# Patent

## Title
Pest control composition

## Abstract

Disclosed is a pest control composition comprising at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof and at least one other pest control agent as active ingredients. The combined use of the two ingredients can provide a better insecticidal effect.

## Background
This application is a U.S. national stage of International Application No. PCT/JP2008/054316 filed Mar. 10, 2008.
CROSS-REFERENCE TO RELATED APPLICATION
The application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 58540/2007, filed on Mar. 8, 2007; the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to a pest control composition that comprises a pyripyropene derivative or an agriculturally and horticulturally acceptable salt thereof and other pest control agent and that is agriculturally and horticulturally useful.
2. Background Art
Applied and Environmental Microbiology (1995), 61(12), 4429-35 and WO 2004/060065 describe insecticidal activity of pyripyropene A, and WO 2006/129714 describes pyripyropene A derivatives and the insecticidal activity of the pyripyropene A derivatives. The Pesticide Manual, the 13th edition, published by The British Crop Protection Council and SHIBUYA INDEX, the 10th edition, 2005, published by SHIBUYA INDEX RESEARCH GROUP describe many pest control agents that have hitherto been developed and used. Up to now, however, there is no document describing the effect of a mixture of the pyripyropene derivative with other pest control agent(s).
On the other hand, control at a low dose is desired from the viewpoints of environmental consideration and influence on organisms that are not target.
SUMMARY OF THE INVENTION
The present inventors have now found a composition that comprises a pyripyropene derivative or an agriculturally and horticulturally acceptable salts thereof and other pest control agent and possesses an excellent control effect, and use of the composition. The present invention has been made based on such finding.
Accordingly, an object of the present invention is to provide a composition that comprises a pyripyropene derivative or an agriculturally and horticulturally acceptable salts thereof and other pest control agent and possesses an excellent control effect, and use of the composition.
According to one aspect of the present invention, there is provided a pest control composition comprising at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof and at least one other pest control agent as active ingredients:




wherein

    
    
        Het1 represents optionally substituted 3-pyridyl,
        R1 represents hydroxyl,
        
            optionally substituted C1-6 alkylcarbonyloxy,
            optionally substituted C2-6 alkenylcarbonyloxy,
            optionally substituted C2-6 alkynylcarbonyloxy,
            optionally substituted C1-6 alkyloxy,
            optionally substituted C2-6 alkenyloxy,
            optionally substituted C2-6 alkynyloxy,
            optionally substituted benzyloxy, or
            oxo in the absence of a hydrogen atom at the 13-position or
        
        
        the bond between 5-position and 13-position represents a double bond in the absence of R1 and a hydrogen atom at the 5-position,
        R2 represents hydroxyl,
        
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted C2-6 alkenylcarbonyloxy,
            optionally substituted C2-6 alkynylcarbonyloxy,
            optionally substituted benzoyloxy, or
            optionally substituted C1-6 alkylsulfonyloxy,
        
        
        R3 represents a hydrogen atom,
        
            hydroxyl,
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted C2-6 alkenylcarbonyloxy,
            optionally substituted C2-6 alkynylcarbonyloxy,
            optionally substituted benzoyloxy,
            optionally substituted C1-6 alkylsulfonyloxy,
            optionally substituted benzenesulfonyloxy, or
            optionally substituted five- or six-membered heterocyclic thiocarbonyloxy, or
        
        
        R2 and R3 together represent —O—CR2′R3′—O— wherein R2′ and R3′, which may be the same or different, represent a hydrogen atom, C1-6 alkyl, C1-6 alkyloxy, C2-6 alkenyl, optionally substituted phenyl, or optionally substituted benzyl, or R2′ and R3′ together represent oxo or C2-6 alkylene, and
        R4 represents a hydrogen atom,
        
            hydroxyl,
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted C2-6 alkenylcarbonyloxy,
            optionally substituted C2-6 alkynylcarbonyloxy,
            optionally substituted benzoyloxy,
            optionally substituted C1-6 alkylsulfonyloxy,
            optionally substituted benzenesulfonyloxy,
            optionally substituted benzyloxy,
            optionally substituted C1-6 alkyloxy,
            optionally substituted C2-6 alkenyloxy,
            optionally substituted C2-6 alkynyloxy,
            C1-6 alkyloxy-C1-6 alkyloxy,
            C1-6 alkylthio-C1-6 alkyloxy,
            C1-6 alkyloxy-C1-6 alkyloxy-C1-6 alkyloxy,
            optionally substituted C1-6 alkyloxycarbonyloxy,
            optionally substituted C1-6 alkylaminocarbonyloxy,
            optionally substituted saturated or unsaturated five- or six-membered heterocyclic oxy,
            optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy,
            optionally substituted thieno[3,2-b]pyridylcarbonyloxy,
            optionally substituted 1H-indolylcarbonyloxy,
            optionally substituted saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy, or
            oxo in the absence of a hydrogen atom at the 7-position.
        
        
    
    


According to a second aspect of the present invention, there is provided a method for protecting useful plants from pests, comprising treating an object pest, an object useful plant, or a seed, a soil, or a cultivation carrier of the object useful plant with the pest control composition.
There is also provided use of the above pest control composition for the protection of useful plants from pests.


