. When p is 2 or more, the plurality of R1s may be the same or different.
R2 and R3 are each independently an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, It represents an unsubstituted or substituted aryl group, or an unsubstituted or substituted heterocyclic group.
In addition, R2 and R3 are bonded together to form a 3- to 8-membered unsubstituted or substituted heterocyclic ring which may contain 1 to 4 nitrogen, oxygen or sulfur atoms. It may be formed.
Q represents a kind of group selected from groups represented by the following formulas Q1 to Q8.

(In the formula, * represents a binding site.
G represents an oxygen atom, an optionally oxidized sulfur atom, or a nitrogen atom that may have a substituent.
R4 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, or an unsubstituted or substituted amino group.
R5 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, unsubstituted or substituted A heteroaryl group having a group, an unsubstituted or substituted alkylcarbonyl group, an unsubstituted or substituted alkoxycarbonyl group, an unsubstituted or substituted benzoyl group, an unsubstituted or substituted aminocarbonyl group, It represents an unsubstituted or substituted alkylsulfonyl group, an unsubstituted or substituted arylsulfonyl group, or an unsubstituted or substituted aminosulfonyl group.
R6 represents a cyano group, an acetyl group, a group represented by the formula: C = NR7, or an unsubstituted or substituted tetrazolyl group.
R7 represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group.
R8 and R9 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group.
R10 and R11 each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted cycloalkyl group.
X represents a group represented by the formula: C (R12) (R13) or a group represented by the formula NR12.
R12 and R13 each independently represents a hydrogen atom or an unsubstituted or substituted alkyl group.
Y represents an oxo group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxycarbonyl group.
m represents an integer of 0 to 4.
When m is 2 or more, a plurality of Y may be the same or different, and Y may be bonded to each other to form an unsubstituted or substituted alkylene group. Moreover, R12 of Y and X may be bonded to form an unsubstituted or substituted alkylene group. ]
A herbicide composition for paddy rice containing one or more of the 4-nitrobenzoyl derivatives or salts thereof represented by the above and other herbicidal active ingredients as active ingredients.   The other herbicidal active ingredients are chloroacetanilide herbicide, aryloxyalkanoic acid herbicide, carbamate herbicide, thiocarbamate herbicide, diphenyl ether herbicide, sulfonylurea herbicide, pyrimidinylcarboxy herbicide, triazine Herbicides, triazolopyrimidine herbicides, quinclolac, oxadiazone, oxadiargyl, piperophos, dimeron, bentazone, benfrate, naproanilide, mesotrione, tefryltrione, dithiopyr, pyrazoxifene, pyrazolate, benzobicyclone, pentoxazone, pyraclonil, cinmethyline Oxadichrome mehon, mefenacet, fentolazamide, indanophan, caffeentrol, piributicalbu, pyrimisulfan, cumylron, bu And at least one selected from the group consisting of mobutide and 5,5-dimethyl-3- {2- [N- (isobutoxycarbonyl) -N- (trifluoromethanesulfonyl) amino] benzyl} -2-oxazolidinone Item 2. The composition according to Item 1.