# Patent

## Title
Pest control agents

## Abstract

Disclosed is a composition for use as a pest control agent, comprising a compound represented by formula (I) or an agriculturally and horticulturally acceptable salt thereof as active ingredient and an agriculturally and horticulturally acceptable carrier:

## Background
This is a divisional application of Ser. No. 12/318,232, filed Dec. 23, 2008 now U.S. Pat. No. 7,838,568 which is continuation of Ser. No. 11/443,299, filed May 31, 2006, now U.S. Pat. No. 7,491,738 which claims priority from provisional application No. 60/687,318, filed Jun. 6, 2005.


BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to a composition for use as a pest control agent comprising a pyripyropene derivative as active ingredient.
2. Background Art
Pyripyropene A has inhibitory activity against ACAT (acyl-CoA: cholesterol acyltransferase) and is expected to be applied, for example, to the treatment of diseases induced by cholesterol accumulation, as described in Japanese Patent No. 2993767 (Japanese Patent Laid-Open Publication No. 360895/1992) and Journal of Antibiotics (1993), 46(7), 1168-9.
Further, pyripyropene analogues and derivatives and ACAT inhibitory activity thereof are described in Journal of Society of Synthetic Organic Chemistry, Japan (1998), Vol. 56, No. 6, pp. 478-488, WO 94/09417, Japanese Patent Laid-Open Publication No. 184158/1994, Japanese Patent Laid-Open Publication No. 239385/1996, Japanese Patent Laid-Open Publication No. 259569/1996, Japanese Patent Laid-Open Publication No. 269062/1996, Japanese Patent Laid-Open Publication No. 269063/1996, Japanese Patent Laid-Open Publication No. 269064/1996, Japanese Patent Laid-Open Publication No. 269065/1996, Japanese Patent Laid-Open Publication No. 269066/1996, Japanese Patent Laid-Open Publication No. 291164/1996, and Journal of Antibiotics (1997), 50(3), 229-36.
Furthermore, Applied and Environmental Microbiology (1995), 61(12), 4429-35 describes that pyripyropene A has insecticidal activity against larvae of Helicoverpa zea. Furthermore, WO 2004/060065 describes that pyripyropene A has insecticidal activity against Plutella xylostella L larvae and Tenebrio molitor L. In these documents, however, there is no specific description on insecticidal activity of pyripyropene A against other pests.
Further, none of the above documents describes insecticidal activity of pyripyropene analogues and derivatives.
Up to now, many compounds having insecticidal activity have been reported and have been used as pest control agents. However, the presence of insect species, which are resistant to or can be hardly controlled by these compounds, has posed a problem. Accordingly, the development of a novel pest control agent having excellent insectidal activity has still been desired.
SUMMARY OF THE INVENTION
The present inventors have now found that pyripyropene derivatives represented by formula (I) have significant insecticidal activity.
The present inventors further found that pyripyropene A and its derivatives represented by formula (Ia) have significant insecticidal activity against hemipteran pests.
Furthermore, the present inventors have found novel pyripyropene derivatives represented by formula (Ib) having significant insecticidal activity.
The present invention has been made based on such finding.
Accordingly, an object of the present invention is to provide a composition useful as a pest control agent, that comprises a pyripyropene derivative having significant insecticidal activity as active ingredient and can reliably exhibit the contemplated effect and can be used safely. Another object of the present invention is to provide a hemipteran pest control agent that comprises pyripyropene A and its derivative as active ingredient and can reliably exhibit the contemplated effect and can be used safely. A further object of the present invention is to provide a novel pyripyropene derivative having significant insecticidal activity.
According to one aspect of the present invention, there is provided a composition for use as a pest control agent, comprising a compound represented by formula (I) or an agriculturally and horticulturally acceptable salt thereof as active ingredient and an agriculturally and horticulturally acceptable carrier:




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, provided that
            a compound wherein
            Het1 represents 3-pyridyl,
            R1 represents hydroxyl, and
            all of R2, R3, and R4 represent acetyloxy,

is excluded.

        
        
    
    


Further, according to another aspect of the present invention, there is provided a composition for use as a a hemipteran pest control agent, comprising a compound represented by formula (Ia) or an agriculturally and horticulturally acceptable salt thereof as active ingredient and an agriculturally and horticulturally acceptable carrier:




wherein

    
    
        Het2 represents optionally substituted 3-pyridyl,
        R11 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 R11 and a hydrogen atom at the 5-position,
        R12 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,
        
        
        R13 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
        
        
        R12 and R13 together represent —O—CR12′R13′—O— wherein R12′ and R13′, 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 R12′ and R13′ together represent oxo or C2-6 alkylene, and
        R14 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.
        
        
    
    


Further, the pyripyropene derivative according to the is present invention comprises a compound represented by formula (Ib) or an agriculturally and horticulturally acceptable salt thereof:




wherein

    
    
        Het1 represents 3-pyridyl,
        R1 represents hydroxyl,
        R2 and R3 represent propionyloxy or optionally substituted cyclic
        C3-6 alkylcarbonyloxy, and
        R4 represents hydroxyl,
        
            optionally substituted cyclic C3-6 alkylcarbonyloxy,
            optionally substituted benzoyloxy, or
            optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy.
        
        
    
    


The pyripyropene derivatives represented by formula (I) or formula (Ib) according to the present invention have excellent control effect against agricultural and horiticultural pests, sanitary pests, parasites of animals, stored grain pests, clothing pests, and house pests and a compositions comprising the pyripyropene derivatives as active ingredient can be advantageously utilized as a novel pest control agent.
Further, it is surprising that, among the compounds represented by formula (Ia), pyripyropene A has excellent control effect against hemipteran pests. Accordingly, a composition according to the present invention comprising the compounds represented by formula (Ia) including pyripyropene A, can be advantageously utilized particularly a hemipteran pest control agent.


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 used herein 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 and Het2 is optionally substituted, and substituents include halogen atoms, C1-4 alkyl, C1-4 alkyloxy, nitro, cyano, formyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, and acetyloxy. Preferred are halogen atoms and trifluoromethyl. A chlorine atom and trifluoromethyl are more preferred.
“C1-6 alkylcarbonyloxy” represented by R1 and R11 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.
“C1-18 alkylcarbonyloxy” represented by R2, R3 and R4, and R12, R13 and R14 is preferably C1-6 alkylcarbonyloxy, more preferably propionyloxy or cyclic C3-6 alkylcarbonyloxy. The C1-18 alkylcarbonyloxy group is optionally substituted, and substituents include halogen atoms, cyano, cyclic C3-6alkyl, phenyl, trifluoromethoxy, trifluoromethylthio, pyridyl, and pyridylthio. More preferred are halogen atoms, cyclic C3-6 alkyl, and pyridyl.
“C2-6 alkenylcarbonyloxy” represented by R1, R2, R3 and R4, and R11, R12, R13 and R14 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.
“C2-6 alkynylcarbonyloxy” represented by R1, R2, R3 and R4, and R11, R12, R13 and R14 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.
“C1-6 alkyloxy” represented by R1 and R4, and R11 and R14 is optionally substituted, and substituents include halogen atoms; cyano; phenyl; trifluoromethoxy; trifluoromethylthio; C1-6 alkylcarbonyl optionally substituted by a halogen atom; and C1-6 alkylcarbonyloxy optionally substituted by a halogen atom.
“C2-6 alkenyloxy” represented by R1 and R4, and R11 and R14 is optionally substituted, and substituents include halogen atoms; cyano; phenyl; trifluoromethoxy; trifluoromethylthio; C1-6 alkylcarbonyl optionally substituted by a halogen atom; and C1-6 alkylcarbonyloxy optionally substituted by a halogen atom.
“C2-6 alkynyloxy” represented by R1 and R4, and R11 and R14 is optionally substituted, and substituents include halogen atoms; cyano; phenyl; trifluoromethoxy; trifluoromethylthio; C1-6 alkylcarbonyl optionally substituted by a halogen atom; and C1-6 alkylcarbonyloxy optionally substituted by a halogen atom.
Phenyl in “benzyloxy” represented by R1 and R4, and R11 and R14 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; and group —CH═N—O—CH3.
Phenyl in “benzoyloxy” represented by R2, R3 and R4, and R12, R13 and R14 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; and group —CH═N—O—CH3. Preferred are halogen atoms, C1-6 alkyl substituted by a halogen atom, cyano, and nitro.
Phenyl in “benzenesulfonyloxy” represented by R3 and R4, and R13 and R14 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; and group —CH═N—O—CH3.
“C1-6 alkylsulfonyloxy” represented by R2, R3 and R4, and R12, R13 and R14 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.
“C1-6 alkyloxycarbonyloxy” represented by R4 and R14 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.
“C1-6 alkylaminocarbonyloxy” represented by R4 and R14 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.
“Phenyl” represented by R2′ and R3′, and R12′ and R13′ and phenyl in “benzyl” represented by R2′ and R3′, and R12′ and R13′ is optionally substituted, and substituents include halogen atoms, C1-4 alkyl, C1-4 alkyloxy, nitro, cyano, formyl, trifluoromethoxy, acetyl, and acetyloxy.
“Saturated or unsaturated five- or six-membered heterocyclic ring” in “saturated or unsaturated five- or six-membered heterocyclic thiocarbonyloxy” represented by R3 and R13, 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 and R14, is preferably, saturated or unsaturated five- or six-membered heterocyclic ring containing one to three heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, more preferably, saturated or unsaturated five- or six-membered heterocyclic ring containing one or two heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, more preferably, saturated or unsaturated five- or six-membered heterocyclic ring containing one or two nitrogen atoms, saturated or unsaturated five- or six-membered heterocyclic ring containing one or two oxygen atoms, saturated or unsaturated five- or six-membered heterocyclic ring containing one or two sulfur atoms, saturated or unsaturated five- or six-membered heterocyclic ring containing one nitrogen atom and one oxygen atom, or saturated or unsaturated five- or six-membered heterocyclic ring containing one nitrogen atom and one sulfur atom.
More specifically, examples of the “saturated or unsaturated five- or six-membered heterocyclic ring” include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazoyl, isoxazolyl, thiazolyl, oxazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, tetrahydropyranyl, piperidinyl, piperazinyl, morpholinyl, and 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, and 2-tetrahydropyranyl, more preferably 2-tetrahydropyranyl, 2-pyrazinyl, and 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 and R14 are optionally substituted, and substituents include halogen atoms, C1-4 alkyl, C1-4 alkyloxy, C1-4 alkylthio, nitro, cyano, formyl, trifluoromethoxy, trifluoromethyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, acetyloxy, benzoyl, and 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, trifluoromethoxy, trifluoromethyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, and acetyloxy. Preferred are hydroxyl and benzyloxy.
A Composition for Use as a Pest Control Agent, Comprising a Compound Represented by Formula (I)
According to a preferred embodiment of the present invention, in the compound represented by formula (I), preferably, Het1 represents 3-pyridyl.
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (I), 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.
According to a preferred embodiment of the present invention, in the compound represented by 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 straight chain or branched chain C1-6 alkylcarbonyloxy (particularly propionyloxy) or optionally substituted cyclic C3-6 alkylcarbonyloxy.
In a preferred embodiment of the present invention, in the compound represented by 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 straight chain or branched chain C2-4 alkylcarbonyloxy (particularly propionyloxy) or optionally substituted cyclic C3-6 alkylcarbonyloxy.
According to a preferred embodiment of the present invention, in the compound represented by 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.
According to a preferred embodiment of the present invention, in the compound represented by 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 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 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 hydroxyl, straight chain or branched chain C2-4 alkylcarbonyloxy (particularly propionyloxy), optionally substituted cyclic C3-6 alkylcarbonyloxy, or optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy.
According to another preferred embodiment of the present invention, in the compound represented by 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—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, and R4 represents 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.
According to another preferred embodiment of the present invention, in the compound represented by 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 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.
According to another preferred embodiment of the present invention, in the compound represented by 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 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.
According to another preferred embodiment of the present invention, in the compound represented by formula (I), Het1 represents 3-pyridyl, R1 represents hydroxyl, and R2 and R3 represent optionally substituted cyclic C3-6 alkylcarbonyloxy.
According to another preferred embodiment of the present invention, in the compound represented by formula (I),

    
    
        Het1 represents 3-pyridyl,
        R1 represents hydroxyl or
        
            optionally substituted 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 C1-18 alkylcarbonyloxy or
        
            optionally substituted benzoyloxy,
        
        
        R3 represents optionally substituted C1-18 alkylcarbonyloxy or
        
            optionally substituted C1-6 alkylsulfonyloxy, and
        
        
        R4 represents hydroxyl,
        
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted C2-6 alkenylcarbonyloxy,
            optionally substituted benzoyloxy,
            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, or
            oxo in the absence of a hydrogen atom at the 7-position.
        