DETAILED DESCRIPTION OF THE INVENTION
The term “halogen” as used herein means fluorine, chlorine, bromine, or iodine, preferably fluorine, chlorine, or bromine.
The terms “alkyl,” “alkenyl,” and “alkynyl” as used herein as a group or a part of a group respectively mean alkyl, alkenyl, and alkynyl that the group is of a straight chain, branched chain, or cyclic type or a type of a combination thereof unless otherwise specified. Further, for example, “C1-6” in “C1-6 alkyl” as a group or a part of a group means that the number of carbon atoms in the alkyl group is 1 to 6. Further, in the case of cyclic alkyl, the number of carbon atoms is at least three.
The term “heterocyclic ring” as used herein means a heterocyclic ring containing one or more, preferably one to four, heteroatoms, which may be the same or different, selected from the group consisting of nitrogen, oxygen, and sulfur atoms. Further, the expression “optionally substituted” alkyl as used herein means that one or more hydrogen atoms on the alkyl group may be substituted by one or more substituents which may be the same or different. It will be apparent to a person having ordinary skill in the art that the maximum number of substituents may be determined depending upon the number of substitutable hydrogen atoms on the alkyl group. This is true of functional groups other than the alkyl group.
3-Pyridyl represented by Het1 is optionally substituted, and substituents include halogen atoms, C1-4 alkyl, C1-4 alkyloxy, nitro, cyano, formyl, trifluoromethyl, trifluoromethyloxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, or acetyloxy. Preferred are halogen atoms and trifluoromethyl. A chlorine atom and trifluoromethyl are more preferred.
“C1-6 alkylcarbonyloxy” represented by R1 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethyloxy, or trifluoromethylthio.
“C1-18 alkylcarbonyloxy” represented by R2, R3 and R4 is preferably C1-6 alkylcarbonyloxy, more preferably ethylcarbonyloxy or C3-6 cyclic alkylcarbonyloxy. The C1-18 alkylcarbonyloxy group is optionally substituted, and substituents include halogen atoms, cyano, C3-6 cycloalkyl, phenyl, trifluoromethyloxy, trifluoromethylthio, pyridyl, or pyridylthio. More preferred are halogen atoms, C3-6 cycloalkyl, and pyridyl.
“C2-6 alkenylcarbonyloxy” represented by R1, R2, R3 and R4 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethyloxy, or trifluoromethylthio.
“C2-6 alkynylcarbonyloxy” represented by R1, R2, R3 and R4 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethyloxy, or trifluoromethylthio.
“C1-6 alkyloxy” represented by R1 and R4 is optionally substituted, and substituents include halogen atoms; cyano; phenyl; trifluoromethyloxy; trifluoromethylthio; C1-6 alkylcarbonyl optionally substituted by a halogen atom; or C1-6 alkylcarbonyloxy optionally substituted by a halogen atom.
“C2-6 alkenyloxy” represented by R1 and R4 is optionally substituted, and substituents include halogen atoms; cyano; phenyl; trifluoromethyloxy; trifluoromethylthio; C1-6 alkylcarbonyl optionally substituted by a halogen atom; or C1-6 alkylcarbonyloxy optionally substituted by a halogen atom.
“C2-6 alkynyloxy” represented by R1 and R4 is optionally substituted, and substituents include halogen atoms; cyano; phenyl; trifluoromethyloxy; trifluoromethylthio; C1-6 alkylcarbonyl optionally substituted by a halogen atom; or C1-6 alkylcarbonyloxy optionally substituted by a halogen atom.
Phenyl in “benzyloxy” represented by R1 and R4 is optionally substituted, and substituents include halogen atoms; C1-6 alkyloxy optionally substituted by a halogen atom; C1-6 alkyl optionally substituted by a halogen atom; C1-6 alkylcarbonyl optionally substituted by a halogen atom; C1-6 alkylcarbonyloxy optionally substituted by a halogen atom; C1-6 alkylcarbonylamino optionally substituted by a halogen atom; C1-6 alkylaminocarbonyloxy optionally substituted by a halogen atom; C1-6 alkylaminocarbonyl optionally substituted by a halogen atom; C1-6 alkylsulfonyloxy optionally substituted by a halogen atom; C1-6 alkylthio optionally substituted by a halogen atom; C1-6 alkylsulfinyl optionally substituted by a halogen atom; C1-6 alkylsulfonyl optionally substituted by a halogen atom; cyano; formyl; azide; guanidyl; group —C(═NH)—NH2; or group —CH═N—O—CH3.
Phenyl in “benzoyloxy” represented by R2, R3 and R4 is optionally substituted, and substituents include halogen atoms; C1-6 alkyloxy optionally substituted by a halogen atom; C1-6 alkyl optionally substituted by a halogen atom; C1-6 alkylcarbonyl optionally substituted by a halogen atom; C1-6 alkylcarbonyloxy optionally substituted by a halogen atom; C1-6 alkylcarbonylamino optionally substituted by a halogen atom; C1-6 alkylaminocarbonyloxy optionally substituted by a halogen atom; C1-6 alkylaminocarbonyl optionally substituted by a halogen atom; C1-6 alkylsulfonyloxy optionally substituted by a halogen atom; C1-6 alkylthio optionally substituted by a halogen atom; C1-6 alkylsulfinyl optionally substituted by a halogen atom; C1-6 alkylsulfonyl optionally substituted by a halogen atom; cyano; nitro; formyl; azide; guanidyl; group —C(═NH)—NH2; or group —CH═N—O—CH3. Preferred are halogen atoms, halogenated C1-6 alkyl, cyano, and nitro.
Phenyl in “benzenesulfonyloxy” represented by R3 and R4 is optionally substituted, and substituents include halogen atoms; C1-6 alkyloxy optionally substituted by a halogen atom; C1-6 alkyl optionally substituted by a halogen atom; C1-6 alkylcarbonyl optionally substituted by a halogen atom; C1-6 alkylcarbonyloxy optionally substituted by a halogen atom; C1-6 alkylcarbonylamino optionally substituted by a halogen atom; C1-6 alkylaminocarbonyloxy optionally substituted by a halogen atom; C1-6 alkylaminocarbonyl optionally substituted by a halogen atom; C1-6 alkylsulfonyloxy optionally substituted by a halogen atom; C1-6 alkylthio optionally substituted by a halogen atom; C1-6 alkylsulfinyl optionally substituted by a halogen atom; C1-6 alkylsulfonyl optionally substituted by a halogen atom; cyano; formyl; azide; guanidyl; group —C(═NH)—NH2; or group —CH═N—O—CH3.
“C1-6 alkylsulfonyloxy” represented by R2, R3 and R4 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethyloxy, or trifluoromethylthio.
“C1-6 alkyloxycarbonyloxy” represented by R4 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethyloxy, or trifluoromethylthio.
“C1-6 alkylaminocarbonyloxy” represented by R4 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethyloxy, or trifluoromethylthio.
“Phenyl” represented by R2′ and R3′ and phenyl in “benzyl” represented by R2′ and R3′ are optionally substituted, and substituents include halogen atoms, C1-4 alkyl, C1-4 alkyloxy, nitro, cyano, formyl, trifluoromethyloxy, acetyl, or acetyloxy.
Examples of “saturated or unsaturated five- or six-membered heterocyclic ring” in saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy represented by R3 and saturated or unsaturated five- or six-membered heterocyclic oxy, saturated or unsaturated five- or six-membered heterocyclic carbonyloxy, and saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy represented by R4 include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazoyl, isoxazolyl, thiazolyl, oxazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, tetrahydropyranyl, piperidinyl, piperazinyl, morpholinyl, tetrahydropyranyl, pyrazinyl, thienyl, or mannosyl. Preferred are pyridyl, furanyl, thiazolyl, imidazolyl, tetrahydropyranyl, and mannosyl. More specific examples thereof include (2- or 3-)thienyl, (2- or 3-)furyl, (1-, 2- or 3-)pyrrolyl, (1-, 2-, 4- or 5-)imidazolyl, (1-, 3-, 4- or 5-)pyrazolyl, (3-, 4- or 5-)isothiazoyl, (3-, 4- or 5-)isoxazolyl, (2-, 4- or 5-)thiazolyl, (2-, 4- or 5-)oxazolyl, (2-, 3- or 4-)pyridyl or, (2-, 4-, 5- or 6-)pyrimidinyl, (2- or 3-)pyrazinyl, (3- or 4-)pyridazinyl, (2-, 3- or 4-)tetrahydropyranyl, (1-, 2-, 3- or 4-)piperidinyl, (1-, 2- or 3-)piperazinyl, and (2-, 3- or 4-)morpholinyl, preferably 3-pyridyl, 2-franyl, 5-thiazolyl, 1-imidazolyl, 5-imidazolyl, or 2-tetrahydropyranyl, more preferably 2-tetrahydropyranyl, 2-pyrazinyl, or 3-pyridyl, particularly preferably 3-pyridyl.
The heterocyclic ring in the saturated or unsaturated five- or six-membered heterocyclic carbonyloxy and saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy and thieno[3,2-b]pyridylcarbonyloxy and 1H-indolylcarbonyloxy represented by R4 are optionally substituted, and substituents include halogen atoms, C1-4 alkyl, C1-4 alkyloxy, C1-4 alkylthio, nitro, cyano, formyl, trifluoromethyloxy, trifluoromethyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, acetyloxy, benzoyl, or C1-4 alkyloxycarbonyl. Preferred are halogen atoms, C1-4 alkyl, C1-4 alkyloxy, and trifluoromethyl.
The heterocyclic ring in the saturated or unsaturated five- or six-membered heterocyclic oxy is optionally substituted, and substituents include hydroxyl, benzyloxy, a halogen atom, C1-4 alkyl, C1-4 alkyloxy, nitro, cyano, formyl, trifluoromethyloxy, trifluoromethyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, or acetyloxy. Preferred are hydroxyl and benzyloxy.
Compounds of Formula (I)
In a preferred embodiment of the present invention, in compounds of formula (I), preferably, Het1 represents 3-pyridyl.
Further, in a preferred embodiment of the present invention, in compounds of formula (I), R1 represents hydroxyl, C1-6 alkylcarbonyloxy, C1-3 alkyloxy, or benzyloxy, or oxo in the absence of a hydrogen atom at the 13-position or the bond between 5-position and 13-position represents a double bond in the absence of R1 and a hydrogen atom at the 5-position. More preferably, R1 represents hydroxyl or C1-6 alkylcarbonyloxy, or the bond between 5-position and 13-position represents a double bond in the absence of R1 and a hydrogen atom at the 5-position. Still more preferably, R1 represents hydroxyl.
In a preferred embodiment of the present invention, in the compounds of formula (I), R2 represents hydroxyl, optionally substituted C1-18 alkylcarbonyloxy, optionally substituted benzoyloxy, or C1-3 alkylsulfonyloxy, more preferably optionally substituted C1-18 alkylcarbonyloxy, still more preferably optionally substituted C1-6 alkylcarbonyloxy, still more preferably optionally substituted cyclic C3-6 alkylcarbonyloxy, particularly preferably cyclopropylcarbonyloxy.
In a preferred embodiment of the present invention, in the compounds of formula (I), R3 represents a hydrogen atom, hydroxyl, optionally substituted C1-18 alkylcarbonyloxy, optionally substituted benzoyloxy, C1-6 alkylsulfonyloxy, optionally substituted benzenesulfonyloxy or saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy, more preferably optionally substituted C1-6 alkylcarbonyloxy or C1-6 alkylsulfonyloxy, still more preferably optionally substituted C1-6 alkylcarbonyloxy, still more preferably optionally substituted cyclic C3-6 alkylcarbonyloxy, particularly preferably cyclopropylcarbonyloxy.
In a preferred embodiment of the present invention, in the compounds of formula (I), R2 and R3 together represent —O—CR2′R3′—O— wherein R2′ and R3′, which may be the same or different, represent a hydrogen atom, C1-6 alkyl, C1-3 alkyloxy, C2-3 alkenyl, benzyl, or optionally substituted phenyl, or R2′ and R3′ together represent oxo or C2-6 alkylene. More preferably, R2 and R3 together represent —O—CR2′R3′—O— wherein R2′ and R3′, which may be the same or different, represent a hydrogen atom, C1-6 alkyl, or optionally substituted phenyl, or R2′ and R3′ together represent oxo or C2-6 alkylene.
In a preferred embodiment of the present invention, in the compounds of formula (I), R4 represents a hydrogen atom, hydroxyl, optionally substituted C1-18 alkylcarbonyloxy, C2-6 alkenylcarbonyloxy, C2-6 alkynyl carbonyloxy, C1-6 alkylsulfonyloxy, benzenesulfonyloxy, benzyloxy, C1-3 alkyloxy, C1-3 alkyloxy-C1-3 alkyloxy, C1-3 alkylthio-C1-3 alkyloxy, C1-3 alkyloxy-C1-3 alkyloxy-C1-3 alkyloxy, optionally substituted C1-3 alkyloxycarbonyloxy, optionally substituted C1-6 alkylaminocarbonyloxy, optionally substituted benzoyloxy, saturated or unsaturated five- or six-membered heterocyclic oxy, optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy, optionally substituted 1H-indolylcarbonyloxy, or saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atom at the 7-position. More preferably, R4 represents a hydrogen atom, hydroxyl, optionally substituted C1-6 alkylcarbonyloxy, saturated or unsaturated five- or six-membered heterocyclic oxy, optionally substituted benzoyloxy, C1-3 alkyloxy-C1-3 alkyloxy, optionally substituted C1-6 alkylaminocarbonyloxy, optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy, optionally substituted 1H-indolylcarbonyloxy, or saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atom at the 7-position. Still more preferably, R4 represents a hydrogen atom, hydroxyl, optionally substituted C1-6 alkylcarbonyloxy, saturated or unsaturated five- or six-membered heterocyclic oxy, optionally substituted benzoyloxy, optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy, or saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy. Still more preferably, R4 represents a hydrogen atom, hydroxyl, optionally substituted cyclic C3-6 alkylcarbonyloxy, or optionally substituted benzoyloxy, or oxo in the absence of a hydrogen atom at the 7-position.
In another preferred embodiment of the present invention, in the compounds of formula (I), Het1 represents 3-pyridyl, R1 represents hydroxyl or C1-6 alkylcarbonyloxy, or the bond between 5-position and 13-position represents a double bond in the absence of R1 and a hydrogen atom at the 5-position, R2 represents optionally substituted C1-6 alkylcarbonyloxy, R3 represents optionally substituted C1-6 alkylcarbonyloxy or C1-6 alkylsulfonyloxy, or R2 and R3 together represent —O—CR21R3′—O— wherein R2′ and R3′, which may be the same or different, represent a hydrogen atom, C1-6 alkyl, or optionally substituted phenyl, or R2′ and R3′ together represent oxo or C2-6 alkylene, and R4 represents a hydrogen atom, hydroxyl, optionally substituted C1-6 alkylcarbonyloxy, saturated or unsaturated five- or six-membered heterocyclic oxy, optionally substituted benzoyloxy, C1-3 alkyloxy-C1-3 alkyloxy, optionally substituted C1-6 alkylaminocarbonyloxy, optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy, optionally substituted 1H-indolylcarbonyloxy, saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atom at the 7-position.
In still another preferred embodiment of the present invention, in the compounds of formula (I), Het1 represents 3-pyridyl, R1 represents hydroxyl, R2 represents optionally substituted C1-6 alkylcarbonyloxy, and R3 represents optionally substituted C1-6 alkylcarbonyloxy or C1-6 alkylsulfonyloxy, and R4 represents a hydrogen atom, hydroxyl, optionally substituted C1-6 alkylcarbonyloxy, saturated or unsaturated five- or six-membered heterocyclic oxy, optionally substituted benzoyloxy, C1-3 alkyloxy-C1-3 alkyloxy, optionally substituted C1-6 alkylaminocarbonyloxy, optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy, optionally substituted 1H-indolylcarbonyloxy, saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atom at the 7-position,
In a further preferred embodiment of the present invention, in the compounds of formula (I), Het1 represents 3-pyridyl, R1 represents hydroxyl, R2 represents optionally substituted C1-6 alkylcarbonyloxy, R3 represents optionally substituted C1-6 alkylcarbonyloxy or C1-6 alkylsulfonyloxy, and R4 represents a hydrogen atom, hydroxyl, optionally substituted C1-6 alkylcarbonyloxy, optionally substituted benzoyloxy, saturated or unsaturated five- or six-membered heterocyclic oxy, optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy, or saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy.
In another preferred embodiment of the present invention, in the compounds of formula (I), Het1 represents 3-pyridyl, R1 represents hydroxyl, and R2 and R3 represent optionally substituted cyclic C3-6 alkylcarbonyloxy, R4 represents a hydrogen atom, hydroxyl, optionally substituted cyclic C3-6 alkylcarbonyloxy, optionally substituted benzoyloxy, or oxo in the absence of a hydrogen atom at the 7-position.
In still another preferred embodiment of the present invention, in the compounds of formula (I), Het1 represents 3-pyridyl, R1 represents hydroxyl, R2 and R3 represent cyclopropylcarbonyloxy, and R4 preferably represents hydroxyl.
Agriculturally and horticulturally acceptable salts in the compounds of formula (I) include, for example, acid addition salts such as hydrochlorides, nitrates, sulfates, phosphates, or acetates.
Specific examples of pyripyropene derivatives of formula (I) or salts thereof preferable as the active ingredient of the composition according to the present invention include compounds shown in Tables 1 to 14 below. The pyripyropene derivatives shown in Tables 1 to 14 can be produced as described in Japanese Patent No. 2993767 (Japanese Patent Application Laid-Open No. 360895/1992) and WO 2006/129714. In the following tables, H(═) means that the bond between 5-position and 13-position represents a double bond in the absence of R1 and a hydrogen atom at the 5-position.












TABLE 1





Compound







No.
R1
R2
R3
R4
Het1




















1
OH
OCOCH3
OCOCH3
OCOCH2CH3
3-pyridyl


2
OH
OCOCH3
OCOCH3
OCOCH2CF3
3-pyridyl


3
OH
OCOCH3
OCOCH3
OCOCH2OCH3
3-pyridyl


4
OH
OCOCH3
OCOCH3
OCOCH2OCOCH3
3-pyridyl


5
OH
OCOCH3
OCOCH3
OCOCH2CH2CN
3-pyridyl


6
OH
OCOCH3
OCOCH3
OCO(CH2)2CH3
3-pyridyl


7
OH
OCOCH3
OCOCH3
OCO(CH2)3CH3
3-pyridyl


8
OH
OCOCH3
OCOCH3
OCO(CH2)4CH3
3-pyridyl


9
OH
OCOCH3
OCOCH3
OCO(CH2)5CH3
3-pyridyl


10
OH
OCOCH3
OCOCH3
OCO(CH2)6CH3
3-pyridyl


11
OH
OCOCH3
OCOCH3
OCO(CH2)16CH3
3-pyridyl


12
OH
OCOCH3
OCOCH3
OCOCH(CH3)2
3-pyridyl


13
OH
OCOCH3
OCOCH3
OCOC(CH3)3
3-pyridyl


14
OH
OCOCH3
OCOCH3
OCOCH2CH(CH3)2
3-pyridyl


15
OH
OCOCH3
OCOCH3
OCO(CH2)2CH(CH3)2
3-pyridyl


16
OH
OCOCH3
OCOCH3
OCO-trans-CH═CHCH2CH3
3-pyridyl


17
OH
OCOCH3
OCOCH3
OCOCH2C≡CCH3
3-pyridyl


18
OH
OCOCH3
OCOCH3
OCOC≡CCH2CH3
3-pyridyl


19
OH
OCOCH3
OCOCH3
OCO(CH2)2C≡CH
3-pyridyl


20
OH
OCOCH3
OCOCH3
OCO(CH2)2CH═CH2
3-pyridyl





















TABLE 2





Compound No.
R1
R2
R3
R4
Het1







21
OH
OCOCH3
OCOCH3
OCOCH2C6H5
3-pyridyl


22
OH
OCOCH3
OCOCH3
OCO(CH2)2C6H5
3-pyridyl


23
OH
OCOCH3
OCOCH3
OCOC6H5
3-pyridyl


24
OH
OCOCH3
OCOCH3
OCO-(4-Br—C6H4)
3-pyridyl


25
OH
OCOCH3
OCOCH3
OCO-(4-N3—C6H4)
3-pyridyl


26
OH
OCOCH3
OCOCH3
OCO-(4-OCF3—C6H4)
3-pyridyl


27
OH
OCOCH3
OCOCH3
OCO-(4-SO2CF3—C6H4)
3-pyridyl


28
OH
OCOCH3
OCOCH3
OCO-(3-pyridyl)
3-pyridyl


29
OH
OCOCH3
OCOCH3
OCO-(2-Cl-3-pyridyl)
3-pyridyl


30
OH
OCOCH3
OCOCH3
OCO-(2-franyl)
3-pyridyl


31
OH
OCOCH3
OCOCH3
OCO-(2-thiazolyl)
3-pyridyl


32
OH
OCOCH3
OCOCH3
OCO-(2-Cl-5-thiazolyl)
3-pyridyl


33
OH
OCOCH3
OCOCH3
OCO-(5-imidazolyl)
3-pyridyl


34
OH
OCOCH3
OCOCH3
OCS-(1-imidazolyl)
3-pyridyl


35
OH
OCOCH3
OCOCH3
OCOOCH2C6H5
3-pyridyl


36
OH
OCOCH3
OCOCH3
OSO2CH3
3-pyridyl


37
OH
OCOCH3
OCOCH3
OSO2C6H5
3-pyridyl


38
OH
OCOCH3
OCOCH3
OCONHCH2CH3
3-pyridyl


39
OH
OCOCH3
OCOCH3
OCONH(CH2)2CH3
3-pyridyl


40
OH
OCOCH3
OCOCH3
OCONHCH2C6H5
3-pyridyl





















TABLE 3





Compound







No.
R1
R2
R3
R4
Het1







41
OH
OCOCH3
OCOCH3
OCH2C6H5
3-pyridyl


42
OH
OCOCH3
OCOCH3
OCH2SCH3
3-pyridyl


43
OH
OCOCH3
OCOCH3
OCH2OCH3
3-pyridyl


44
OH
OCOCH3
OCOCH3
OCH2OCH2CH2OCH3
3-pyridyl


45
OH
OCOCH3
OCOCH3
O-(2-tetrahydropyranyl)
3-pyridyl


46
OH
OCOCH3
OCOCH3
O-(tetra-O-benzyl-mannosyl)
3-pyridyl


47
OH
OCOCH3
OCOCH3
H
3-pyridyl


48
OH
OCOCH3
OCOCH3
OCO-c-C3H5
3-pyridyl


49
OH
OCOCH3
OCOCH3
OH
3-pyridyl


50
OH
OCOCH3
OCOCH3
═O
3-pyridyl


51
OH
OCOCH3
OCOCH2CH3
OCOCH3
3-pyridyl


52
OH
OCOCH3
OCOCH2CH3
OCOCH2CH3
3-pyridyl


53
OH
OCOCH3
OCOCH2CH3
H
3-pyridyl


54
OH
OCOCH3
OCO(CH2)2CH3
OCOCH3
3-pyridyl


55
OH
OCOCH3
OCO(CH2)2CH3
OH
3-pyridyl


56
OH
OCOCH3
OCO(CH2)3CH3
OCOCH3
3-pyridyl


57
OH
OCOCH3
OCOCH(CH3)2
OCOCH3
3-pyridyl


58
OH
OCOCH3
OCOC6H5
OCOCH3
3-pyridyl


59
OH
OCOCH3
OCOC6H5
OH
3-pyridyl


60
OH
OCOCH3
OCS-
OCOCH3
3-pyridyl





(1-imidazolyl)





