        
    
    


According to another preferred embodiment of the present invention, in the compound represented by formula (I),

    
    
        Het1 represents 3-pyridyl,
        R1 represents hydroxyl or
        
            optionally substituted 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 C1-18 alkylcarbonyloxy,
        R3 represents optionally substituted C1-18 alkylcarbonyloxy or
        
            optionally substituted C1-6 alkylsulfonyloxy, and
        
        
        R4 represents hydroxyl,
        
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted C2-6 alkenylcarbonyloxy,
            optionally substituted benzoyloxy,
            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, or
            oxo in the absence of a hydrogen atom at the 7-position.
        
        
    
    


According to another preferred embodiment of the present invention, in the compound represented by formula (I),

    
    
        Het1 represents 3-pyridyl,
        R1 represents hydroxyl or
        
            optionally substituted 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 C1-18 alkylcarbonyloxy,
        R3 represents optionally substituted C1-18 alkylcarbonyloxy,
        R4 represents hydroxyl,
        
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted benzoyloxy,
            optionally substituted saturated or unsaturated five- or six-membered heterocyclic oxy, or
            optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy.
        
        
    
    


According to another preferred embodiment of the present invention, in the compound represented by formula (I), Het1 represents 3-pyridyl, R1 represents hydroxyl, R2 represents C1-6 alkylcarbonyloxy, and R3 and/or R4 represent C2-4 alkylcarbonyloxy.
Further, an agriculturally and horticulturally acceptable salt of the compound represented by formula (I) include the same as that of the compound represented by formula (Ib) described below.
A Composition for Use as a Hemipteran Pest Control Agent, Comprising a Compound Represented by Formula (Ia)
According to a preferred embodiment of the present invention, in the compound represented by formula (Ia), preferably, Het2 represents 3-pyridyl.
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (Ia), R11 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 R11 and a hydrogen atom at the 5-position. More preferably, R11 represents hydroxyl or C1-6 alkylcarbonyloxy, or the bond between 5-position and 13-position represents a double bond in the absence of R11 and a hydrogen atom at the 5-position, still more preferably R11 represents hydroxyl.
According to a preferred embodiment of the present invention, in the compound represented by formula (Ia), R12 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 straight chain or branched chain C1-6 alkylcarbonyloxy (particularly propionyloxy) or optionally substituted cyclic C3-6 alkylcarbonyloxy.
In a preferred embodiment of the present invention, in the compound represented by formula (Ia), R13 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 straight chain or branched chain C2-4 alkylcarbonyloxy (particularly propionyloxy) or optionally substituted cyclic C3-6 alkylcarbonyloxy.
According to a preferred embodiment of the present invention, in the compound represented by formula (Ia), R12 and R13 together represent —O—CR12′R13′—O—, wherein R12′ and R13′, 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 R12′ and R13′ together represent oxo or C2-6 alkylene. More preferably, R12 and R13 together represent —O—CR12′R13′—O—, wherein R12′ and R13′, which may be the same or different, represent a hydrogen atom, C1-6 alkyl, or optionally substituted phenyl, or R12′ and R13′ together represent oxo or C2-6 alkylene.
According to a preferred embodiment of the present invention, in the compound represented by formula (Ia), R14 represents a hydrogen atom, hydroxyl, optionally substituted C1-16 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, R14 represents hydroxyl, optionally substituted C1-6 alkylcarbonyloxy, optionally substituted benzoyloxy, saturated or unsaturated five- or six-membered heterocyclic oxy, 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, R14 represents 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, R14 represents straight chain or branched chain C2-4 alkylcarbonyloxy (particularly propionyloxy), optionally substituted cyclic C3-6 alkylcarbonyloxy, or optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy.
According to another preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents 3-pyridyl, R11 represents hydroxyl or C1-6 alkylcarbonyloxy, or the bond between 5-position and 13-position represents a double bond in the absence of R11 and a hydrogen atom at the 5-position, R12 represents optionally substituted C1-6 alkylcarbonyloxy, R13 represents optionally substituted C1-6 alkylcarbonyloxy or C1-6 alkylsulfonyloxy, or R12 and R13 together represent —O—CR12′R13′—O— wherein R12′ and R13′, which may be the same or different, represent a hydrogen atom, C1-6 alkyl, or optionally substituted phenyl, or R12′ and R13′ together represent oxo or C2-6 alkylene, and R14 represents 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.
According to another preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents 3-pyridyl, R11 represents hydroxyl, R12 represents optionally substituted C1-6 alkylcarbonyloxy, and R13 represents optionally substituted C1-6 alkylcarbonyloxy or C1-6 alkylsulfonyloxy, and R14 represents 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.
According to another preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents 3-pyridyl, R11 represents hydroxyl, R12 represents optionally substituted C1-6 alkylcarbonyloxy, R13 represents optionally substituted C1-6 alkylcarbonyloxy or C1-6 alkylsulfonyloxy, and R14 represents 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.
According to another preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents 3-pyridyl, R11 represents hydroxyl, and R12 and R13 represent optionally substituted cyclic C3-6 alkylcarbonyloxy.
According to another preferred embodiment of the present invention, in the compound represented by formula (Ia),

    
    
        Het2 represents 3-pyridyl,
        R11 represents hydroxyl or
        
            optionally substituted C1-6 alkylcarbonyloxy, or
        
        
        the bond between 5-position and 13-position represents a double bond in the absence of R11 and a hydrogen atom at the 5-position,
        R12 represents optionally substituted C1-18 alkylcarbonyloxy or
        
            optionally substituted benzoyloxy,
        
        
        R13 represents optionally substituted C1-18 alkylcarbonyloxy or
        
            optionally substituted C1-6 alkylsulfonyloxy, and
        
        
        R14 represents hydroxyl,
        
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted C2-6 alkenylcarbonyloxy,
            optionally substituted benzoyloxy,
            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, or
            oxo in the absence of a hydrogen atom at the 7-position.
        
        
    
    


According to another preferred embodiment of the present invention, in the compound represented by formula (Ia),

    
    
        Het2 represents 3-pyridyl,
        R11 represents hydroxyl or
        
            optionally substituted C1-6 alkylcarbonyloxy, or
        
        
        the bond between 5-position and 13-position represents a double bond in the absence of R11 and a hydrogen atom at the 5-position,
        R12 represents optionally substituted C1-18 alkylcarbonyloxy,
        R13 represents optionally substituted C1-18 alkylcarbonyloxy or
        
            optionally substituted C1-6 alkylsulfonyloxy, and
        
        
        R14 represents hydroxyl,
        
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted C2-6 alkenylcarbonyloxy,
            optionally substituted benzoyloxy,
            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, or
            oxo in the absence of a hydrogen atom at the 7-position.
        
        
    
    


According to another preferred embodiment of the present invention, in the compound represented by formula (Ia),

    
    
        Het2 represents 3-pyridyl,
        R11 represents hydroxyl or
        
            optionally substituted C1-6 alkylcarbonyloxy, or
        
        
        the bond between 5-position and 13-position represents a double bond in the absence of R11 and a hydrogen atom at the 5-position,
        R12 represents optionally substituted C1-18 alkylcarbonyloxy,
        R13 represents optionally substituted C1-18 alkylcarbonyloxy,
        R14 represents hydroxyl,
        
            optionally substituted C1-18 alkylcarbonyloxy,
            optionally substituted benzoyloxy,
            optionally substituted saturated or unsaturated five- or six-membered heterocyclic oxy, or
            optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy.
        
        
    
    


According to another preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents 3-pyridyl, R11 represents hydroxyl, R12 represents C1-6 alkylcarbonyloxy, and R13 and/or R14 represent C2-4 alkylcarbonyloxy.
Further, an agriculturally and horticulturally acceptable salt of the compound represented by formula (Ia) include the same as that of the compound represented by formula (Ib) described below.
Compounds of Formula (Ib) or its Agriculturally and Horticulturally Acceptable Salts
Compounds of formula (Ib) are novel pyripyropene derivatives that are comprised as a part in the compound represented by formula (I). In particular, they have significant insecticidal activity.
According to an embodiment of the present invention, there is provided the compounds of formula (Ib), excluding a compound wherein Het1 represents 3-pyridyl, R1 represents hydroxyl, and R2 and R3 represent propionyloxy, and R4 represents hydroxyl.
According to another preferred embodiment of the present invention, in the compound represented by formula (Ib), R2 and R3 represent optionally substituted cyclic C3-6 alkylcarbonyloxy, R4 represents hydroxyl, optionally substituted cyclic C3-6 alkylcarbonyloxy, or optionally substituted benzoyloxy. Alternatively, R2 and R3 represent propionyloxy, R4 represents optionally substituted cyclic C3-6 alkylcarbonyloxy, or optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy.
According to another preferred embodiment of the present invention, in the compounds represented by formula (Ib), R2 and R3 represent optionally substituted cyclic C3-6 alkylcarbonyloxy, R4 represents hydroxyl, optionally substituted cyclic C3-6 alkylcarbonyloxy, or optionally substituted benzoyloxy.
According to another preferred embodiment of the present invention, in the compounds represented by formula (Ib), R2 and R3 represent propionyloxy, R4 represents optionally substituted cyclic C3-6 alkylcarbonyloxy or optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy.
According to still another preferred embodiment of the present invention, there is provided a pest control agent comprising a compound represented by formula (Ib) or an agriculturally and horticulturally acceptable salt thereof as an active ingredient.
Agriculturally and horticulturally acceptable salts in the compounds of formula (Ib) include, for example, acid addition salts such as hydrochlorides, nitrates, sulfates, phosphates, or acetates.
Specific examples of the compounds represented by formula (I), (Ia), or (Ib) include compounds shown in Tables 1 to 14 below. 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-
3-pyridyl






CH═CHCH2CH3


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-(1-
OCOCH3
3-pyridyl





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


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


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






pyridyl)



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






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-
3-pyridyl






pyridyl)



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






pyridyl)



231
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3-
3-pyridyl






OCH2CH2CH3-2-







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



c-C3H5
C3H5





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




C3H5





238
OH
OCO-(1-CH3-
OCO-(1-CH3-2,2-
OCO-(1-CH3-2,2-diF-
3-pyridyl




2,2-diF-c-C3H2)
diF-c-C3H2)
c-C3H2)



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






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-
3-pyridyl






pyridyl)



242
OH
OCOCH2CH3
OCOCH2CH3
OCO-[5-(CF3)-
3-pyridyl






thieno[3,2-b]pyridin-6-yl]



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-
3-pyridyl






pyridyl)



249
OH
OCOCH2CH3
OCOCH2CH3
OCH2OCH3
3-pyridyl


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




c-C3H3)





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






pyridyl)



252
OH
OCOCH2CH3
OCOCH2CH3
OCO-(3,5-diF-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-
3-pyridyl






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-
3-pyridyl






pyridyl)



267
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2(3-
3-pyridyl






pyridyl)



268
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2S(4-
3-pyridyl






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-
3-pyridyl






pyridyl)



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






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









Production Process
The composition according to the present invention can be prepared by mixing the compound represented by formula (I), (Ia), or (Ib) as active ingredient with an agriculturally and horticulturally acceptable carrier. The compound represented by formula (I), (Ia), or (Ib) according to the present invention can be produced according to the following procedure.
Among the compounds according to the present invention, the compounds represented by formula (II) can be synthesized by the method described in Japanese Patent Laid-Open Publication No. 259569/1996, Japanese Patent Laid-Open Publication No. 269062/1996, Japanese Patent Laid-Open Publication No. 269065/1996, or Journal of Antibiotics (1997), 50(3), pp. 229-36. When pyripyropene A is used as a starting material, pyripyropene A, produced by the method described in Journal of Society of Synthetic Organic Chemistry, Japan (1998), Vol. 56, No. 6, pp. 478-488 or WO 94/09417, may be used as the starting material.




wherein

    
    
        R1 represents hydroxyl, optionally substituted C1-6 alkylcarbonyloxy, optionally substituted C2-6 alkenylcarbonyloxy, optionally substituted C2-6 alkynyl carbonyloxy, 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, and
    
    


R2, R3 and R4 are as defined in formula (I).
Further, among the compounds according to the present invention, the compounds represented by formula (III) can be synthesized by the method described in Japanese Patent Laid-Open Publication No. 269063/1996, or Japanese Patent Laid-Open Publication No. 269066/1996.