TABLE 4





Compound No.
R1
R2
R3
R4
Het1







61
OH
OCOCH3
OSO2CH3
OCOCH3
3-pyridyl


62
OH
OCOCH3
OSO2CH3
OCO(CH2)3CH3
3-pyridyl


63
OH
OCOCH3
OSO2C6H5
OCOCH3
3-pyridyl


64
OH
OCOCH3
OSO2CH2CH3
OCOCH3
3-pyridyl


65
OH
OCOCH3
OSO2CH2CH2CH3
OCOCH3
3-pyridyl


66
OH
OCOCH3
OSO2CH2CH3
OH
3-pyridyl


67
OH
OCOCH3
OSO2CH2CH2CH3
OH
3-pyridyl


68
OH
OCOCH3
OH
OH
3-pyridyl


69
OH
OCOCH3
OH
OCOCH3
3-pyridyl


70
OH
OCOCH3
H
H
3-pyridyl


71
OH
OCOCH3
H
OCOCH2CH3
3-pyridyl


72
OH
OCOCH2CH3
OCOCH3
OCOCH3
3-pyridyl


73
OH
OCOCH2CH3
OCOCH2CH3
OH
3-pyridyl


74
OH
OCOCH2CH3
OCOCH2CH3
OCOCH3
3-pyridyl


75
OH
OCOCH2CH3
OCOCH3
OCOCH2CH3
3-pyridyl


76
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
3-pyridyl


77
OH
OCOCH2CH3
OCOCH2CH3
OCOC6H5
3-pyridyl


78
OH
OCOCH2CH3
OCOCH2CH3
H
3-pyridyl


79
OH
OCOCH2CH3
H
H
3-pyridyl


80
OH
OCO(CH2)2CH3
OCOCH3
OCOCH3
3-pyridyl





















TABLE 5





Compound







No.
R1
R2
R3
R4
Het1




















81
OH
OCO(CH2)2CH3
OCO(CH2)2CH3
OH
3-pyridyl


82
OH
OCO(CH2)2CH3
OCO(CH2)2CH3
OCO(CH2)2CH3
3-pyridyl


83
OH
OCO(CH2)2CH3
OCO(CH2)2CH3
OCOCH3
3-pyridyl


84
OH
OCO(CH2)3CH3
OCOCH3
OCOCH3
3-pyridyl


85
OH
OCO(CH2)3CH3
OCO(CH2)3CH3
OCO(CH2)3CH3
3-pyridyl


86
OH
OCO(CH2)3CH3
OSO2CH3
OCO(CH2)3CH3
3-pyridyl


87
OH
OCO(CH2)3CH3
OSO2CH3
OH
3-pyridyl


88
OH
OCO(CH2)16CH3
OCO(CH2)16CH3
OCO(CH2)16CH3
3-pyridyl


89
OH
OCOCH(CH3)2
OCOCH3
OCOCH3
3-pyridyl


90
OH
OCOCH(CH3)2
OCOCH(CH3)2
OCOCH(CH3)2
3-pyridyl


91
OH
OCOC(CH3)3
OCOC(CH3)3
OCOC(CH3)3
3-pyridyl


92
OH
OCOC6H5
OCOCH3
OCOCH3
3-pyridyl


93
OH
OCOC6H5
OSO2CH3
OH
3-pyridyl


94
OH
OCOC6H5
OSO2CH3
OCOCH3
3-pyridyl


95
OH
OCOC6H5
OSO2CH3
OCO(CH2)3CH3
3-pyridyl


96
OH
OCO-(4-Br—C6H4)
OCO-(4-Br—C6H4)
OCO-(4-Br—C6H4)
3-pyridyl


97
OH
OCO-(4-N3—C6H4)
OSO2CH3
OCOCH3
3-pyridyl


98
OH
OSO2CH3
OSO2CH3
OH
3-pyridyl


99
OH
OSO2CH3
OSO2CH3
OSO2CH3
3-pyridyl


100
OH
OSO2CH3
OSO2CH3
OCOCH3
3-pyridyl





















TABLE 6





Compound







No.
R1
R2
R3
R4
Het1







101
OH
OSO2CH3
OH
OH
3-pyridyl


102
OH
OH
OH
OH
3-pyridyl


103
OH
OH
OH
OCOCH3
3-pyridyl


104
OH
OH
OH
OCO(CH2)3CH3
3-pyridyl


105
OH
OH
OH
OCH2OCH2CH2OCH3
3-pyridyl


106
OH
OH
OCOCH3
OH
3-pyridyl


107
OH
OH
OCOCH2CH3
OH
3-pyridyl


108
OH
OH
OCO(CH2)2CH3
OH
3-pyridyl


109
OH
OH
OCO(CH2)3CH3
OH
3-pyridyl


110
OH
OH
OCOCH(CH3)2
OH
3-pyridyl


111
OH
OH
OSO2CH3
OH
3-pyridyl


112
OH
OH
OSO2CH2CH3
OH
3-pyridyl


113
OH
OH
OSO2CH2CH2CH3
OH
3-pyridyl


114
OH
OH
OSO2CH(CH3)2
OH
3-pyridyl


115
OH
OH
OSO2C6H5
OH
3-pyridyl


116
OH
OH
OSO2-(4-CH3—C6H4)
OH
3-pyridyl


117
OH
OH
OCO-(4-Br—C6H4)
OH
3-pyridyl


118
OH
OH
OCO(CH2)3CH3
OCO(CH2)3CH3
3-pyridyl


119
OH
OH
OSO2CH3
OSO2CH3
3-pyridyl


120
OH
OH
OSO2CH3
OCOCH3
3-pyridyl





















TABLE 7





Compound







No.
R1
R2
R3
R4
Het1







121
OH
OH
OSO2CH3
OCOCH3
3-pyridyl


122
OH
OH
OSO2CH3
OCO(CH2)3CH3
3-pyridyl


123
OH
OH
OSO2C6H5
OCOCH3
3-pyridyl


124
OH
OH
OSO2C6H5
OSO2C6H5
3-pyridyl











125
OH
—O—CH(CH3)—O—
OCO(CH2)3CH3
3-pyridyl


126
OH
—O—CH(C2H5)—O—
OH
3-pyridyl


127
OH
—O—CH(C2H5)—O—
OCO(CH2)3CH3
3-pyridyl


128
OH
—O—CH(CH═CH2)—O—
OH
3-pyridyl


129
OH
—O—CH(CH═CH2)—O—
OCO(CH2)3CH3
3-pyridyl


130
OH
—O—CH(CH(CH3)2)—O—
OH
3-pyridyl


131
OH
—O—CH(CH(CH3)2)—O—
OCO(CH2)3CH3
3-pyridyl


132
OH
—O—CH(OCH3)—O—
OH
3-pyridyl


142
OH
—O—CH(OCH3)—O—
OCO(CH2)3CH3
3-pyridyl


133
OH
—O—CH(C(CH3)3)—O—
OCO(CH2)3CH3
3-pyridyl


134
OH
—O—CH(CH2C6H5)—O—
OH
3-pyridyl


135
OH
—O—C(CH3)2—O—
OH
3-pyridyl


136
OH
—O—C(CH3)2—O—
OCOCH3
3-pyridyl


137
OH
—O—C(CH3)2—O—
OCO(CH2)3CH3
3-pyridyl


138
OH
—O—C(CH3)(C6H5)—O—
OH
3-pyridyl


139
OH
—O—C(CH3)(C6H5)—O—
OCO(CH2)3CH3
3-pyridyl


140
OH
—O—CH(C6H5)—O—
OH
3-pyridyl





















TABLE 8





Compound







No.
R1
R2
R3
R4
Het1



















141
OH
—O—CH(C6H5)—O—
OCOCH3
3-pyridyl


143
OH
—O—CH(C6H5)—O—
OCO(CH2)3CH3
3-pyridyl


144
OH
—O—CH(3-CH3—C6H4)—O—
OH
3-pyridyl


145
OH
—O—CH(3-CH3—C6H4)—O—
OCO(CH2)3CH3
3-pyridyl


146
OH
—O—CH(2-CH3—C6H4)—O—
OH
3-pyridyl


147
OH
—O—CH(4-CH3—C6H4)—O—
OCO(CH2)3CH3
3-pyridyl


148
OH
—O—CH(3-F—C6H4)—O—
OH
3-pyridyl


149
OH
—O—CH(2-F—C6H4)—O—
OCO(CH2)3CH3
3-pyridyl


150
OH
—O—CH(4-F—C6H4)—O—
OCO(CH2)3CH3
3-pyridyl


151
OH
—O—CH(4-NO2—C6H4)—O—
OH
3-pyridyl


152
OH
—O—CH(4-NO2—C6H4)—O—
OCO(CH2)3CH3
3-pyridyl


153
OH
—O—CH(4-OCH3—C6H4)—O—
OH
3-pyridyl


154
OH
—O—CH(4-OCH3—C6H4)—O—
OCO(CH2)3CH3
3-pyridyl


155
OH
—O—C(spiro-c-C5H8)—O—
OH
3-pyridyl


156
OH
—O—C(spiro-c-C5H8)—O—
OCO(CH2)3CH3
3-pyridyl


157
OH
—O—C(spiro-c-C6H10)—O—
OH
3-pyridyl


158
OH
—O—C(spiro-c-C6H10)—O—
OCO(CH2)3CH3
3-pyridyl


159
OH
—O—CO—O—
OH
3-pyridyl


160
OH
—O—CO—O—
OCO-1-imidazolyl
3-pyridyl





















TABLE 9





Compound







No.
R1
R2
R3
R4
Het1



















161
OH
—O—CO—O—
OCO(CH2)3CH3
3-pyridyl












162
OCOCH3
OCOCH3
OCOCH3
OCOCH3
3-pyridyl


163
OCOCH3
OCOCH3
OCOCH3
OH
3-pyridyl


164
OCOCH3
OCOCH3
OCO(CH2)2CH3
OCOCH3
3-pyridyl


165
OCOCH3
OH
OH
OCOCH3
3-pyridyl


166
OCOCH3
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
3-pyridyl


167
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
3-pyridyl


168
OCOCH2CH3
OCOCH3
OCOCH3
OCOCH3
3-pyridyl


169
OCO(CH2)3CH3
OCOCH3
OCOCH3
OCOCH3
3-pyridyl


170
OCO(CH2)3CH3
OCOCH3
OCOCH3
OCO(CH2)3CH3
3-pyridyl


171
OCO(CH2)2CH3
OCOCH3
OCOCH3
OCOCH3
3-pyridyl


172
OCH3
OCOCH3
OCOCH3
OCOCH3
3-pyridyl


173
H(═)
OSO2CH3
OSO2CH3
OH
3-pyridyl


174
H(═)
OCOC6H5
OSO2CH3
OCOCH3
3-pyridyl


175
H(═)
OH
OH
OCOCH3
3-pyridyl


176
H(═)
OCOCH3
OCOCH3
═O
3-pyridyl











177
H(═)
—O—CH(C6H5)—O—
OCOCH3
3-pyridyl


178
H(═)
—O—CH(CH(CH3)2)—O—
OH
3-pyridyl


179
H(═)
—O—CH(4-NO2—C6H4)—O—
OH
3-pyridyl












180
H(═)
OCOCH3
OCOCH3
OCOCH3
3-pyridyl





















TABLE 10





Compound







No.
R1
R2
R3
R4
Het1







181
H(═)
OH
OH
OH
3-pyridyl


182
H(═)
OCOCH3
OCOCH3
OH
3-pyridyl


183
H(═)
OCOCH3
OCOCH3
OCH2SCH3
3-pyridyl


184
H(═)
OCOCH3
OCOCH3
OCH2OCH3
3-pyridyl


185
H(═)
OCOCH3
OCOCH3
OCO(CH2)3CH3
3-pyridyl


186
H(═)
OCOCH3
OCOCH3
OCO(CH2)2Ph
3-pyridyl


187
H(═)
OCOCH3
OSO2CH3
OCOCH3
3-pyridyl


188
H(═)
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
3-pyridyl


189
H(═)
OCOCH2CH3
OCOCH2CH3
OH
3-pyridyl


190
H(═)
OH
OSO2CH3
OH
3-pyridyl


191
H(═)
OH
OH
OCO(CH2)3CH3
3-pyridyl











192
H(═)
—O—C(CH3)2—O—
OH
3-pyridyl


193
H(═)
—O—C(CH3)2—O—
OCO(CH2)3CH3
3-pyridyl


194
H(═)
—O—CH(C6H5)—O—
OH
3-pyridyl


195
H(═)
—O—CH(C6H5)—O—
OCO(CH2)3CH3
3-pyridyl


196
H(═)
—O—CH(4-OCH3—C6H4)—O—
OH
3-pyridyl


197
H(═)
—O—CH(C2H5)—O—
OH
3-pyridyl


198
H(═)
—O—CH(C(CH3)2)—O—
OH
3-pyridyl


199
H(═)
—O—CH(CH2C6H5)—O—
OH
3-pyridyl












200
═O
OH
OH
OH
3-pyridyl





















TABLE 11





Compound







No.
R1
R2
R3
R4
Het1







201
═O
OCOCH3
OCOCH3
═O
3-pyridyl


202
═O
OCOCH3
OCOCH3
OH
3-pyridyl


203
═O
OCOCH3
OCOCH3
OCOCH3
3-pyridyl


204
═O
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
3-pyridyl


205
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-pyridyl)
3-pyridyl


206
OH
OCOCH2CH3
OCOCH2CH3
OCOCH(CH3)2
3-pyridyl


207
OH
OCOCH2CH3
OCOCH2CH3
OCOC(CH3)3
3-pyridyl


208
OH
OCOCH2CH3
OCOCH2CH3
OCO-(4-CF3—C6H4)
3-pyridyl


209
OH
OCOCH2CH3
OCOCH2CH3
OCO-(1-imidazolyl)
3-pyridyl


210
OH
OCOCH2CH3
OCOCH2CH3
OCONH(CH2)2CH3
3-pyridyl


211
OH
OCOCH2CH3
OCOCH2CH3
O-(2-tetrahydropyranyl)
3-pyridyl


212
OH
OCOCH2CH3
OCOCH2CH3
OCO-(6-Cl-3-pyridyl)
3-pyridyl


213
OH
OCOCH2CH3
OCOCH2CH3
OCO-c-C3H5
3-pyridyl


214
OH
OCOCH2CH3
OCOCH2CH3
OCO-c-C4H7
3-pyridyl


215
OH
OCOCH2CH3
OCOCH2CH3
OCOCH═CH
3-pyridyl


216
OH
OCOCH2CH3
OCOCH2CH3
OCO-(4-pyridyl)
3-pyridyl


217
OH
OCOCH2CH3
OCOCH2CH3
OCO-(2-pyridyl)
3-pyridyl


218
OH
OCO-c-C3H5
OCO-c-C3H5
OCO-c-C3H5
3-pyridyl


219
OH
OCO-c-C4H7
OCO-c-C4H7
OCO-c-C4H7
3-pyridyl


220
OH
OCOC6H5
OCOC6H5
OCOC6H5
3-pyridyl





















TABLE 12





Compound







No.
R1
R2
R3
R4
Het1







221
OH
OCOCH2CH3
OCOCH2CH3
OCO-(6-CF3-3-pyridyl)
3-pyridyl


222
OH
OCOCH2CH3
OCOCH2CH3
OCO-(4-CF3-3-pyridyl)
3-pyridyl


223
OH
OCOCH2CF3
OCOCH2CF3
OCOCH2CF3
3-pyridyl


224
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CF3
3-pyridyl


225
═O
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
6-Cl-3-pyridyl


226
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
6-Cl-3-pyridyl


227
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-F-4-pyridyl)
3-pyridyl


228
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-Cl-4-pyridyl)
3-pyridyl