wherein R2, R3 and R4 are as defined in formula (I).
Use
Insect species against which pyripyropene derivatives of formula (I) or (Ib) according to the present invention have control effect include: lepidopteran pests, for example, Spodoptera litura, Mamestra brassicae, Pseudaletia separata, green caterpillar, Plutella xylostella, Spodoptera exigua, Chilo suppressalis, Cnaphalocrocis medinalis, Tortricidae, Carposinidae, Lyonetiidae, Lymantriidae, pests belonging to the genus Agrotis spp., pests belonging to the genus Helicoverpa spp., and pests belonging to the genus Heliothis spp.; hemipteran pests, for example, Aphidoidea including Aphididae, Adelgidae and Phylloxeridae such as 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, 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 coelestialium; Aleyrodidae such as Bemisia argentifolii, Bemisia tabaci, and Trialeurodes vaporariorum; Diaspididae, Margarodidae, Ortheziidae, Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae, Eriococcidae, Asterolecaniidae, Beesonidae, Lecanodiaspididae, or Cerococcidae, such as Pseudococcus comstocki and Planococcus citri Rissoz; Coleoptera 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, Carposinidae, and Cerambycidae; Acari, for example, Tetranychus urticae, Tetranychus kanzawai, and Panonychus citri; Hymenopteran pests, for example, Tenthredinidae; Orthopteran pests, for example, Acrididae; Dipteran pests, for example, Muscidae and Agromyzidae; Thysanopteran pests, for example, Thrips palmi and Frankliniella occidentalis; Plant Parasitic Nematodes, for example, Meloidogyne hapla, Pratylenchus spp., Aphelenchoides besseyi and Bursaphelenchus xylophilus; and parasites of animals, for example, Siphonaptera, Anoplura, mites such as Boophilus microplus, Haemaphysalis longicornis, Rhipicephalus sanguineus, and Scarcoptes scabiei. Preferred are hemipteran pests.
The compound represented by formula (Ia) accordingly to the present invention has significant control effect against hemipteran pests. Preferred hemipteran pests are selected from Aphidoidea such as Aphididae, Adelgidae, and Phylloxeridae, particularly preferably Aphididae; Coccoidea such as Diaspididae, Margarodidae, Ortheziidae, Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae, Eriococcidae, Asterolecaniidae, Beesonidae, Lecanodiaspididae, and Cerococcidae; and 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, and Pseudococcus comstocki. 
The composition according to the present invention can be prescribed in any suitable formulation, such as emulsifiable concentrates, liquid formulations, suspension, wettable powder, flowables, dust, granules, tablets, oil solutions, aerosols, or smoking agents by using suitable agriculturally and horticulturally acceptable carriers. Accordingly, the carrier include solid carriers, liquid carriers, gaseous carriers, surfactants, dispersants and/or other adjuvants for formulations, and the like.
Solid carriers usable herein include, for example, talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, and calcium carbonate.
Examples of liquid carriers include: 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, alkylsulfonic 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 adjuvant may be used either solely or in combination according to need.
The content of the active ingredient in the formulation is not particularly limited. In general, however, the content of the active ingredient is 1 to 75% by weight for emulsifiable concentrates, 0.3 to 25% by weight for dust, 1 to 90% by weight for wettable powder, and 0.5 to 10% by weight for granules.
The compound represented by formula (I), (Ia), (Ib), or an agriculturally and horticulturally acceptable salt thereof and the above formulations comprising the same may be applied as such or after dilution to plants or soil. Therefore, according to another aspect of the present invention, there is provided a method for controlling a pest, comprising applying an effective amount of a compound represented by formula (I) or an agriculturally and horticulturally acceptable salt thereof to a plant or soil. According to still another aspect of the present invention, there is provided a method for controlling a hemipteran pest, comprising applying an effective amount of a compound represented by formula (Ia) or an agriculturally and horticulturally acceptable salt thereof to a plant or soil. According to a further aspect of the present invention, there is provided a method for controlling a pest, comprising applying an effective amount of a compound represented by formula (Ib) or an agriculturally and horticulturally acceptable salt thereof to a plant or soil. Preferred methods usable for applying the compound or formulation to plants or soil include spreading treatment, soil treatment, surface treatment, and fumigation treatment.
Spreading treatments include, for example, spreading, spraying, misting, atomizing, granule application, and submerged application. Soil treatments include, for example, soil affusion and soil mixing. Examples of surface treatments include, for example, coating, dust coating, and covering. Fumigation treatments include, for example, covering of soil with a polyethylene film after soil injection. Accordingly, the control method according to the present invention comprises a method in which the compound represented by formula (I), (Ia), or (Ib) or a formulation comprising the same is applied by fumigation in a sealed space.
The composition according to the present invention may be used as a mixture or in a combination with, for example, other insecticides, fungicides, miticides, herbicides, plant growth-regulating agents, or fertilizers. Agents which may be mixed or used in combination include those described, for example, in The Pesticide Manual, 13th edition, published by The British Crop Protection Council; and SHIBUYA INDEX, the 10th edition, 2005, published by SHIBUYA INDEX RESEARCH GROUP. More specifically, insecticides usable herein include, for example, organophosphate ester compounds such as acephate, dichlorvos, EPN, fenitrothion, fenamifos, prothiofos, profenofos, pyraclofos, chlorpyrifos-methyl, and diazinon; carbamate compounds such as methomyl, thiodicarb, aldicarb, oxamyl, propoxur, carbaryl, fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran, and benfuracarb; nereistoxin derivatives such as cartap and thiocyclam; organochlorine compounds such as dicofol and tetradifon; pyrethroid compounds such as permethrin, tefluthrin, cypermethrin, deltamethrin, cyhalothrin, fenvalerate, fluvalinate, ethofenprox, and silafluofen; benzoylurea compounds such as diflubenzuron, teflubenzuron, flufenoxuron, and chlorfluazuron; juvenile hormone-like compounds such as methoprene; and molting hormone-like compounds such as chromafenozide. Other compounds usable herein include buprofezin, hexythiazox, amitraz, chlordimeform, pyridaben, fenpyroxymate, pyrimidifen, tebufenpyrad, fluacrypyrim, acequinocyl, cyflumetofen, flubendiamide, ethiprole, fipronil, ethoxazole, imidacloprid, chlothianidin, pymetrozine, bifenazate, spirodiclofen, spiromesifen, flonicamid, chlorfenapyr, pyriproxyfene, indoxacarb, pyridalyl, or spinosad, avermectin, milbemycin, organometallic compounds, dinitro compounds, organosulfur compounds, urea compounds, triazine compounds, hydrazine compounds.
The composition according to the present invention may also be used as a mixture or in a combination with microbial pesticides such as BT formulations and entomopathogenic viral agents.
Fungicides usable herein include, for example, strobilurin compounds such as azoxystrobin, kresoxym-methyl, and trifloxystrobin; 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, ofurace, benalaxyl, furalaxyl, and cyprofuram; sulfenic acid compounds such as dichlofluanid; 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; dicarboxyimide 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 compounds usable herein include fthalide, fluazinam, cymoxanil, triforine, pyrifenox, fenarimol, fenpropidin, pencycuron, cyazofamid, iprovalicarb, and benthiavalicarb-isopropyl and the like.
According to another aspect of the present invention, there is provided use of a compound represented by formula (I) or an agriculturally and horticulturally acceptable salt thereof as a pest control agent. According to still another aspect of the present invention, there is provided use of a compound represented by formula (Ia) or an agriculturally and horticulturally acceptable salt thereof as a hemipteran pest control agent. According to still another aspect of the present invention, there is provided use of a compound represented by formula (Ib) or an agriculturally and horticulturally acceptable salt thereof as a pest control agent.
EXAMPLES
The present invention is further illustrated by the following Examples that are not intended as a limitation of the invention. The compound Nos. correspond to the compound Nos. in Tables 1 to 14.
Example 1
Synthesis of Compound 73
Compound 76 (890 mg) synthesized by the method described in Japanese Patent Laid-Open Publication No. 259569/1996 was dissolved in an 80% aqueous methanol solution. Next, 1,8-diazabicyclo[5.4.0]-undeca-7-ene (216 mg) was added to the solution, and the mixture was stirred at room temperature for 1.5 hr. The reaction mixture was added with acetic acid to quench the reaction, and the solvent was removed by evaporation under the reduced pressure. Water was added to the precipitated crystal, followed by extraction with chloroform. The chloroform layer was washed with saturated brine, was dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation under the reduced pressure to give a crude product of compound 73. The crude product was purified by chromatography on silica gel (Mega Bond Elut (Varian), acetone:hexane=1:1) to give compound 73 (451 mg).
Mass spectrometric data (FAB+): 570(M+H)+
Example 2
Synthesis of Compound 218
Compound 102 (30 mg) synthesized by the method described in Japanese Patent Laid-Open Publication No. 259569/1996 and cyclopropanecarboxylic acid (112 mg) were dissolved in anhydrous N,N-dimethylformamide (2 ml), and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (76 mg) and 4-(dimethylamino)pyridine (32 mg) were added to the solution. The reaction solution was stirred at room temperature for 68 hr and was then poured into water, followed by extraction with ethyl acetate. The ethyl acetate layer was washed with saturated brine and was dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation under the reduced pressure to give a crude product of compound 218. The crude product was purified by preparative thin-layer chromatography (Merck Silica Gel 60 F254 0.5 mm, acetone:hexane=1:1) to give compound 218 (33 mg).
Mass spectrometric data (FAB+): 662(M+H)+
Example 3
Synthesis of Compound 261
Compound 218 (1.07 g) prepared in Example 2 was dissolved in an 80% aqueous methanol solution. 1,8-Diazabicyclo[5.4.0]-undeca-7-ene (271 mg) was added to the solution, and the mixture was stirred at room temperature for 24.5 hr. The reaction mixture was added with acetic acid to quench the reaction, and the solvent was removed by evaporation under the reduced pressure. Water was added to the precipitated crystal, followed by extraction with chloroform. The chloroform layer was washed with saturated brine and was dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation under the reduced pressure to give a crude product of compound 261. The crude product was purified by chromatography on silica gel (Mega Bond Elut (Varian), acetone:hexane=1:1) to give compound 261 (233 mg).
Mass spectrometric data (ESI+): 594(M+H)+
Example 4
Synthesis of Compound 222
Compound 73 (30 mg) prepared in Example 1 and 4-(trifluoromethyl)nicotinic acid (30 mg) was dissolved in anhydrous N,N-dimethylformamide (3 ml). Next, 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (15 mg) and 4-(dimethylamino)pyridine (4 mg) were added to the solution, and the reaction solution was stirred at room temperature for 15 hr and was then poured into water, followed by extraction with ethyl acetate. The ethyl acetate layer was washed with saturated brine and was dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation under the reduced pressure to give a crude produce of compound 222. The crude product was purified by preparative thin-layer chromatography (Merck Silica Gel 60 F254 0.5 mm, acetone:hexane=1:1) to give compound 222 (19 mg).
Mass spectrometric data (FAB+): 743(M+H)+
Example 5
Synthesis of Compound 269
Compound 261 (20 mg) prepared in Example 3 and 2-cyanobenzoic acid (30 mg) were dissolved in anhydrous N,N-dimethylformamide (1 ml), and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (26 mg) and 4-(dimethylamino)pyridine (4 mg) were added to the solution. The reaction solution was stirred at room temperature for 12 hr, and the reaction solution was added to water, followed by extraction with ethyl acetate. The ethyl acetate layer was washed with saturated brine and was dried over anhydrous magnesium sulfate. The solvent was removed by evaporation under the reduced pressure to give a crude product of compound 269. The crude product was purified by preparative thin-layer chromatography (Merck Silica Gel 60 F254 0.5 mm, acetone:hexane=1:1) to give compound 269 (18 mg).
Mass spectrometric data (ESI+): 723 (M+H)+
Example 6
Synthesis of Compound 225
1,7,11-Trideacetyl-13-oxo-6′′-chloropyripyropene A (10 mg) described in Journal of Antibiotics (1997), 50 (3), 229-36 was dissolved in anhydrous N,N-dimethylformamide (1 ml). Triethylamine (24 mg) and 4-(dimethylamino)pyridine (0.5 mg) were added to the solution, and the mixture was stirred at room temperature for 30 min. Thereafter, propionic acid anhydride (8 mg) was added. The reaction solution was stirred at the same temperature for 4 hr. The reaction solution was added to water, 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 to give a crude product of compound 225. The crude product was purified by preparative thin-layer chromatography (Merck Silica Gel 60 F254 0.5 mm, acetone:hexane=1:1) to give compound 225 (5.6 mg).
Mass spectrometric data (ESI+): 658 (M+H)+
Example 7
Synthesis of Compound 226
Compound 225 (10 mg) prepared in Example 6 was dissolved in methanol (1 ml). Cerium(III) chloride heptahydrate (57 mg) and sodium borohydride (6 mg) were added to the solution. The mixture was stirred at 0° C. for 7 hr, and water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate layer was washed with saturated brine and was dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation under the reduced pressure to give a crude product of compound 226. The crude product was purified by preparative thin-layer chromatography (Merck Silica Gel 60 F254 0.5 mm, acetone:hexane=1:1) to give compound 226 (8.5 mg).
Mass spectrometric data (ESI+): 660 (M+H)+
Example 8
Synthesis of Compound 273
1,7,11-Trideacetyl-1,11-o-p-methoxybenzylidene pyripyropene A (10 mg) described in Japanese Patent Laid-Open Publication No. 269065/1996 was dissolved in anhydrous dichloromethane (0.5 ml), and pyridinium dichromate (PDC) (39 mg) was added to the solution. The reaction solution was stirred at room temperature for 4 hr, and the reaction solution was added to water. The dichloromethane layer was washed with saturated brine, and was dried over anhydrous sodium sulfate, and the solvent was then removed by evaporation under the reduced pressure to give a crude product of compound 273. The crude product was purified by preparative thin-layer chromatography (Merck Silica Gel 60 F254 0.5 mm, chloroform:methanol=12.5:1) to give compound 273 (4.4 mg).
Mass spectrometric data (ESI4): 574 (M+H)+
Example 9
Synthesis of Compound 274
1,11-o-Cyclic carbonate1,7,11-trideacetyl-pyripyropene A (4 mg) described in Japanese Patent Laid-Open Publication No. 269065/1996 was dissolved in anhydrous dichloromethane (1 ml). Triethylamine (5 μl) and 4-(dimethylamino)pyridine (1 mg) were added to the solution. The reaction solution was stirred at room temperature for 30 min, and valeric acid anhydride (5 μl) was added thereto. Next, the reaction solution was stirred at room temperature for 3 hr. The reaction solution was added to water, and the dichloromethane layer was washed with saturated brine and was dried over anhydrous sodium sulfate. The solvent was then removed by evaporation under the reduced pressure to give a crude product of compound 274. The crude product was purified by preparative thin-layer chromatography (Merck Silica Gel 60 F254 0.5 mm, chloroform:methanol=25:1) to give compound 274 (0.1 mg).
Mass spectrometric data (ESI+): 652 (M+H)+
Example 10
Compounds shown in Tables 15 to 17 were synthesized using starting materials, reaction reagents 1 and 2 and solvents described in these tables. Further, the 1H-NMR data about some of the compounds in Tables 15 to 17 was described in Tables 18 to 29. In addition, CDCl3 was used as the solvent for the 1H-NMR measurement. Tetramethylsilane was used as a standard substance for the 1H-NMR measurement.










TABLE 15








Starting

Mass 



material

spectrometric data
















Compound
(Compound






Measuring



No.
No.)
Amount
Reaction reagent 1
Amount
Reaction reagent 2
Solvent
Yield
Method
Data



















74
73
30 mg
acetic anhydride
32.7 mg
Et3N 64.0 mg,
DMF
13.6 mg
FAB
612 (M + H)+







DMAP 12.8 mg






77
73
30 mg
benzoic acid
84.8 mg
EDCI 49.2 mg,
DMF
36.4 mg
FAB
674 (M + H)+







DMAP 46.4 mg






91
102
30 mg
pivalic anhydride
 220 mg
Et3N 60.0 mg,
DMF
27.7 mg
FAB
710 (M + H)+







DMAP 8.0 mg






205
73
30 mg
nicotinic acid
12.9 mg
EDCI 15.1 mg,
DMF
27.1 mg
FAB
675 (M + H)+







DMAP 6.4 mg






206
73
30 mg
isobutyric anhydride
50.0 mg
Et3N 64.0 mg,
DMF
11.4 mg
FAB
640 (M + H)+







DMAP 12.8 mg






207
73
30 mg
pivalic anhydride
58.9 mg
Et3N 64.0 mg,
DMF
23.4 mg
FAB
654 (M + H)+







DMAP 12.8 mg






208
73
30 mg
4-(trifluoromethyl)benzoic
 114 mg
Et3N 64.0 mg,
DMF
32.2 mg
FAB
742 (M + H)+





anhydride

DMAP 12.8 mg






209
73
40 mg
1,1-carbonyl diimidazole
34.0 mg
—
toluene
 5.1 mg
FAB
664 (M + H)+


210
73
30 mg
propyl isocyanate
26.9 mg
Et3N 64.0 mg,
DMF
 3.2 mg
FAB
655 (M + H)+







DMAP 12.8 mg






211
73
30 mg
3,4-dihydro-2H-pyran
 155 mg
pyridine hydrochloride
CH2Cl2
22.7 mg
FAB
654 (M + H)+


212
73
30 mg
6-chloro nicotinic acid
16.5 mg
EDCI 15.2 mg,
DMF
39.8 mg
FAB
709 (M + H)+







DMAP 6.4 mg






213
73
30 mg
cyclopropane carboxylic acid
  27 mg
EDCI 15.2 mg,
DMF
18.2 mg
FAB
638 (M + H)+







DMAP 6.4 mg






214
73
30 mg
cyclobutane carboxylic acid
  31 mg
EDCI 15.2 mg,
DMF
14.9 mg
FAB
652 (M + H)+







DMAP 6.4 mg






215
73
30 mg
acrylic acid
22.5 mg
EDCI 15.2 mg,
DMF
 5.6 mg
FAB
624 (M + H)+







DMAP 6.4 mg






216
73
30 mg
isonicotinic acid
12.9 mg
EDCI 15.2 mg,
DMF
 8.2 mg
FAB
675 (M + H)+







DMAP 6.4 mg






217
73
30 mg
picolinic acid
12.9 mg
EDCI 15.2 mg,
DMF
40.6 mg
FAB
675 (M + H)+







DMAP 6.4 mg






219
102
30 mg
cyclobutane carboxylic acid
 131 mg
EDCI 76 mg,
DMF
38.9 mg
FAB
704 (M + H)+







DMAP 32 mg






220
102
30 mg
benzoic acid
 160 mg
EDCI 126 mg,
DMF
37.9 mg
FAB
770 (M + H)+







DMAP 80 mg






221
73
30 mg
6-(trifluoromethyl)nicotinic
  30 mg
EDCI 15.2 mg,
DMF
35.4 mg
FAB
743 (M + H)+





acid

DMAP 6.4 mg






223
102
30 mg
3,3,3-trifluoropropionic acid
 168 mg
EDCI 126 mg,
DMF
10.4 mg
FAB
788 (M + H)+







DMAP 80 mg






224
73
30 mg
3,3,3-trifluoropropionic acid
  20 mg
EDCI 15.2 mg,
DMF
 8.0 mg
FAB
680 (M + H)+