229
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-CH3-2-pyridyl)
3-pyridyl


230
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-COC6H5-2-pyridyl)
3-pyridyl


231
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-OCH2CH2CH3-2-pyridyl)
3-pyridyl


232
OH
OCOCH2CH3
OCOCH2CH3
OCO-(6-F-3-pyridyl)
3-pyridyl


233
OH
OCO-c-C5H9
OCO-c-C5H9
OCO-c-C5H9
3-pyridyl


234
OH
OCO-c-C6H11
OCO-c-C6H11
OCO-c-C6H11
3-pyridyl


235
OH
OCOCH2CN
OCOCH2CN
OCOCH2CN
3-pyridyl


236
OCOCH2-c-C3H5
OCOCH2-c-C3H5
OCOCH2-c-C3H5
OCOCH2-c-C3H5
3-pyridyl


237
OH
OCOCH2-c-C3H5
OCOCH2-c-C3H5
OCOCH2-c-C3H5
3-pyridyl


238
OH
OCO-(1-CH3-2,
OCO-(1-CH3-2,
OCO-(1-CH3-2,2-F2-c-C3H2)
3-pyridyl




2-F2-c-C3H2)
2-F2-c-C3H2)


239
OH
OCOCH2CH3
OCOCH2CH3
OCO-(4-CH3-3-pyridyl)
3-pyridyl


240
OH
OCOCH2CH3
OCOCH2CH3
OCO-(4-Cl-3-pyridyl)
3-pyridyl





















TABLE 13





Compound







No.
R1
R2
R3
R4
Het1







241
OH
OCOCH2CH3
OCOCH2CH3
OCO-(4-COOCH3-3-pyridyl)
3-pyridyl


242
OH
OCOCH2CH3
OCOCH2CH3
OCO-[5-(CF3)-thieno[3,2-b]-pyridin-6-yl]
3-pyridyl


243
OH
OCOCH2CH3
OCOCH2CH3
OCO-(2-CN—C6H4)
3-pyridyl


244
OH
OCOCH2CH3
OCOCH2CH3
OCO-(2-CF3—C6H4)
3-pyridyl


245
OH
OCOCH2CH3
OCOCH2CH3
OCO-(2-F—C6H4)
3-pyridyl


246
OH
OCOCH2CH3
OCOCH2CH3
OCO-(2-NO2—C6H4)
3-pyridyl


247
OH
OCOCH2CH3
OCOCH2CH3
OCO-(2-Cl-3-pyridyl)
3-pyridyl


248
OH
OCOCH2CH3
OCOCH2CH3
OCO(2-Cl-6-CH3-3-pyridyl)
3-pyridyl


249
OH
OCOCH2CH3
OCOCH2CH3
OCH2OCH3
3-pyridyl


250
OH
OCO-(2,2-F2-
OCO-(2,2-F2-
OCO-(2,2-F2-c-C3H3)
3-pyridyl




c-C3H3)
c-C3H3)


251
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-SC(CH3)3-2-pyridyl)
3-pyridyl


252
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3,5-2F-2-pyridyl)
3-pyridyl


253
OH
OCOCH2CH3
OCOCH2CH3
OCO-2-pyrazinyl
3-pyridyl


254
OH
OCOCH2CH3
OCOCH2CH3
OCO-4-thiazolyl
3-pyridyl


255
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-Cl-2-thienyl)
3-pyridyl


256
OH
OCOCH2CH3
OCOCH2CH3
OCO-(6-CH3-3-pyridyl)
3-pyridyl


257
OH
OCOCH2CH3
OCOCH2CH3
OCO-(6-Cl-2-pyridyl)
3-pyridyl


258
OH
OCOCH2CH3
OCOCH2CH3
OCO-(6-F-2-pyridyl)
3-pyridyl


259
OH
OCOCH2CH3
OCOCH2CH3
OCO-(1-CH3-1H-indolyl)
3-pyridyl


260
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-Cl-2-pyridyl)
3-pyridyl





















TABLE 14





Compound







No.
R1
R2
R3
R4
Het1







261
OH
OCO-c-C3H5
OCO-c-C3H5
OH
3-pyridyl


262
OH
OCOCH2CH3
OCOCH2CH3
OCO-(2-F-3-pyridyl)
3-pyridyl


263
OH
OCOCH2CH3
OCOCH2CH3
OCO-(4-CN—C6H4)
3-pyridyl


264
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-CN—C6H4)
3-pyridyl


265
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-CF3—C6H4)
3-pyridyl


266
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2(2-pyridyl)
3-pyridyl


267
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2(3-pyridyl)
3-pyridyl


268
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2S(4-pyridyl)
3-pyridyl


269
OH
OCO-c-C3H5
OCO-c-C3H5
OCO-(2-CN—C6H4)
3-pyridyl


270
OH
OCO-c-C3H5
OCO-c-C3H5
OCO(4-CF3-3-pyridyl)
3-pyridyl


271
OH
OCO-c-C3H5
OCO-c-C3H5
OCO(3-Cl-2-pyridyl)
3-pyridyl











272
OH
—O—CH(C6H5)—O—
═O
3-pyridyl


273
OH
—O—CH(4-OCH3—C6H4)—O—
═O
3-pyridyl


274
OCO(CH2)3CH3
—O—CO—O—
OCO(CH2)3CH3
3-pyridyl


275
OCOCH3
—O—CH(C6H5)—O—
OCOCH3
3-pyridyl


276
═O
—O—CH(4-OCH3—C6H4)—O—
OH
3-pyridyl












277
OH
OCO-c-C3H5
OCO-c-C3H5
═O
3-pyridyl


278
OH
OCO-c-C3H5
OCO-c-C3H5
H
3-pyridyl


279
OH
OCOCH3
OCOCH3
OCOCH3
3-pyridyl









Other pest control agents mixable into the pyripyropene derivatives in the present invention include, for example, fungicides, miticides, herbicides, or plant growth-regulating agents. Specific examples of such agents are described, for example, in The Pesticide Manual, the 13th edition, published by The British Crop Protection Council; and SHIBUYA INDEX, the 10th edition, 2005, published by SHIBUYA INDEX RESEARCH GROUP.
Preferred other pest control agents mixable into the pyripyropene derivatives include insecticide, for example, acephate, dichlorvos, EPN, fenitrothion, fenamifos, prothiofos, profenofos, pyraclofos, chlorpyrifos-methyl, chlorfenvinphos, demeton, ethion, malathion, coumaphos, isoxathion, fenthion, diazinon, thiodicarb, aldicarb, oxamyl, propoxur, carbaryl, fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran, carbosulfan, furathiocarb, hyquincarb, alanycarb, methomyl, benfuracarb, cartap, thiocyclam, bensultap, dicofol, tetradifon, acrinathrin, bifenthrin, cycloprothrin, cyfluthrin, dimefluthrin, empenthrin, fenfluthrin, fenpropathrin, imiprothrin, metofluthrin, permethrin, phenothrin, resmethrin, tefluthrin, tetramethrin, tralomethrin, transfluthrin, cypermethrin, deltamethrin, cyhalothrin, fenvalerate, fluvalinate, ethofenprox, flufenprox, halfenprox, silafluofen, cyromazine, diflubenzuron, teflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, penfluoron, triflumuron, chlorfluazuron, diafenthiuron, methoprene, fenoxycarb, pyriproxyfen, halofenozide, tebufenozide, methoxyfenozide, chromafenozide, dicyclanil, buprofezin, hexythiazox, amitraz, chlordimeform, pyridaben, fenpyroxymate, flufenerim, pyrimidifen, tebufenpyrad, tolfenpyrad, fluacrypyrim, acequinocyl, cyflumetofen, flubendiamide, ethiprole, fipronil, ethoxazole, imidacloprid, nitenpyram, clothianidin, acetamiprid, dinotefuran, thiacloprid, thiamethoxam, pymetrozine, bifenazate, spirodiclofen, spiromesifen, flonicamid, chlorfenapyr, pyriproxyfene, indoxacarb, pyridalyl, spinosad, avermectin, milbemycin, azadirachtin, nicotine, rotenone, BT formulations, insect pathological viral agents, emamectinbenzoate, spinetoram, pyrifluquinazon, chiorantraniliprole, cyenopyrafen, spirotetramat, lepimectin, metaflumizone, pyrafluprole, pyriprole, dimefluthrin, fenazaflor, hydramethylnon, triazamate, and compounds of formula (II) described in WO 2006/013896:




wherein R101 represents COR104 or COOR105 wherein R104 and R105 represent C1-4 alkyl, preferably COR104,
R102 represents C1-4 alkyl,
R103 represents C1-4 alkyl,
X101 and X102 each independently represent a hydrogen atom or C1-4 alkyl optionally substituted by a halogen atom, preferably X101 represents a hydrogen atom while X102 represents C1-4 alkyl,
provided that X101 and X102 do not simultaneously represent a hydrogen atom, and
Y101, Y102, Y103, Y104, and Y105 each independently represent a hydrogen atom, C1-8 alkyloxy, wherein the C1-8 alkyloxy group is substituted by one or more halogen atoms, which may be the same or different, and/or C1-4 alkyloxy substituted by one or more halogen atoms, which may be the same or different, or a halogen atom, preferably Y101 represents a hydrogen atom or a halogen atom, Y102 and Y103 represent C1-4 alkyloxy substituted by a halogen atom, and Y104 and Y105 represent a hydrogen atom,
provided that at least one of Y101, Y102, Y103, Y104, and Y105 represents C1-8 alkyloxy, wherein the C1-8 alkyloxy group is substituted by one or more halogen atoms, which may be the same or different, and/or C1-4 alkyloxy substituted by one or more halogen atoms which may be the same or different,
or two adjacent groups of Y101, Y102, Y103, Y104, and Y105 together may represent —O—(CH2)n—O—, wherein n is 1 or 2, substituted by one or more halogen atoms.
Examples of further preferred other pest control agents mixable into the pyripyropene derivatives include flonicamid, acetamiprid, fipronil, imidacloprid, chlorfenapyr, clothianidin, thiamethoxam, dinotefuran, and compounds of compound Nos. A120, A190, A257, and A648 included in the compounds of formula (II) wherein R101 represents methoxycarbonyl, R102 represents methyl, R103 represents ethyl, X101, Y104, and Y105 represent a hydrogen atom, X102 represents methyl, and Y101, Y102/and Y103 represent a group shown in Table 15 below:










TABLE 15





Compound





No.
Y101
Y102
Y103







A120
H
H
OCF3


A190
H
H
OCF2CHF2


A257
Cl
H
OCF3









A648
H
—OCF2CF2O—









Particularly preferred are flonicamid, acetamiprid, fipronil, imidacloprid, and compounds of compound Nos. A120 and A190.