DMAP 6.4 mg



















TABLE 16







Compound
Starting material




No.
(Compound No.)
Amount
Reaction reagent 1





227
73
20 mg
3-fluoro-isonicotinic acid


228
73
20 mg
3-chloro-isonicotinic acid


229
73
20 mg
3-methylpicolinic acid


230
73
20 mg
3-benzoyl-2-pyridine carboxylic acid


231
73
20 mg
3-n-propoxy picolinic acid


232
73
20 mg
6-fluoro nicotinic acid


233
102
20 mg
cyclopentane carboxylic acid


234
102
20 mg
cyclohexane carboxylic acid


235
102
20 mg
cyano acetic acid


236
102
20 mg
cyclopropyl acetic acid


237
102
20 mg
cyclopropylacetic acid


238
102
20 mg
2,2-difluoro-1-methylcyclopropanecarboxylic acid


239
73
20 mg
4-methylnicotinic acid


240
73
20 mg
4-chloro nicotinic acid


241
73
20 mg
(4-methoxy carbonyl) nicotinic acid


242
73
20 mg
5-(trifluoromethyl)thieno[3,2-b]pyridine-6-carboxylic acid


243
73
20 mg
2-cyano benzoic acid


244
73
20 mg
2-(trifluoromethyl)benzoic acid


245
73
20 mg
2-fluoro benzoic acid


246
73
20 mg
2-nitro benzoic acid


247
73
20 mg
2-chloro nicotinic acid












Mass spectrometric data













Compound




Measuring



No.
Amount
Reaction reagent 2
Solvent
Yield
Method
Data





227
15 mg
EDCI 14 mg, DMAP 4 mg
DMF
 5.4 mg
FAB
693 (M + H)+


228
17 mg
EDCI 14 mg, DMAP 4 mg
DMF
 7.8 mg
FAB
709 (M + H)+


229
14 mg
EDCI 28 mg, DMAP 8 mg
DMF
16.7 mg
FAB
689 (M + H)+


230
48 mg
EDCI 28 mg, DMAP 8 mg
DMF
16.4 mg
FAB
779 (M + H)+


231
38 mg
EDCI 28 mg, DMAP 8 mg
DMF
17.3 mg
FAB
733 (M + H)+


232
30 mg
EDCI 28 mg, DMAP 8 mg
DMF
 5.3 mg
FAB
693 (M + H)+


233
99 mg
EDCI 84 mg, DMAP 5 mg
DMF
28.3 mg
FAB
746 (M + H)+


234
112 mg 
EDCI 84 mg, DMAP 5 mg
DMF
21.5 mg
FAB
788 (M + H)+


235
74 mg
EDCI 84 mg, DMAP 5 mg
DMF
 3.3 mg
FAB
659 (M + H)+


236
87 mg
EDCI 84 mg, DMAP 5 mg
DMF
16.7 mg
FAB
786 (M + H)+


237
87 mg
EDCI 84 mg, DMAP 5 mg
DMF
 8.2 mg
FAB
704 (M + H)+


238
118 mg 
EDCI 84 mg, DMAP 5 mg
DMF
 6.1 mg
FAB
812 (M + H)+


239
36 mg
EDCI 28 mg, DMAP 8 mg
DMF
16.1 mg
FAB
689 (M + H)+


240
33 mg
EDCI 28 mg, DMAP 8 mg
DMF
13.8 mg
FAB
709 (M + H)+


241
38 mg
EDCI 28 mg, DMAP 8 mg
DMF
18.8 mg
FAB
733 (M + H)+


242
38 mg
EDCI 28 mg, DMAP 8 mg
DMF
20.3 mg
FAB
799 (M + H)+


243
31 mg
EDCI 28 mg, DMAP 8 mg
DMF
 6.6 mg
FAB
699 (M + H)+


244
40 mg
EDCI 28 mg, DMAP 8 mg
DMF
10.2 mg
FAB
742 (M + H)+


245
29 mg
EDCI 28 mg, DMAP 8 mg
DMF
16.1 mg
FAB
692 (M + H)+


246
35 mg
EDCI 28 mg, DMAP 8 mg
DMF
 9.8 mg
FAB
719 (M + H)+


247
33 mg
EDCI 28 mg, DMAP 8 mg
DMF
13.1 mg
FAB
709 (M + H)+




















TABLE 17







Compound
Starting material





No.
(Compound No.)
Amount
Reaction reagent 1
Amount





248
73
20 mg
2-chloro-6-methylnicotinic acid
36 mg


249
73
20 mg
methoxymethylbromide
31 mg


250
102
20 mg
2,2-difluorocyclopropane carboxylic acid
106 mg 


251
73
20 mg
3-tert-buthylthio-2-carboxy piridine
44 mg


252
73
20 mg
3,5-difluoropyridine-2-carboxylic acid
33 mg


253
73
20 mg
pyrazine carboxylic acid
26 mg


254
73
20 mg
4-thiazole carboxylic acid
27 mg


255
73
20 mg
3-chloro thiophene-2-carboxylic acid
34 mg


256
73
20 mg
6-methylnicotinic acid
29 mg


257
73
20 mg
6-chloro pyridine-2-carboxylic acid
33 mg


258
73
20 mg
6-fluoro pyridine-2-carboxylic acid
30 mg


259
73
20 mg
1-methyl indole-2-carboxylic acid
37 mg


260
73
20 mg
3-chloropyridine-2-carboxylic acid
33 mg


262
73
20 mg
2-fluoro nicotinic acid
30 mg


263
73
20 mg
4-cyano benzoic acid
31 mg


264
73
20 mg
3-cyano benzoic acid
31 mg


265
73
20 mg
3-(trifluoromethyl)benzoic acid
40 mg


266
73
20 mg
2-pyridylacetic acid
36 mg


267
73
20 mg
3-pyridylacetic acid
36 mg


268
73
20 mg
(4-pyridylthio) acetic acid
36 mg


270
261
20 mg
4-(trifluoromethyl)nicotinic acid
39 mg


271
261
20 mg
3-chloropyridine-2-carboxylic acid
32 mg












Mass spectrometric data














Compound



Measuring




No.
Reaction reagent 2
Solvent
Yield
Method
Data






248
EDCI 28 mg, DMAP 8 mg
DMF
17.2 mg
FAB
723 (M + H)+



249
[(CH3)2CH]2NEt 18 mg
DMF
 1.2 mg
ESI
614 (M + H)+



250
EDCI 84 mg, DMAP 5 mg
DMF
23.2 mg
ESI
770 (M + H)+



251
EDCI 28 mg, DMAP 8 mg
DMF
 7.6 mg
ESI
763 (M + H)+



252
EDCI 28 mg, DMAP 8 mg
DMF
10.9 mg
ESI
711 (M + H)+



253
EDCI 28 mg, DMAP 8 mg
DMF
10.9 mg
ESI
676 (M + H)+



254
EDCI 28 mg, DMAP 8 mg
DMF
18.5 mg
ESI
681 (M + H)+



255
EDCI 28 mg, DMAP 8 mg
DMF
15.8 mg
ESI
714 (M + H)+



256
EDCI 28 mg, DMAP 8 mg
DMF
15.1 mg
ESI
689 (M + H)+



257
EDCI 28 mg, DMAP 8 mg
DMF
12.7 mg
ESI
709 (M + H)+



258
EDCI 28 mg, DMAP 8 mg
DMF
14.4 mg
ESI
693 (M + H)+



259
EDCI 28 mg, DMAP 8 mg
DMF
18.8 mg
ESI
727 (M + H)+



260
EDCI 28 mg, DMAP 8 mg
DMF
14.6 mg
ESI
709 (M + H)+



262
EDCI 28 mg, DMAP 8 mg
DMF
 9.9 mg
ESI
693 (M + H)+



263
EDCI 28 mg, DMAP 8 mg
DMF
14.0 mg
ESI
699 (M + H)+



264
EDCI 28 mg, DMAP 8 mg
DMF
16.9 mg
ESI
699 (M + H)+



265
EDCI 28 mg, DMAP 8 mg
DMF
14.3 mg
ESI
742 (M + H)+



266
EDCI 28 mg, DMAP 8 mg
DMF
11.7 mg
ESI
689 (M + H)+



267
EDCI 28 mg, DMAP 8 mg
DMF
 8.6 mg
ESI
689 (M + H)+



268
EDCI 28 mg, DMAP 4 mg
DMF
16.5 mg
ESI
721 (M + H)+



270
EDCI 26 mg, DMAP 4 mg
DMF
 8.3 mg
ESI
767 (M + H)+



271
EDCI 26 mg, DMAP 4 mg
DMF
14.5 mg
ESI
733 (M + H)+

















TABLE 18





Compound 



No.
1H-NMR δ (ppm)
















73
0.91 (3H, s), 1.13 (3H, t, J = 5.1 Hz), 1.14 (3H, t, J = 5.1 Hz), 



1.26 (1H, s), 1.32-1.40 (1H, m), 1.42 (3H, s), 1.45 (1H, d, J = 



2.7 Hz), 1.49-1.51 (2H, m), 1.66 (3H, s), 1.81-1.91 (2H, m), 



2.13-2.18 (1H, m), 2.24-2.37 (4H, m), 2.90 (1H, m), 3.79 (3H, 



m), 4.80 (1H, dd, J = 3.5, 7.6 Hz), 4.99-5.00 (1H, m), 6.52 



(1H, s), 7.42 (1H, dd, J = 3.5, 5.4 Hz), 8.11 (1H, dt, J = 1.4, 



5.4 Hz), 8.70 (1H, d, J = 2.4 Hz), 9.00 (1H, s)


77
0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.37-1.46 (1H, m), 1.51 (3H, s), 1.62 (1H, d, J = 



3.8 Hz), 1.68-1.82 (2H, m), 1.87 (3H, s), 1.91-2.00 (2H, m), 



2.18-2.23 (1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.43 (2H, dq, J = 



1.4, 7.6 Hz), 2.97 (1H, s), 3.70 (1H, d, J = 11.9 Hz), 3.84 (1H, 



d, J = 11.9 Hz), 4.83 (1H, dd, J = 5.1, 11.1 Hz), 5.05 (1H, d, 



J = 4.3 Hz), 5.27 (1H, dd, J = 4.6, 11.1 Hz), 6.45 (1H, s), 7.39-



7.66 (4H, m), 8.05-8.13 (3H, m), 8.70 (1H, d, J = 4.6 Hz), 9.00 



(1H, s)


74
0.90 (3H, s), 1.12 (3H, t, J = 7.8 Hz), 1.13 (3H, t, J = 7.8 Hz), 



1.19 (1H, s), 1.25-1.34 (1H, m), 1.44 (3H, s), 1.53-1.63 (3H, 



m), 1.69 (3H, s), 1.73-1.90 (2H, m), 2.10 (1H, m), 2.16 (3H, 



s), 2.33 (2H, dq, J = 2.4, 7.6 Hz), 2.36 (2H, dq, J = 3.2, 7.6 



Hz), 2.87 (1H, m), 3.72 (2H, m), 4.81 (1H, dd, J = 4.6, 11.6 



Hz), 4.97-5.00 (2H, m), 6.46 (1H, s), 7.40 (1H, dd, J = 4.6, 8.1 



Hz), 8.10 (1H, m), 8.69 (1H, d, J = 4.9 Hz), 9.00 (1H, s)


205
0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.42-1.50 (1H, m), 1.59 (3H, s), 1.61-1.83 (3H, 



m), 1.85 (3H, s), 1.83-2.00 (2H, m), 2.18-2.23 (1H, m), 2.33 



(2H, q, J = 7.6 Hz), 2.43 (2H, q, J = 7.6 Hz), 2.94 (1H, m), 



3.72 (1H, d, J = 11.9 Hz), 3.82 (1H, d, J = 12.7 Hz), 4.83 (1H, 



dd, J = 4.9, 11.3 Hz), 5.03-5.06 (1H, m), 5.27 (1H, dd, J = 4.9,



11.3 Hz), 6.42 (1H, s), 7.38 (1H, dd, J = 4.9, 8.1 Hz), 7.45 



(1H, dd, J = 4.9, 8.1 Hz), 8.07 (1H, dt, J = 2.2, 8.1 Hz), 8.36 



(1H, dt, J = 1.9, 8.1 Hz), 8.67 (1H, dd, J = 1.9, 5.1 Hz), 8.83 



(1H, dd, J = 1.9, 4.9 Hz), 8.97 (1H, d, J = 1.9 Hz), 9.30 (1H, d, 



J = 1.9 Hz)


206
0.90 (3H, s), 1.13 (6H, t, J = 7.6 Hz), 1.19 (1H, s), 1.24 (3H, d, 



J = 4.6 Hz), 1.26 (3H, d, J = 4.6 Hz), 1.33-1.38 (1H, m), 1.45 



(3H, s), 1.54 (1H, d, J = 3.8 Hz), 1.60-1.64 (2H, m), 1.67 (3H, 



s), 1.75-1.90 (2H, m), 2.15-2.19 (1H, m), 2.32 (2H, q, J = 7.6 



Hz), 2.38 (2H, q, J = 7.6 Hz), 2.65 (1H, quint, J = 7.6 Hz), 



2.88 (1H, d, J = 1.6 Hz), 3.68 (1H, d, J = 12.4 Hz), 3.83 (1H, 



d, J = 11.9 Hz), 4.80 (1H, dd, J = 4.9, 11.3 Hz), 5.00 (2H, m), 



6.38 (1H, s), 7.40 (1H, dd, J = 4.6, 8.1 Hz), 8.09 (1H, dt, J = 



1.9, 8.1 Hz), 8.69 (1H, dd, J = 1.6, 4.6 Hz), 9.00 (1H, d, J = 



1.6 Hz)

















TABLE 19





 
1H-NMR δ (ppm)







208
0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.21 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.39-1.47 (1H, m), 1.50 (3H, s), 1.61 (1H, m), 



1.68-1.83 (2H, m), 1.86 (3H, s), 1.91-2.05 (2H, m), 2.18-2.23 



(1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.43 (2H, dq, J = 1.4, 7.6 



Hz), 2.95 (1H, d, J = 2.4 Hz), 3.72 (1H, d, J = 11.9 Hz), 3.82 



(1H, d, J = 11.9 Hz), 4.83 (1H, dd, J = 5.1, 11.1 Hz), 5.03-5.06 



(1H, m), 5.26 (1H, dd, J = 4.9, 11.1 Hz), 6.40 (1H, s), 7.38 (1H, 



dd, J = 4.9, 8.4 Hz), 7.76 (2H, d, J = 8.4 Hz), 8.06 (1H, dt, J = 



2.2, 8.1 Hz), 8.22 (2H, d, J = 8.4 Hz), 8.66 (1H, dd, J = 1.6, 4.9 



Hz), 8.96 (1H, d, J = 2.2 Hz)


211
0.90 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.15 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.29-1.38 (1H, m), 1.41 (3H, s), 1.43-1.71 (5H, 



m), 1.59 (3H, s), 1.75-1.89 (6H, m), 2.12-2.17 (1H, m), 2.26-



2.38 (4H, m), 2.86 (1H, m), 3.45-4.00 (5H, m), 4.82 (1H, dd, 



J = 5.4, 10.8 Hz), 4.97-5.03 (2H, m), 6.41 (1H, s), 7.40 (1H, dd, 



J = 4.9, 7.8 Hz), 8.07-8.13 (1H, m), 8.67-8.70 (1H, m), 9.01 



(1H, d, J = 2.4 Hz)


212
0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.38-1.46 (1H, m), 1.50 (3H, s), 1.61 (1H, m), 



1.66-1.78 (2H, m), 1.84 (3H, s), 1.87-1.99 (2H, m), 2.12-2.23 



(1H, m), 2.31 (2H, q, J = 7.6 Hz), 2.41 (2H, q, J = 7.6 Hz), 2.95 



(1H, m), 3.73 (1H, d, J = 11.9 Hz), 3.81 (1H, d, J = 11.9 Hz),



4.83 (1H, dd, J = 4.9, 11.3 Hz), 5.04 (1H, m), 5.25 (1H, dd, J = 



4.9, 11.3 Hz), 6.40 (1H, s), 7.38 (1H, dd, J = 4.6, 7.8 Hz), 7.47 



8(1H, d, J = 8.1 Hz), .06 (1H, dt, J = 1.6, 7.8 Hz), 8.30 (1H, dd, 



J = 2.4, 8.1 Hz), 8.67 (1H, dd, J = 1.4, 4.6 Hz), 8.97 (1H, d, J = 



2.4 Hz), 9.06 (1H, d, J = 2.7 Hz)


213
0.90 (3H, s), 0.93 (2H, d, J = 2.7 Hz), 0.96 (2H, d, J = 2.7 Hz),



1.03-1.19 (6H, m), 1.26 (1H, s), 1.32-1.39 (1H, m), 1.45 (3H, 



s), 1.52 (1H, d, J = 3.8 Hz), 1.61-1.69 (3H, m), 1.71 (3H, s), 



1.73-1.94 (2H, m), 2.14-2.19 (1H, m), 2.24-2.40 (4H, m), 2.95 



(1H, m), 3.68 (1H, d, J = 11.9 Hz), 3.81 (1H, d, J = 11.9 Hz),



4.79 (1H, dd, J = 5.4, 11.3 Hz), 4.96-5.00 (2H, m), 6.45 (1H, s),



7.40 (1H, dd, J = 4.6, 8.1 Hz), 8.10 (1H, dt, J = 1.9, 8.1 Hz), 



8.68 (1H, m), 9.01 (1H, m)


214
0.90 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.17 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.34-1.40 (1H, m), 1.44 (3H, s), 1.54 (1H, d, J = 