Fungicides mixable into the pyripyropene derivatives include, for example, strobilrin compounds such as azoxystrobin, kresoxym-methyl, trifloxystrobin, orysastrobin, picoxystrobin, and fuoxastrobin; anilinopyrimidine compounds such as mepanipyrim, pyrimethanil, and cyprodinil; azole compounds such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, myclobutanil, cyproconazole, tebuconazole, hexaconazole, prochloraz, and simeconazole; quinoxaline compounds such as quinomethionate; dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, and propineb; phenylcarbamate compounds such as diethofencarb; organochlorine compounds such as chlorothalonil and quintozene; benzimidazole compounds such as benomyl, thiophanate-methyl, and carbendazole; phenylamide compounds such as metalaxyl, oxadixyl, ofurase, benalaxyl, furalaxyl, and cyprofuram; sulfenic acid compounds such as dichiofluanid; copper compounds such as copper hydroxide and oxine-copper; isoxazole compounds such as hydroxyisoxazole; organophosphorus compounds such as fosetyl-aluminium and tolclofos-methyl; N-halogenothioalkyl compounds such as captan, captafol, and folpet; dicarboxylmide compounds such as procymidone, iprodione, and vinchlozolin; benzanilide compounds such as flutolanil and mepronil; morpholine compounds such as fenpropimorph and dimethomorph; organotin compounds such as fenthin hydroxide, and fenthin acetate; and cyanopyrrole compounds such as fludioxonil and fenpiclonil. Other fungicides include fthalide, probenazole, acibenzolar-S-methyl, tiadinil, isotianil, carpropamid, diclocymet, fenoxanil, tricyclazole, pyroquilon, ferimzone, fluazinam, cymoxanil, triforine, pyrifenox, fenarimol, fenpropidin, pencycuron, cyazofamid, cyflufenamid, boscalid, penthiopyrad, proquinazid, quinoxyfen, famoxadone, fenamidone, iprovalicarb, benthiavalicarb-isopropyl, fluopicolide, pyribencarb, kasugamycin, and validamycin.
In another preferred embodiment of the present invention, the pest control composition comprises, as active ingredients, a pyripyropene derivative of formula (I), wherein Het1 represents 3-pyridyl, R1 represents hydroxyl, R2 and R3 represents cyclopropylcarbonyloxy, R4 represents hydroxyl, or an agriculturally and horticulturally acceptable salt thereof and
an insecticide as other pest control agent, the insecticide being a compound selected from the group consisting of flonicamid, acetamiprid, fipronil, imidacloprid, chlorfenapyr, clothianidin, thiamethoxam, and dinotefuran and compounds of formula (II) wherein R101 represents methoxycarbonyl, R102 represents methyl, R103 represents ethyl, X101, Y104, and Y105 represent a hydrogen atom, X102 represents methyl, and Y101, Y102, and Y103 represent a group shown in Table 16 below:










TABLE 16





Compound





No.
Y101
Y102
Y103







A120
H
H
OCF3


A190
H
H
OCF2CHF2


A257
Cl
H
OCF3









A648
H
—OCF2CF2O—









According to another aspect of the present invention, there is provided a pest control composition that, in addition to the above ingredients, comprises a suitable agriculturally and horticulturally acceptable carrier. The pest control composition may be formulated into any suitable dosage forms, for example, emulsifiable concentrates, liquid formulations, suspensions, wettable powders, water dispersible granules, floables, dusts, DL dusts, granules, micro granule fines, tablets, oils, aerosols, smoking agents, or microcapsules. These dosage forms may be produced as described, for example, in “Noyaku Seizai Gaido (Guide for Pesticide Formulation)” edited by “Seyoho Kenkyukai (Special Committee on Agricultural Formulation and Application)”, Japan Plant Protection Association, 1997.
Carriers usable herein include solid carriers, liquid carriers, gaseous carriers, surfactants, dispersants, and other adjuvants for formulations.
Solid carriers include, for example, talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, and calcium carbonate.
Liquid carriers include, for example, alcohols such as methanol, n-hexanol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as n-hexane, kerosine, and kerosene; aromatic hydrocarbons such as toluene, xylene, and methylnaphthalene; ethers such as diethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; nitriles such as acetonitrile and isobutyronitrile; acid amides such as dimethylformamide and dimethylacetamide; vegetable oils such as soy bean oil and cotton seed oil; dimethylsulfoxide; and water.
Gaseous carriers include, for example, LPG, air, nitrogen, carbon dioxide, and dimethyl ether.
Surfactants or dispersants usable, for example, for emulsifying, dispersing, or spreading include, for example, alkylsulfuric esters, alkyl(aryl)sulfonic acid salts, polyoxyalkylene alkyl(aryl)ethers, polyhydric alcohol esters, and lignin sulfonic acid salts.
Adjuvants usable for improving the properties of formulations include, for example, carboxymethylcellulose, gum arabic, polyethylene glycol, and calcium stearate.
The above carriers, surfactants, dispersants, and adjuvants may be used either solely or in combination according to need.
The total content of the active ingredients in the composition according to the present invention is 0.1 to 99.9% by weight, preferably 0.2 to 80% by weight. The mixing ratio between the pyripyropene derivative of formula (I) and the other pest control agent(s) may vary in a wide range. In general, the composition according to the present invention contains 0.1 to 80% by weight of the pyripyropene derivative.
Pest control compositions, which further comprise agriculturally and horticulturally acceptable carriers, in a preferred embodiment include:
(1) a composition in a wettable powder form comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, 0.6 to 30% by weight of a wetting agent and a dispersant, and 20 to 95% by weight of an extender,
(2) a composition in a water dispersible granule form comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, 0.6 to 30% by weight of a wetting agent, a dispersant, and a binder, and 20 to 95% by weight of an extender,
(3) a composition in a floable form comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, 5 to 40% by weight of a dispersant, a thickening agent, an antifreezing agent, an antiseptic, and an antifoaming agent, and 20 to 94% by weight of water,
(4) a composition in an emulsifiable concentrate comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, 1 to 30% by weight of an emulsifier and an emulsion stabilizer, and 20 to 97% by weight of an organic solvent,
(5) a composition in a dust form comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, and 70 to 99.8% by weight of an extender,
(6) a composition in a DL dust (low drift dust) form comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, and 70 to 99.8% by weight of an extender,
(7) a composition in a micro granule fine form comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, 0.2 to 10% by weight of a solvent or a binder, and 70 to 99.6% by weight of an extender,
(8) a composition in a granule form comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, 0.5 to 30% by weight of a granulation assistant (a surfactant) and a binder, and 20 to 98% by weight of an extender, and
(9) a composition in a microcapsule form comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of an insecticide as the other pest control agent, 1 to 50% by weight of a coating agent, an emulsifier, a dispersant, and an antiseptic, and 20 to 98% by weight of water. Among them, the composition (1), (2), (3), (4), (7), or (8) is preferred, and the composition (2), (3), (4), or (8) is more preferred.
In the pest control composition according to the present invention, a method may be adopted in which a first composition containing, as active ingredient, only a first active ingredient of the pest control composition according to the present invention, i.e., at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof, and a second composition containing, as active ingredient, only a second active ingredient of the pest control composition according to the present invention, i.e., at least one other pest control agent, are prepared and, in use, these two compositions are mixed together on site.
Thus, according to still another aspect of the present invention, there is provided a combination comprising at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof and at least one other pest control agent.
In another preferred embodiment of the present invention, in the combination, the at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof is provided as a first composition containing the at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof as active ingredient, and at least one other pest control agent is provided as a second composition containing the at least one other pest control agent as active ingredient. In this case, as with the above pest control composition, the first and second compositions may be in any desired dosage form using a suitable carrier or adjuvant. The combination may also be provided in a form like a drug set.
According to a further aspect of the present invention, there is provided a method protecting useful plants from pests, comprising applying at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof and at least one other pest control agent simultaneously or separately from each other to an area to be treated.
In this method, applying “simultaneously” embraces a case where at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof and at least one other pest control agent are mixed together before application to an area to be treated and the mixture is applied to the object area. On the other hand, applying “separately” embraces a case where, without previously mixing at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof and at least one other pest control agent together, at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof is applied before the application of at least one other pest control agent, and a case where, without previously mixing at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof and at least one other pest control agent together, at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof is applied after the application of at least one other pest control agent.
According to another aspect of the present invention, there is provided a method for protecting useful plants from pests, comprising applying
(1) a first composition comprising at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof as active ingredient and
(2) a second composition comprising at least one other pest control agent as active ingredient to an area to be treated.
According to still another aspect of the present invention, there is provided a method for protecting useful plants from pests, comprising treating an object pest, an object useful plant, or a seed, a soil, or a cultivation carrier of the object useful plant with the pest control composition or the combination according to the present invention as such or after dilution.
According to a further aspect of the present invention, there is provided use of the pest control composition or the combination according to the present invention for the protection of useful plants from pests.
Methods for treating the object pest, the object useful plant, or the seed, soil, or cultivation carrier of the object useful plant with the pest control composition according to the present invention include, for example, spreading treatment, soil treatment, surface treatment, and fumigation. Spreading treatments include, for example, spreading, spraying, misting, atomizing, granule, application, and application to water surface. Soil treatments include, for example, soil drenching and soil admixing. Surface treatments include, for example, coating, dressing, and covering. Fumigation treatments include, for example, covering of soil with a polyethylene film after soil injection. Accordingly, the use of the pest control composition according to the present invention includes the application of the pest control composition according to the present invention by fumigation in a sealed space.
Insect pest species against which the composition according to the present invention exhibits control effect include: lepidopteran insect pests, for example, Spodoptera litura, Mamestra brassicae, Pseudaletia separata, green caterpillar, Plutella xylostella, Spodoptera exigua, Chilo suppressalis, Cnaphalocrocis medinalis, Tortricidae, Carposimidae, Lyonetiidae, Lymantriidae, insect pests belonging to the genus Agrotis spp., insect pests belonging to the genus Helicoverpa spp., and insect pests belonging to the genus Heliothis spp.; hemipteran insect pests, for example, Aphididae, Adelgidae or Phylloxeridae such as Myzus persicae, Aphis gossypii, Aphis fabae, Aphis maidis (corn-leaf aphid), Acyrthosiphon pisum, Aulacorthum solani, Aphis craccivora, Macrosiphum euphorbiae, Macrosiphum avenae, Methopolophium dirhodum, Rhopalosiphum padi, Schizaphis graminum, Brevicoryne brassicae, Lipaphis erysimi, Aphis citricola, Rosy apple aphid, Eriosoma lanigerum, Toxoptera aurantii, and Toxoptera citricidus, Deltocephalidae such as Nephotettix cincticeps, Delphacidae such as Laodelphax striatellus, Nilaparvata lugens, and Sogatella furcifera, Pentatomidae such as Eysarcoris ventralis, Nezara viridula, and Trigonotylus ruficornis, Aleyrodidae such as Bemisia tabaci Genn., Bemisia tabaci, and Trialeurodes vaporariorum, and Diaspididae, Margarodidae, Ortheziidae, Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae, Eriococcidae, Asterolecamidae, Beesonidae, Lecanodiaspididae, or Cerococcidae, such as Pseudococcus comstocki and Planococcus citri Risso; Coleoptera insect pests, for example, Lissorhoptrus oryzophilus, Callosobruchuys chienensis, Tenebrio molitor, Diabrotica virgifera virgifera, Diabrotica undecimpunctata howardi, Anomala cuprea, Anomala rufocuprea, Phyllotreta striolata, Aulacophora femoralis, Leptinotarsa decemlineata, Oulema oryzae, Bostrychidae, and Cerambycidae; Acari, for example, Tetranychus urticae, Tetranychus kanzawai, and Panonychus citri; Hymenopteran insect pests, for example, Tenthredimidae; Orthopteran insect pests, for example, Acrididae; Dipteran insect pests, for example, Muscidae and Agromyzidae; Thysanopteran insect pests, for example, Thrips palmi and Frankliniella occidentalis; Plant Parasitic Nematodes, for example, Meloidogyne hapla, Pratylenchus, Aphelenchoides besseyi, and Bursaphelenchus xylophilus; and zooparasite, for example, Aphaniptera, Anoplura, mites such as Boophilus spp., Haemaphysalis longicornis, Rhipicephalus sanguineus, and Sarcoptes spp. Preferred are hemipteran insect pests and lepidopteran insect pests.
Preferred hemipteran insect pests are selected from Aphididae, Adelgidae, and Phylloxeridae, particularly preferably Aphididae; Diaspididae, Margarodidae, Ortheziidae, Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae, Eriococcidae, Asterolecamidae, Beesonidae, Lecanodiaspididae, and Cerococcidae; or Aleyrodidae. More preferred are Myzus persicae, Aphis gossypii, Aphis fabae, Aphis maidis (corn-leaf aphid), Acyrthosiphon pisum, Aulacorthum solani, Aphis craccivora, Macrosiphum euphorbiae, Macrosiphum avenae, Metopolophium dirhodum, Rhopalosiphum padi, Schizaphis graminum, Brevicoryne brassicae, Lipaphis erysimi, Aphis citricola, Rosy apple aphid, Eriosoma lanigerum, Toxoptera aurantii, Toxoptera citricidus, Pseudococcus comstocki, or Trialeurodes vaporariorum (Greenhouse whitefly).
EXAMPLES
The present invention is further illustrated by the following Examples that are not intended as a limitation of the invention. In the Examples, compounds 261 and 237 were synthesized as described in WO 2006/129714, and compounds A120, A190, A257, and A648 were synthesized as described in WO 2006/013896.
Synthetic Examples
Synthetic Example 1
Synthetic Example of Compound 277
Compound 261 (20 mg) was dissolved in dichloromethane (1 ml). Dess-Martin periodinane (21 mg) was added to the solution at 0° C., and, in this state, the mixture was stirred for 2 hr 40 min. A saturated aqueous sodium thiosulfate solution was added to the reaction solution, and the mixture was extracted with chloroform. The chloroform layer was washed with saturated brine and was dried over anhydrous magnesium sulfate. The solvent was then removed by evaporation under the reduced pressure, and the crude product thus obtained was purified by preparative thin-layer chromatography (Merck silica gel 60 F (0.5 mm), acetone:hexane=1:1) to give compound 277 (5.4 mg).
Synthetic Example 2
Synthetic Example of Compound 278
Compound 261 (50 mg) was dissolved in toluene (3 ml). 1,1′-Thiocarbonyldiimidazole (90 mg) was added to the solution at room temperature, and the mixture was heated under reflux for 2.5 hr. The reaction solution was cooled to room temperature. Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine and was dried over anhydrous magnesium sulfate, and the solvent was then removed by evaporation under the reduced pressure. The crude product thus obtained was purified by preparative thin-layer chromatography (Merck silica gel 60 F (0.5 mm), acetone:hexane=1:1). The product (41 mg) thus obtained was dissolved in toluene (2 ml), tri-n-butyltin hydride (20 mg) was added to the solution at room temperature, and the mixture was heated under reflux for 2.5 hr. The reaction solution was cooled to room temperature, water was added to the cooled reaction solution, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine and was dried over anhydrous magnesium sulfate, and the solvent was then removed by evaporation under the reduced pressure. The crude product thus obtained was purified by preparative thin-layer chromatography (Merck silica gel 60 F (0.5 mm), acetone:hexane=1:1) to give compound 278 (3.5 mg).
For compounds 227 and 278 produced in Synthetic Examples 1 and 2, 1H-NMR data and mass spectrometric data are shown in Table 17.