4.3 Hz), 1.61-1.67 (2H, m), 1.69 (3H, s), 1.72-2.42 (13H, m), 



2.91 (1H, m), 3.23 (1H, quint., J = 8.1 Hz), 3.69 (1H, d, J = 



11.9 Hz), 3.81 (1H, d, J = 11.9 Hz), 4.80 (1H, dd, J = 4.9, 11.3 



Hz), 4.99-5.04 (2H, m), 6.40 (1H, s), 7.39 (1H, dd, J = 4.9, 8.1 



Hz), 8.09 (1H, dt, J = 1.6, 8.1 Hz), 8.69 (1H, dd, J = 1.6, 4.6 



Hz), 9.01 (1H, d, J = 1.6 Hz)


215
0.90 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.17 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.41-1.46 (1H, m), 1.59 (3H, s), 1.65-1.68 (3H, 



m), 1.73 (3H, s), 1.84-1.90 (2H, m), 2.18 (1H, m), 2.31 (2H, q, 



J = 7.6 Hz), 2.38 (2H, q, J = 7.6 Hz), 2.93 (1H, m), 3.69 (1H, d, 



J = 11.9 Hz), 3.81 (1H, d, J = 11.9 Hz), 4.80 (1H, m), 5.01-5.09 



(2H, m), 5.92 (1H, dd, J = 1.6, 10.5 Hz), 6.15-6.24 (1H, m), 



6.45 (1H, s), 6.45-6.53 (1H, m), 7.40 (1H, dd, J = 4.6, 7.8 Hz),



8.07-8.11 (1H, m), 8.68 (1H, dd, J = 1.9, 4.9 Hz), 9.00 (1H, d, 



J = 2.2 Hz)

















TABLE 20





 
1H-NMR δ (ppm)







216
0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.38-1.42 (1H, m), 1.50 (3H, s), 1.64-1.78 (3H, m), 



1.85 (3H, s), 1.88-2.05 (2H, m), 2.17-2.23 (1H, m), 2.33 (2H, q, 



J = 7.6 Hz), 2.42 (2H, dq, J = 1.1, 7.6 Hz), 2.99 (1H, m), 3.72 



(1H, d, J = 12.4 Hz), 3.81 (1H, d, J = 11.5 Hz), 4.83 (1H, dd, J = 



4.9, 11.5 Hz), 5.03-5.05 (1H, m), 5.25 (1H, dd, J = 5.4, 11.5 



Hz), 6.41 (1H, s), 7.37 (1H, dd, J = 5.2, 8.1 Hz), 7.91 (2H, dd, 



J = 1.6, 4.6 Hz), 8.07 (1H, dt, J = 1.6, 8.1 Hz), 8.67 (1H, dd, J = 



1.9, 4.9 Hz), 8.83 (2H, dd, J = 1.6, 4.3 Hz), 8.97 (1H, d, J = 1.6 



Hz)


217
0.91 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.37-1.46 (1H, m), 1.50 (3H, s), 1.63-1.75 (3H, m), 



1.87 (3H, s), 1.83-1.96 (2H, m), 2.13-2.23 (1H, m), 2.32 (2H, q, 



J = 7.6 Hz), 2.41 (2H, dq, J = 1.4, 7.6 Hz), 2.99 (1H, m), 3.67 



(1H, d, J = 11.9 Hz), 3.83 (1H, d, J = 11.9 Hz), 4.83 (1H, dd, J = 



5.4, 11.3 Hz), 4.98-5.06 (1H, m), 5.38 (1H, dd, J = 5.4, 10.8 



Hz), 6.43 (1H, s), 7.35-7.44 (1H, m), 7.50-7.55 (1H, m), 7.89 



(1H, dt, J = 1.6, 7.6 Hz), 8.07 (1H, dt, J = 1.6, 8.1 Hz), 8.18 



(1H, d, J = 7.6 Hz), 8.67 (1H, dd, J = 1.6, 4.9 Hz), 8.82-8.84 



(1H, m), 8.97 (1H, d, J = 2.4 Hz)


218
0.83-1.12 (12H, m), 0.91 (3H, s), 1.26 (1H, s), 1.33-1.41 (1H, 



m), 1.45 (3H, s), 1.52-1.69 (6H, m), 1.71 (3H, s), 1.81-1.93 (2H, 



m), 2.14-2.18 (1H, m), 2.92 (1H, m), 3.72 (1H, d, J = 11.9 Hz), 



3.82 (1H, d, J = 11.9 Hz), 4.80 (1H, dd, J = 4.9, 11.4 Hz), 4.99-



5.04 (2H, m), 6.46 (1H, s), 7.41 (1H, dd, J = 4.9, 8.3 Hz), 8.10 



(1H, dt, J = 1.7, 8.3 Hz), 8.69 (1H, dd, J = 1.5, 4.9 Hz), 9.01 



(1H, d, J = 1.4 Hz)


219
0.90 (3H, s), 1.26 (1H, s), 1.32-1.41 (1H, m), 1.44 (3H, s), 1.51-



1.63 (3H, m), 1.69 (3H, s), 1.79-2.04 (8H, m), 2.17-2.40 (14H, 



m), 2.89 (1H, m), 3.08-3.26 (3H, m), 3.67 (1H, d, J = 11.9 Hz), 



3.78 (1H, d, J = 11.9 Hz), 4.79 (1H, dd, J = 5.4, 11.1 Hz), 4.97-



5.00 (2H, m), 6.41 (1H, s), 7.41 (1H, dd, J = 4.9, 8.1 Hz), 8.09 



(1H, dt, J = 1.9, 8.4 Hz), 8.68 (1H, m), 9.00 (1H, m)


220
1.17 (3H, s), 1.26 (1H, s), 1.57 (3H, s), 1.65 (1H, m), 1.77-1.82 



(2H, m), 1.88 (3H, s), 1.94-2.05 (3H, m), 2.13-2.31 (1H, m), 



2.95 (1H, m), 4.16 (2H, s), 5.06 (1H, dd, J = 2.4, 6.5 Hz), 5.17-



5.32 (2H, m), 6.42 (1H, s), 7.34-7.64 (10H, m), 8.01-8.12 (7H, 



m), 8.66 (1H, dd, J = 1.6, 5.1 Hz), 8.97 (1H, d, J = 1.9 Hz)


221
0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.21 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.44 (1H, m), 1.50 (3H, s), 1.57-1.62 (1H, m), 



1.67-1.80 (2H, m), 1.85 (3H, s), 1.91-1.95 (2H, m), 2.17-2.24 



(1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.42 (2H, q, J = 7.6 Hz), 2.92 



(1H, m), 3.74 (1H, d, J = 11.9 Hz), 3.81 (1H, d, J = 11.9 Hz),



4.84 (1H, dd, J = 4.9, 11.1 Hz), 5.04 (1H, m), 5.27 (1H, dd, J = 



4.9, 11.1 Hz), 6.40 (1H, s), 7.38 (1H, dd, J = 4.9, 8.1 Hz), 7.84 



(1H, d, J = 8.4 Hz), 8.05-8.08 (1H, m), 8.54 (1H, d, J = 8.1 Hz), 



8.67 (1H, d, J = 4.6 Hz), 8.96 (1H, d, J = 2.2 Hz), 9.38 (1H, s)

















TABLE 21





 
1H-NMR δ (ppm)







222
0.94 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.38-1.47 (1H, m), 1.48 (3H, s), 1.57-1.71 (3H, m), 



1.75 (3H, s), 1.83-1.97 (2H, m), 2.10-2.22 (1H, m), 2.33 (2H, q, 



J = 7.6 Hz), 2.41 (2H, dq, J = 1.6, 7.6 Hz), 2.96 (1H, m), 3.74-



3.80 (2H, m), 4.83 (1H, dd, J = 5.7, 11.6 Hz), 5.02-5.03 (1H, 



m), 5.28 (1H, dd, J = 5.4, 11.6 Hz), 6.41 (1H, s), 7.40 (1H, dd, 



J = 5.4, 7.6 Hz), 7.69 (1H, d, J = 5.4 Hz), 8.08 (1H, dt, J = 2.2, 



8.1 Hz), 8.69 (1H, dd, J = 1.6, 4.9 Hz), 8.97 (1H, d, J = 4.6 Hz), 



9.00 (1H, d, J = 2.4 Hz), 9.16 (1H, s)


223
0.94 (3H, s), 1.26 (1H, s), 1.37 (1H, m), 1.47 (3H, s), 1.48-1.66 



(3H, m), 1.71 (3H, s), 1.75-1.96 (2H, m), 2.17-2.24 (1H, m), 



2.96 (1H, m), 3.14-3.35 (6H, m), 3.85 (1H, d, J = 12.2 Hz), 3.93 



(1H, d, J = 12.2 Hz), 4.87 (1H, dd, J = 5.7, 10.8 Hz), 4.99-5.08 



(2H, m), 6.41 (1H, s), 7.41 (1H, dd, J = 4.6, 8.1 Hz), 8.09 (1H, 



m), 8.69 (1H, m), 9.02 (1H, m)


224
0.91 (3H, s), 1.13 (3H, t, J = 7.3 Hz), 1.17 (3H, t, J = 7.3 Hz), 



1.26 (1H, s), 1.40 (1H, m), 1.45 (3H, s), 1.58-1.63 (3H, m), 1.70 



(3H, s), 1.73-1.89 (2H, m), 2.10-2.18 (1H, m), 2.32 (2H, q, J = 



7.6 Hz), 2.36 (2H, q, J = 7.6 Hz), 2.96 (1H, m), 3.25 (1H, d, J = 



9.7 Hz), 3.32 (1H, d, J = 9.7 Hz), 3.69-3.81 (2H, m), 4.80 (1H, 



dd, J = 5.4, 11.3 Hz), 5.00-5.08 (2H, m), 6.40 (1H, s), 7.41 (1H, 



dd, J = 4.9, 8.1 Hz), 8.09 (1H, m), 8.69 (1H, dd, J = 1.4, 5.1 



Hz), 9.01 (1H, d, J = 2.4 Hz)


225
0.88 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.5 Hz), 



1.22 (3H, t, J = 7.6 Hz), 1.24 (3H, s), 1.26 (1H, m), 1.50-1.55 



(1H, m), 1.56 (3H, s), 1.55-1.64 (3H, m), 1.70-1.84 (2H, m), 



2.31 (2H, dq, J = 1.2, 7.8 Hz), 2.42 (2H, dq, J = 3.4, 13.6 Hz), 



52.44 (2H, dq, J = 2.0, 7.5 Hz), 2.79 (1H, dt, J = 1.4, .1 Hz), 



3.69 (1H, d, J = 11.9 Hz), 3.79 (1H, d, J = 11.9 Hz), 4.79 (1H, 



dd, J = 4.9, 11.4 Hz), 5.24 (1H, dd, J = 4.9, 11.4 Hz), 6.45 (1H, 



s), 7.47 (1H, d, J = 8.5 Hz), 8.12 (1H, dd, J = 2.7, 8.5 Hz), 8.83 



(1H, d, J = 2.7 Hz)


226
0.89 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.6 Hz),



1.10-1.24 (3H, m), 1.26 (1H, s), 1.31-1.39 (1H, m), 1.44 (3H, s), 



1.53 (1H, d, J = 3.8 Hz), 1.61-1.67 (2H, m), 1.69 (3H, s), 1.72-



1.92 (2H, m), 2.08-2.18 (1H, m), 2.31 (2H, dq, J = 2.7, 7.6 Hz), 



2.44 (2H, dq, J = 1.6, 7.6 Hz), 2.26-2.64 (2H, m), 2.85 (1H, s), 



3.69 (1H, d, J = 11.9 Hz), 3.80 (1H, d, J = 11.9 Hz), 4.80 (1H, 



dd, J = 5.4, 11.3 Hz), 4.92-5.10 (2H, m), 6.41 (1H, s), 7.44 (1H,



d, J = 8.4 Hz), 8.05 (1H, dd, J = 2.4, 8.4 Hz), 8.78 (1H, d, J = 



2.4 Hz)


227
0.88 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz),



1.23-1.33 (1H, m), 1.43 (1H, m), 1.49 (3H, s), 1.61-1.74 (3H, 



m), 1.82 (3H, s), 1.87-2.23 (3H, m), 2.33 (2H, q, J = 7.6 Hz), 



2.42 (2H, q, J = 7.6 Hz), 2.96 (1H, m), 3.73 (1H, d, J = 12.4 



Hz), 3.82 (1H, d, J = 12.4 Hz), 4.83 (1H, dd, J = 5.4, 11.3 Hz), 



5.03 (1H, m), 5.26 (1H, dd, J = 5.4, 11.3 Hz), 6.43 (1H, s),



7.39 (1H, dd, J = 4.9, 8.1 Hz), 7.86 (1H, t, J = 5.4 Hz), 8.08 



(1H, dt, J = 1.9, 7.8 Hz), 8.60 (1H, d, J = 2.2 Hz), 8.66-8.68 



(2H, m), 8.98 (1H, d, J = 2.2 Hz)

















TABLE 22





 
1H-NMR δ (ppm)







228
0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.32-1.44 (1H, m), 1.49 (3H, s), 1.61 (1H, d, J = 



4.1 Hz), 1.67-1.75 (2H, m), 1.81 (3H, s), 1.79-2.05 (2H, m), 



2.13-2.22 (1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 



1.4, 7.6 Hz), 2.92 (1H, m), 3.74 (1H, d, J = 11.9 Hz), 3.82 (1H, 



d, J = 11.9 Hz), 4.84 (1H, dd, J = 5.4, 10.8 Hz), 5.04 (1H, m), 



5.27 (1H, dd, J = 5.4, 10.8 Hz), 6.43 (1H, s), 7.40 (1H, dd, J = 



4.9, 8.1 Hz), 7.74 (1H, d, J = 5.1 Hz), 8.08 (1H, dt, J = 2.2, 8.1 



Hz), 8.65 (1H, d, J = 4.9 Hz), 8.69 (1H, dd, J = 4.1, 7.6 Hz), 



8.78 (1H, s), 8.99 (1H, d, J = 1.9 Hz)


229
0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 6.5 Hz), 



1.26 (1H, s), 1.34-1.45 (1H, m), 1.49 (3H, s), 1.62 (1H, m), 



1.71-1.77 (2H, m), 1.83 (3H, s), 1.88-2.01 (2H, m), 2.14-2.22 



(1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 2.2, 7.6 Hz), 



2.64 (3H, s), 2.96 (1H, m), 3.72 (1H, d, J = 11.9 Hz), 3.84 (1H, 



d, J = 11.9 Hz), 4.84 (1H, dd, J = 5.4, 11.3 Hz), 5.04 (1H, m),



5.36 (1H, dd, J = 5.4, 10.8 Hz), 6.42 (1H, s), 7.35-7.42 (2H, m), 



7.66 (1H, d, J = 7.8 Hz), 8.08 (1H, dt, J = 1.9, 7.8 Hz), 8.60 



(1H, d, J = 4.1 Hz), 8.68 (1H, dd, J = 1.6, 4.9 Hz), 8.98 (1H, d, 



J = 2.4 Hz),


230
0.78 (3H, s), 1.09 (3H, t, J = 7.8 Hz), 1.12 (3H, t, J = 7.8 Hz), 



1.26 (1H, s), 1.33 (3H, s), 1.36-1.38 (1H, m), 1.40-1.48 (2H, m), 



1.55 (3H, s), 1.59-1.85 (2H, m), 2.09-2.18 (1H, m), 2.32 (4H, q, 



J = 7.6 Hz), 2.96 (1H, m), 3.40 (1H, d, J = 11.9 Hz), 3.75 (1H, 



d, J = 11.9 Hz), 4.72 (1H, dd, J = 4.9, 11.3 Hz), 4.95 (1H, m), 



5.17 (1H, dd, J = 5.4, 11.9 Hz), 6.45 (1H, s), 7.40 (1H, dd, J = 



4.9, 8.1 Hz), 7.49-7.67 (3H, m), 7.83-7.88 (4H, m), 8.02 (1H, s), 



8.07 (1H, dt, J = 2.2, 8.1 Hz), 8.68 (1H, dd, J = 1.4, 4.6 Hz), 



8.95 (1H, dd, J = 1.6, 4.6 Hz), 8.99 (1H, d, J = 1.9 Hz)


231
0.91 (3H, s), 1.09 (3H, t, J = 7.6 Hz), 1.14 (3H, t, J = 7.6 Hz), 



1.18 (3H, t, J = 7.6 Hz), 1.26 (1H, s), 1.34-1.43 (1H, m), 1.48 



(3H, s), 1.63 (1H, m), 1.67-1.75 (2H, m), 1.80 (3H, s), 1.83-2.08 



(4H, m), 2.17-2.25 (1H, m), 2.32 (2H, q, J = 7.6 Hz), 2.40 (2H, 



dq, J = 7.6, 1.9 Hz), 2.96 (1H, m), 3.64 (1H, d, J = 11.9 Hz),



3.87 (1H, d, J = 11.9 Hz), 4.05 (2H, t, J = 6.2 Hz), 4.82 (1H, dd, 



J = 5.4, 10.8 Hz), 5.04 (1H, m), 5.40 (1H, dd, J = 5.4, 10.8 Hz), 



6.47 (1H, s), 7.19-7.44 (3H, m), 8.08 (1H, dt, J = 1.9, 8.1 Hz), 



8.32 (1H, dd, J = 1.6, 4.3 Hz), 8.68 (1H, dd, J = 4.6, 1.6 Hz), 



8.98 (1H, d, J = 1.6 Hz)


232
0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.34-1.43 (1H, m), 1.50 (3H, s), 1.61 (1H, m), 



1.67-1.78 (2H, m), 1.84 (3H, s), 1.87-1.97 (2H, m), 2.13-2.23 



(1H, m), 2.18 (1H, s), 2.32 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 



1.4, 7.6 Hz), 3.73 (1H, d, J = 11.9 Hz), 3.80 (1H, d, J = 11.9 



Hz), 4.83 (1H, dd, J = 5.4, 11.1 Hz), 5.04 (1H, d, J = 3.8 Hz),



5.25 (1H, dd, J = 5.1, 11.1 Hz), 6.41 (1H, s), 7.06 (1H, dd, J = 



3.0, 8.6 Hz), 7.38 (1H, dd, J = 4.9, 8.1 Hz), 8.08 (1H, dt, J = 1.9, 



8.1 Hz), 8.43-8.50 (1H, m), 8.67 (1H, dd, J = 1.6, 4.6 Hz), 8.95-



8.98 (2H, m)

















TABLE 23





 
1H-NMR δ (ppm)







233
0.91 (3H, s), 1.26 (1H, s), 1.45 (3H, s), 1.70 (3H, s), 1.32-1.97 



(29H, m), 2.14-2.19 (1H, m), 2.66-2.90 (3H, m), 3.06 (1H, s), 



3.67 (1H, d, J = 11.9 Hz), 3.78 (1H, d, J = 11.9 Hz), 4.78 (1H, 



dd, J = 5.4, 10.8 Hz), 4.98-5.01 (2H, m), 6.40 (1H, s), 7.42 (1H, 



dd, J = 4.9, 8.1 Hz), 8.11 (1H, dt, J = 1.6, 8.1 Hz), 8.69 (1H, d, 



J = 4.6 Hz), 9.01 (1H, s)


234
0.91 (3H, s), 1.45 (3H, s), 1.70 (3H, s), 1.10-2.05 (37H, m), 



2.14-2.49 (3H, m), 3.04 (1H, s), 3.65 (1H, d, J = 11.3 Hz), 3.77 



(1H, d, J = 11.9 Hz), 4.78 (1H, dd, J = 5.4, 10.8 Hz), 4.97-5.01 



(2H, m), 6.41 (1H, s), 7.42 (1H, dd, J = 4.9, 8.1 Hz), 8.11 (1H, 



dd, J = 1.9, 8.1 Hz), 8.69 (1H, d, J = 4.3 Hz), 9.01 (1H, s)


235
1.00 (3H, s), 1.25-1.33 (3H, m), 1.48 (3H, s), 1.55 (1H, m), 1.71 



(1H, m), 1.75 (3H, s), 1.79-1.98 (2H, m), 2.11-2.21 (1H, m), 



3.48 (2H, s), 3.54 (2H, s), 3.60 (2H, s), 3.90 (1H, d, J = 11.9 



Hz), 3.99 (1H, d, J = 11.9 Hz), 4.86 (1H, m), 4.98 (1H, m), 



5.07-5.12 (1H, m), 6.53 (1H, s), 7.53 (1H, dd, J = 4.9, 8.1 Hz), 



8.23 (1H, m), 8.30 (1H, m), 8.70 (1H, m), 9.05 (1H, m)


236
0.11-0.27 (8H, m), 0.52-0.65 (8H, m), 0.88 (3H, s), 0.99-1.14 



(5H, m), 1.15 (3H, s), 1.25-1.43 (2H, m), 1.61-1.76 (4H, m), 



1.72 (3H, s), 2.18-2.54 (9H, m), 3.74 (1H, d, J = 11.9 Hz), 3.83 



(1H, d, J = 11.9 Hz), 4.86 (1H, dd, J = 4.6, 11.6 Hz), 5.01-5.12 



(2H, m), 6.41 (1H, s), 7.45 (1H, dd, J = 4.9, 7.8 Hz), 8.16 (1H, 



m), 8.71 (1H, m), 9.02 (1H, s)


237
0.14-0.26 (6H, m), 0.52-0.64 (6H, m), 0.92 (3H, s), 0.97-1.16 



(4H, m), 1.26-1.38 (1H, m), 1.45 (3H, s), 1.52 (1H, m), 1.63-



1.70 (2H, m), 1.70 (3H, s), 1.82-1.91 (2H, m), 2.12-2.41 (7H, 



m), 2.96 (1H, m), 3.74 (1H, d, J = 11.9 Hz), 3.86 (1H, d, J = 



11.9 Hz), 4.84 (1H, dd, J = 4.9, 11.3 Hz), 5.00-5.03 (2H, m), 



6.43 (1H, s), 7.42 (1H, dd, J = 4.6, 7.8 Hz), 8.11 (1H, m), 8.70 



(1H, d, J = 4.3 Hz), 9.01 (1H, s)


238
0.91 (3H, s), 1.26 (1H, s), 1.44 (3H, s), 1.45 (3H, s), 1.46 (3H, 



s), 1.34-1.53 (7H, m), 1.52 (3H, s), 1.70 (3H, s), 1.81-2.02 (2H, 



m), 2.15-2.31 (3H, m), 2.96 (1H, s), 3.67 (1H, m), 4.00 (1H, m), 



4.85-5.00 (3H, m), 6.46 (1H, s), 7.45 (1H, dd, J = 4.9, 8.1 Hz), 



8.13 (1H, m), 8.70 (1H, m), 9.02 (1H, s)


239
0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.33-1.44 (1H, m), 1.50 (3H, s), 1.61 (1H, m), 



1.68-1.77 (2H, m), 1.84 (3H, s), 1.91-1.99 (2H, m), 2.17-2.23 



(1H, m), 2.32 (2H, q, J = 7.6 Hz), 2.43 (2H, dq, J = 3.0, 7.6 Hz), 



2.69 (3H, s), 2.96 (1H, m), 3.75 (1H, d, J = 12.2 Hz), 3.80 (1H, 



d, J = 12.2 Hz), 4.48 (1H, dd, J = 5.1, 11.1 Hz), 5.04 (1H, d, J = 



4.1 Hz), 5.23 (1H, d, J = 5.4, 10.8 Hz), 6.42 (1H, s), 7.24 (1H, 



d, J = 5.9 Hz), 7.39 (1H, dd, J = 4.9, 8.1 Hz), 8.08 (1H, d, J = 



8.4 Hz), 8.61 (1H, d, J = 5.1 Hz), 8.67 (1H, d, J = 3.5 Hz), 8.98 



(1H, s), 9.17 (1H, s)

















TABLE 24





 
1H-NMR δ (ppm)







240
0.93 (3H, s), 1.13 (3H, t, J = 7.9 Hz), 1.19 (3H, t, J = 7.9 Hz), 



1.26 (1H, s), 1.39-1.43 (1H, m), 1.49 (3H, s), 1.61 (1H, m), 



1.68-1.79 (2H, m), 1.82 (3H, s), 1.88-2.04 (2H, m), 2.17-2.23 



(1H, m), 2.32 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 1.9, 7.6 Hz), 



2.96 (1H, s), 3.74 (1H, d, J = 11.9 Hz), 3.83 (1H, d, J = 11.9 



Hz), 4.83 (1H, dd, J = 1.6, 5.4 Hz), 5.04 (1H, d, J = 4.1 Hz), 



5.27 (1H, dd, J = 5.4, 11.6 Hz), 6.43 (1H, s), 7.39 (1H, dd, J = 



4.9, 8.1 Hz), 7.47 (1H, d, J = 5.1 Hz), 8.08 (1H, dt, J = 1.9, 8.1 



Hz), 8.68 (1H, dd, J = 1.4, 4.6 Hz), 8.64 (1H, d, J = 5.1 Hz), 



8.99 (1H, d, J = 1.9 Hz), 9.14 (1H, s)