TABLE 17









Mass spectrometric



data











NMR data
Measuring












Compound
Solvent
1H-NMR δ (ppm)
method
Data





227
CDCl3
0.83-1.00 (8H, m), 0.96 (3H, s),
ESI
592




1.44 (1H, m), 1.53-1.61 (2H, m),

(M + H)+




1.63 (3H, s), 1.76 (1H, d, J = 3.7 Hz),




1.81 (3H, s), 1.87 (2H, m),




1.94-1.97 (1H, m), 2.21 (1H, m),




2.53 (1H, dd, J = 2.6, 14.9 Hz),




2.78 (1H, t, J = 14.9 Hz),




2.91 (1H, d, J = 1.5 Hz), 3.66




(1H, d, J = 12.0 Hz),




3.84 (1H, d, J = 12.0 Hz),




4.82 (1H, dd, J = 4.8, 11.7 Hz),




5.06 (1H, m), 6.71 (1H, s),




7.41 (1H, dd, J = 4.8, 8.0 Hz),




8.09 (1H, dt, J = 1.7, 8.0 Hz),




8.70 (1H, dd, J = 1.7, 4.8 Hz),




9.02 (1H, d, J = 1.7 Hz)


278
CDCl3
0.84-1.00 (8H, m), 0.90 (3H, s),
ESI
578




1.12-1.16 (1H, m), 1.25 (1H, s),

(M + H)+




1.35-1.46 (1H, m), 1.41 (3H, s),




1.56-1.70 (5H, m), 1.66 (3H, s),




1.78-1.89 (2H, m),




2.12-2.17 (2H, m), 2.82




(1H, d, J = 1.4 Hz),




3.69 (1H, d, J = 11.9 Hz),




3.91 (1H, d, J = 11.9 Hz),




4.83 (1H, dd, J = 5.1, 11.5 Hz),




4.99 (1H, m), 6.46 (1H, s), 7.42 (1H,




m), 8.11 (1H, dt, J = 1.7, 8.0 Hz),




8.69 (1H, m), 9.01 (1H, m)









PREPARATION EXAMPLES
Preparation Example 1
Wettable Powder
















Pyripyropene derivative (compound 261)
10
wt %



Imidacloprid
20
wt %



Clay
50
wt %



White carbon
2
wt %



Diatomaceous earth
13
wt %



Calcium lignin sulfonate
4
wt %



Sodium lauryl sulfate
1
wt %









The above ingredients were intimately mixed together, and the mixture was ground to prepare wettable powder.
Preparation Example 2
Water Dispersible Granule
















Pyripyropene derivative (compound 237)
10
wt %



Imidacloprid
20
wt %



Clay
60
wt %



Dextrin
5
wt %



Alkylmaleic acid copolymer
4
wt %



Sodium lauryl sulfate
1
wt %









The above ingredients were homogeneously ground and intimately mixed together. Water was added to the mixture, followed by thorough kneading. Thereafter, the kneaded product was granulated and dried to prepare a water dispersible granule.
Preparation Example 3
Floables
















Pyripyropene derivative (compound 261)
5
wt %



Flonicamid
20
wt %



POE polystyryl phenyl ether sulfate
5
wt %



Propylene glycol
6
wt %



Bentonite
1
wt %



1% aqueous xanthan gum solution
3
wt %



PRONAL EX-300
0.05
wt %



(Toho Chemical Industry Co., Ltd.)





ADDAC 827
0.02
wt %



(K.I. Chemical Industry Co., Ltd.)





Water
To 100
wt %









All the above ingredients except for the 1% aqueous xanthan gum solution and a suitable amount of water were premixed together, and the mixture was then ground by a wet grinding mill. Thereafter, the 1% aqueous xanthan gum solution and the remaining water were added to the ground product to prepare 100 wt % floables.
Preparation Example 4
Emulsifiable Concentrate















Pyripyropene derivative (compound 237)
 2 wt %



Acetamiprid
13 wt %



N,N-dimethylformamide
20 wt %



Solvesso 150 (Exxon Mobil Corporation)
55 wt %



Polyoxyethylene alkyl aryl ether
10 wt %









The above ingredients were intimately mixed together and dissolved to prepare an emulsifiable concentrate.
Preparation Example 5
Dust
















Pyripyropene derivative (compound 277)
0.5
wt %



Acetamiprid
1.5
wt %



Clay
60
wt %



Talc
37
wt %



Calcium stearate
1
wt %









The above ingredients were intimately mixed together to prepare dust.
Preparation Example 6
DL Dust
















Pyripyropene derivative (compound 277)
1
wt %



Fipronil
1
wt %



DL clay
94.5
wt %



White carbon
2
wt %



Calcium stearate
1
wt %



Light liquid paraffin
0.5
wt %









The above ingredients were intimately mixed together to prepare DL dust.
Preparation Example 7
Micro Granule Fine















Pyripyropene derivative (compound 261)
1 wt %



Flonicamid
1 wt %



Carrier
94 wt % 



White carbon
2 wt %



Hisol SAS-296
2 wt %









The above ingredients were intimately mixed together to prepare micro granule fine.
Preparation Example 8
Granules
















Pyripyropene derivative (compound 278)
2
wt %



Flonicamid
3
wt %



Bentonite
40
wt %



Talc
10
wt %



Clay
43
wt %



Calcium lignin sulfonate
2
wt %









The above ingredients were homogeneously ground and intimately mixed together. Water was added to the mixture, followed by thorough kneading. Thereafter, the kneaded product was granulated and dried to prepare granules.
Preparation Example 9
Microcapsules
















Pyripyropene derivative (compound 237)
2
wt %



Imidacloprid
3
wt %



Urethane resin
25
wt %



Emulsifying dispersant
5
wt %



Antiseptic
0.2
wt %



Water
64.8
wt %









The above ingredients were polymerized by interfacial polymerization to form a urethane resin film on the surface of pyripyropene derivative particles and imidacloprid particles and thus prepare microcapsules.
TEST EXAMPLES
Test Example 1
Pesticidal Effect Against Aphis gossypii (Part 1)
A leaf disk having a diameter of 2.0 cmφ was cut out from a cucumber grown in a pot and was placed in a 5.0 cm-Schale. Test admixture solutions, prepared by diluting the composition of the present invention with a 50% aqueous acetone solution (0.05% Tween 20 added) to predetermined concentrations specified in Table 18, test single active ingredient solutions in which only compound 261 had been dissolved without mixing other insecticides, or test single active ingredient solutions in which only other insecticides had been dissolved without mixing any pyripyropene derivative were spread over the cucumber leaf disk. The leaf disk was then air dried. Ten larvae at the first instar born of Aphis gossypii were released in the Schale. Thereafter, the Schale was lidded and was allowed to stand in a humidistat chamber (light period 16 hr-dark period 8 hr) (25° C.). Three days after the initiation of standing of the Schale, the larvae were observed for survival or death, and the death rate of larvae was calculated by the following equation. The results are shown in Table 18.

Death rate(%)={number of dead larvae/(number of survived larvae+number of dead larvae)}×100

Further, theoretical values, which do not exhibit a synergistic effect, were calculated by the following Colby's formula, and the results are shown in Table 19.

Colby's formula: Theoretical value(%)=100−(A×B)/100

wherein A: 100−(death rate when treatment was performed only with compound 261); and
B: 100−(death rate when treatment was performed only with each of flonicamid, acetamiprid, fipronil, imidacloprid)
Method for Determining Synergistic Effect
When the pesticidal effect (Table 18) of the composition of the present invention in, an admixture form against Aphis gossypii exceeded the theoretical value calculated by the Colby's formula shown in Table 19, the admixture was determined to have a synergistic effect.
All the tested admixtures had the death rate beyond the theoretical values, demonstrating that they had a synergistic effect.







TABLE 18







Death rate of Aphis gossypii by single active


ingredient or admixture (%)










Compound 261













Other insecticides

0 ppm
0.01 ppm















—

0
30












Flonicamid
0.078 ppm
10
60



Acetamiprid
0.078 ppm
58
100



Fipronil
0.078 ppm
0
63



Imidacloprid
0.078 ppm
20
95
















TABLE 19







Theoretical value calculated by Colby's formula (%)










Compound 261













Other insecticides

0 ppm
0.01 ppm















—

0
30












Flonicamid
0.078 ppm
10
37



Acetamiprid
0.078 ppm
58
71



Fipronil
0.078 ppm
0
30



Imidacloprid
0.078 ppm
20
44









Test Example 2
Pesticidal Effect Against Aphis gossypii (Part 2)
The same test as in Test Example 1 was performed, except that the other insecticides were changed to those specified in Table 20. The pesticidal effect and theoretical values were calculated, and the results are shown in Tables 20 and 21.
All the tested admixtures had the death rate beyond the theoretical values, demonstrating that they had a synergistic effect.







TABLE 20







Pesticidal effect against Aphis gossypii, death rate (%)










Compound 261













Other insecticides

0 ppm
0.01 ppm















—

0
53












Clothianidin
0.078 ppm
79
100



Thiamethoxam
0.078 ppm
65
90



Dinotefuran
0.078 ppm
40
75
















TABLE 21







Theoretical value calculated by Colby's formula (%)










Compound 261













Other insecticides

0 ppm
0.01 ppm















—

0
53












Clothianidin
0.078 ppm
79
90



Thiamethoxam
0.078 ppm
65
84



Dinotefuran
0.078 ppm
40
72









Test Example 3
Pesticidal Effect Against Plutella xylostella 
A leaf disk having a diameter of 5.0 cmφ was cut out from a cabbage grown in a pot and was placed in a plastic cup. Test admixture solutions, prepared by diluting the composition of the present invention with a 50% aqueous acetone solution (0.05% Tween 20 added) to predetermined concentrations specified in Table 22, test single active ingredient solutions in which only compound 261 had been dissolved without mixing other insecticides, or test single active ingredient solutions in which only other insecticides had been dissolved without mixing any pyripyropene derivative were spread over the cabbage leaf disk. The leaf disk was then air dried. Five larvae at the second instar born of Plutella xylostella were released in the cup. Thereafter, the cup was lidded and was allowed to stand in a humidistat chamber (light period 16 hr-dark period 8 hr) (25° C.). Three days after the initiation of standing of the cup, the larvae were observed for survival or death, and the death rate of larvae was calculated by the following equation. The results are shown in Table 22.

Death rate(%)={number of dead larvae/(number of survived larvae+number of dead larvae)}×100

The death rates are shown below.
Further, theoretical values, which do not exhibit a synergistic effect, were calculated by the following Colby's formula, and the results are shown in Table 23.

Colby's formula: Theoretical value(%)=100−(A×B)/100

wherein A: 100−(death rate when treatment was performed only with compound 261); and
B: 100−(death rate when treatment was performed only with each compound, i.e., A120, A190, or chlorfenapyr)
Method for Determining Synergistic Effect
When the pesticidal effect (Table 22) of the composition of the present invention in an admixture form against Plutella xylostella exceeded the theoretical value calculated by the Colby's formula shown in Table 23, the admixture was determined to have a synergistic effect.
All the tested admixtures had the death rate beyond the theoretical values, demonstrating that they had a synergistic effect.







TABLE 22







Pesticidal effect against Plutella xylostella, deathrate (%)









Compound 261









Other insecticides
0 ppm
10 ppm












—
0
0










Compound A120 (WO2006/013896)
0.156 ppm
10
50


Compound A190 (WO2006/013896)
0.313 ppm
0
20


Chlorfenapyr
0.156 ppm
0
20
















TABLE 23







Theoretical value calculated by Colby's formula (%)









Compound 261










Other insecticides

0 ppm
10 ppm












—
0
0










Compound A120 (WO2006/013896)
0.156 ppm
10
10


Compound A190 (WO2006/013896)
0.313 ppm
0
0


Chlorfenapyr
0.156 ppm
0
0

## Claims

1. A pest control composition comprising at least one pyripyropene derivative of formula (I) or an agriculturally and horticulturally acceptable salt thereof and at least one other pest control agent as active ingredients:



wherein

Het1 represents 3-pyridyl,
R1 represents hydroxyl,
R2 and R3 each represent —OCO-c-C3H5, and R4 represents hydroxyl, and
wherein the other pest control agent is selected from the group consisting of acetamiprid, imidacloprid, and a compound of formula (II):




wherein R101 represents methoxycarbonyl, R102 represents methyl, R103 represents ethyl, X101, Y101, Y102, Y104 and Y105 represent a hydrogen atom, X102 represents methyl, and Y103 represents OCF3 or OCF2CHF2, and
wherein the pest control composition comprises 0.1 to 80% by weight of the at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof and 0.1 to 80% by weight of the at least one other pest control agent.

2. The composition according to claim 1, which further comprises an agriculturally and horticulturally acceptable carrier.

3. The composition according to claim 1, which is a wettable powder comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of the other pest control agent selected from the group consisting of acetamiprid, imidacloprid and a compound of formula (II), 0.6 to 30% by weight of a wetting agent and a dispersant, and 20 to 95% by weight of an extender.

4. The composition according to claim 1, which is a water dispersible granule comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of the other pest control agent selected from the group consisting of acetamiprid, imidacloprid and a compound of formula (II), 0.6 to 30% by weight of a wetting agent, a dispersant, and a binder, and 20 to 95% by weight of an extender.

5. The composition according to claim 1, which is a flowable preparation comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of the other pest control agent selected from the group consisting of acetamiprid, imidacloprid and a compound of formula (II), 5 to 40% by weight of a dispersant, a thickening agent, an antifreezing agent, an antiseptic, and an antifoaming agent, and 20 to 94% by weight of water.

6. The composition according to claim 1, which is a emulsifiable concentrate comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of the other pest control agent selected from the group consisting of acetamiprid, imidacloprid and a compound of formula (II), 1 to 30% by weight of an emulsifier and an emulsion stabilizer, and 20 to 97% by weight of an organic solvent.

7. The composition according to claim 1, which is a micro granule fine comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of the other pest control agent selected from the group consisting of acetamiprid, imidacloprid and a compound of formula (II), 0.2 to 10% by weight of a solvent or a binder, and 70 to 99.6% by weight of an extender.

8. The composition according to claim 1, which is a granule comprising 0.1 to 80% by weight of the pyripyropene derivative of formula (I), 0.1 to 80% by weight of the other pest control agent selected from the group consisting of acetamiprid, imidacloprid and a compound of formula (II), 0.5 to 30% by weight of a granulation assistant and a binder, and 20 to 98% by weight of an extender.

9. A method for protecting useful plants from pests, comprising applying an effective amount of at least one pyripyropene derivative of formula (I) or agriculturally and horticulturally acceptable salt thereof




wherein
Het1 represents 3-pyridyl,
R1 represents hydroxyl,
R2 and R3 each represent —OCO-c-C3H5, and R4 represents hydroxyl, and at least one other pest control agent selected from the group consisting of acetamiprid, imidacloprid and a compound of formula (II),




wherein R101 represents methoxycarbonyl, R102 represents methyl, R103 represents ethyl, X101, Y101, Y102, Y104 and Y105 represent a hydrogen atom, X102 represents methyl, and Y103 represents OCF3 or OCF2CHF2, as active ingredients simultaneously or separately from each other to an area to be treated.

10. The method according to claim 9, wherein the ingredients are simultaneously applied to the area to be treated.

11. A method for protecting useful plants from pests, comprising treating an object pest, an object useful plant, or a seed, a soil, or a cultivation carrier of the object useful plant with the pest control composition according to claim 1.