241
0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.38-1.43 (1H, m), 1.49 (3H, s), 1.59 (1H, d, J = 



4.4 Hz), 1.66-1.73 (2H, m), 1.78 (3H, s), 1.82-2.05 (2H, m), 



2.18-2.23 (1H, m), 2.31 (2H, q, J = 7.6 Hz), 2.41 (2H, dq, J = 



1.4, 7.6 Hz), 2.96 (1H, s), 3.72 (1H, d, J = 7.6 Hz), 3.81 (1H, d, 



J = 7.6 Hz), 3.98 (3H, s), 4.84 (1H, dd, J = 5.4, 11.3 Hz), 5.04 



(1H, m), 5.24 (1H, dd, J = 4.9, 10.8 Hz), 6.54 (1H, s), 7.39 (1H, 



dd, J = 4.9, 8.1 Hz), 7.53 (1H, d, J = 4.9 Hz), 8.08 (1H, dt, J = 



1.9, 8.1 Hz), 8.68 (1H, d, J = 4.1 Hz), 8.88 (1H, d, J = 4.9 Hz), 



9.00 (1H, s), 9.17 (1H, s)


242
0.95 (3H, s), 1.15 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.38-1.44 (1H, m), 1.49 (3H, s), 1.61 (1H, d, J = 



4.1 Hz), 1.68-1.72 (2H, m), 1.76 (3H, s), 1.82-2.06 (2H, m), 



2.18-2.23 (1H, m), 2.34 (2H, q, J = 7.6 Hz), 2.43 (2H, dq, J = 



2.2, 7.6 Hz), 2.96 (1H, s), 3.78 (1H, d, J = 12.2 Hz), 3.83 (1H, 



d, J = 12.2 Hz), 4.84 (1H, dd, J = 5.4, 11.3 Hz), 5.04 (1H, d, J =



4.1 Hz), 5.2-5.34 (1H, m), 6.40 (1H, s), 7.40 (1H, dd, J = 4.9, 



8.1 Hz), 7.76 (1H, d, J = 5.4 Hz), 8.02-8.11 (2H, m), 8.69 (1H, 



d, J = 4.3 Hz), 8.74 (1H, s), 9.00 (1H, s)


243
0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.39-1.44 (1H, m), 1.50 (3H, s), 1.62 (1H, m), 



1.68-1.75 (2H, m), 1.84 (3H, s), 1.93-1.96 (2H, m), 2.14-2.23 



(1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 2.4, 7.6 Hz), 



2.96 (1H, s), 3.72 (1H, d, J = 11.9 Hz), 3.83 (1H, d, J = 11.9 



Hz), 4.83 (1H, dd, J = 1.6, 5.4 Hz), 5.04 (1H, m), 5.36 (1H, dd, 



J = 4.9, 11.3 Hz), 6.46 (1H, s), 7.38 (1H, dd, J = 5.4, 7.6 Hz), 



7.68-7.78 (2H, m), 7.83-7.88 (1H, m), 8.07 (1H, dt, J = 1.9, 8.1 



Hz), 8.19-8.23 (1H, m), 8.67 (1H, dd, J = 1.6, 4.9 Hz), 8.98 (1H, 



d, J = 2.2 Hz)


244
0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.34-1.43 (1H, m), 1.48 (3H, s), 1.60 (1H, d, J = 



4.1 H z), 1.66-2.02 (4H, m), 1.73 (3H, s), 2.11-2.23 (1H, m), 



2.33 (2H, q, J = 7.6 Hz), 2.41 (2H, dq, J = 2.2, 7.6 Hz), 2.90 



(1H, s), 3.74 (1H, d, J = 11.9 Hz), 5.83 (1H, d, J = 11.9 Hz),



4.82 (1H, dd, J = 4.9, 11.1 Hz), 5.03 (1H, m), 5.27 (1H, dd, J = 



5.1, 11.6 Hz), 6.43 (1H, s), 7.41 (1H, dd, J = 4.9, 8.1 Hz), 7.65-



7.70 (2H, m), 7.78-7.86 (2H, m), 8.09 (1H, dt, J = 1.9, 8.1 Hz), 



8.69 (1H, d, J = 3.8 Hz), 9.00 (1H, s)

















TABLE 25





 
1H-NMR δ (ppm)







245
0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.20 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.39-1.46 (1H, m), 1.49 (3H, s), 1.62 (1H, d, J = 



4.1 Hz), 1.83 (3H, s), 1.66-2.02 (4H, m), 2.11-2.23 (1H, m), 



2.33 (2H, dq, J = 1.2, 7.6 Hz), 2.42 (2H, dq, J = 3.2, 7.6 Hz), 



2.96 (1H, m), 3.70 (1H, d, J = 12.0 Hz), 3.85 (1H, d, J = 12.0 



Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz), 5.04 (1H, m), 5.27 (1H, dd, 



J = 5.1, 11.9 Hz), 6.45 (1H, s), 7.18 (1H, dd, J = 8.5, 10.9 Hz), 



7.27 (1H, m), 7.38 (1H, dd, J = 4.8, 8.1 Hz), 7.55-7.61 (1H, m), 



8.03 (1H, dt, J = 1.7, 7.3 Hz), 8.08 (1H, dt, J = 1.7, 8.3 Hz), 8.67 



(1H, d, J = 3.9 Hz), 8.98 (1H, s)


246
0.93 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.32-1.42 (1H, m), 1.45 (3H, s), 1.59 (1H, d, J = 



3.0 Hz), 1.66 (3H, s), 1.69-1.92 (4H, m), 2.02-2.21 (1H, m), 



2.33 (2H, dq, J = 1.1, 5.1 Hz), 2.42 (2H, dq, J = 2.2, 5.1 Hz), 



2.96 (1H, m), 3.76 (1H, d, J = 11.9 Hz), 3.84 (1H, d, J = 12.0 



Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz), 5.03 (1H, d, J = 4.2 Hz),



5.19 (1H, dd, J = 5.4, 11.7 Hz), 6.60 (1H, s), 7.42 (1H, dd, J = 



4.6, 8.1 Hz), 7.66-7.76 (2H, m), 7.84 (1H, dd, J = 1.5, 7.5 Hz), 



7.93 (1H, dd, J = 1.5, 7.8 Hz), 8.11 (1H, dt, J = 2.1, 8.1 Hz), 



8.69 (1H, d, J = 4.6 Hz), 9.03 (1H, s)


247
0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.42-1.46 (1H, m), 1.49 (3H, s), 1.61 (1H, d, J = 



3.0 Hz), 1.68-1.79 (2H, m), 1.82 (3H, s), 1.86-2.02 (2H, m), 



2.16-2.22 (1H, m), 2.33 (2H, dq, J = 1.1, 5.1 Hz), 2.42 (2H, dq, 



J = 2.4, 5.1 Hz), 2.96 (1H, m), 3.74 (1H, d, J = 12.0 Hz), 3.82 



(1H, d, J = 12.0 Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz), 5.04 (1H, 



m), 5.27 (1H, dd, J = 5.1, 11.7 Hz), 6.44 (1H, s), 7.40 (1H, dd, 



J = 4.6, 7.8 Hz), 7.72 (1H, dd, J = 1.7, 8.3 Hz), 8.08 (1H, dt, J = 



2.2, 8.5 Hz), 8.26 (1H, dd, J = 1.9, 7.8 Hz), 8.58 (1H, dd, J = 



91.9, 4.9 Hz), 8.68 (1H, d, J = 3.6 Hz), .03 (1H, d, J = 1.7 Hz)


248
0.93 (3H, s), 1.16 (3H, t, J = 7.6 Hz), 1.22 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.42-1.46 (1H, m), 1.49 (3H, s), 1.61 (1H, d, J = 



3.0 Hz), 1.68-1.78 (2H, m), 1.82 (3H, s), 1.86-2.01 (2H, m), 



2.17-2.22 (1H, m), 2.33 (2H, dq, J = 1.1, 5.1 Hz), 2.42 (2H, dq, 



J = 2.4, 5.1 Hz), 2.62 (3H, s), 2.98 (1H, m), 3.73 (1H,d, J = 12.0 



Hz), 3.84 (1H, d, J = 11.9 Hz), 4.83 (1H, dd, J = 4.8, 11.5 Hz),



5.04 (1H, d, J = 3.4 Hz), 5.25 (1H, dd, J = 5.1, 11.4 Hz), 6.44 



(1H, s), 7.22 (1H, d, J = 7.8 Hz), 7.40 (1H, dd, J = 4.9, 8.0 Hz), 



8.08 (1H, dt, J = 2.2, 8.0 Hz), 8.18 (1H, d, J = 7.8 Hz), 8.69 



(1H, d, J = 3.7 Hz), 8.99 (1H, d, J = 1.7 Hz)


249
0.91 (3H, s), 1.14 (3H, t, J = 7.8 Hz), 1.15 (3H, t, J = 7.8 Hz), 



1.26 (1H, s), 1.29-1.39 (1H, m), 1.42 (3H, s), 1.45 (1H, m), 



1.57-1.64 (2H, m), 1.66 (3H, s), 1.81-1.88 (2H, m), 2.14-2.18 



(1H, m), 2.33 (2H, q, J = 7.8 Hz), 2.35 (2H, q, J = 7.8 Hz), 2.84 



(1H, m), 3.46 (3H, s), 3.68 (1H, d, J = 11.7 Hz), 3.93 (1H, d, J = 



11.9 Hz), 4.73-4.87 (4H, m), 4.95-5.00 (1H, m), 6.43 (1H, s), 



7.42 (1H, dd, J = 4.8, 8.0 Hz), 8.12 (1H, m), 8.69 (1H, m), 9.01 



(1H, d, J = 2.2 Hz)


250
0.92 (3H, s), 1.26 (1H, s), 1.34-1.55 (3H, m), 1.46 (3H, s), 1.71 



(3H, s), 1.66-1.92 (6H, m), 2.01-2.18 (4H, m), 2.38-2.57 (3H, 



m), 3.66-3.78 (1H, m), 3.95-4.13 (1H, m), 4.73-4.84 (1H, m), 



4.89-4.95 (1H, m), 4.99-5.10 (1H, m), 6.45 (1H, s), 7.43 (1H, 



dd, J = 4.9, 8.3 Hz), 8.11 (1H, m), 8.70 (1H, d, J = 4.9 Hz), 9.02 



(1H, s)

















TABLE 26





 
1H-NMR δ (ppm)







251
0.93 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.17 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.36 (9H, s), 1.42 (1H, m), 1.47 (3H, s), 1.62-1.70 



(3H, m), 1.75 (3H, s), 1.80-1.95 (2H, m), 2.07-2.21 (1H, m), 



2.32 (2H, dq, J = 1.5, 7.5 Hz), 2.40 (2H, dq, J = 3.9, 7.6 Hz), 



2.96 (1H, m), 3.69 (1H, d, J = 11.9 Hz), 3.87 (1H, d, J = 11.9 



Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz), 5.04 (1H, m), 5.36 (1H, dd,



J = 5.1, 11.7 Hz), 6.53 (1H, s), 7.39-7.43 (1H, m), 7.98 (1H, dd, 



J = 1.7, 8.0 Hz), 8.02 (1H, s), 8.10 (1H, dt, J = 1.7, 8.0 Hz), 8.65 



(1H, dd, J = 1.5, 4.7 Hz), 8.69 (1H, d, J = 3.7 Hz), 8.99 (1H, s)


252
0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.42-1.45 (1H, m), 1.49 (3H, s), 1.62-1.73 (3H, m), 



1.82 (3H, s), 1.84-2.00 (2H, m), 2.18-2.22 (1H, m), 2.32 (2H, 



dq, J = 1.5, 7.5 Hz), 2.41 (2H, dq, J = 2.5, 7.5 Hz), 2.96 (1H, 



m), 3.68 (1H, d, J = 11.9 Hz), 3.85 (1H, d, J = 11.9 Hz), 4.82 



(1H, dd, J = 4.9, 11.7 Hz), 5.04 (1H, m), 5.37 (1H, dd, J = 4.8,



11.7 Hz), 6.44 (1H, s), 7.36-7.41 (2H, m), 8.08 (1H, dt, J = 1.7, 



8.0 Hz), 8.53 (1H, d, J = 2.0 Hz), 8.68 (1H, dd, J = 0.7, 4.9 Hz), 



8.98 (1H, d, J = 2.6 Hz)


253
0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.20 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.40-1.47 (1H, m), 1.51 (3H, s), 1.64 (1H, d, J = 



2.4 Hz), 1.73 (2H, m), 1.87 (3H, s), 1.85-2.00 (2H, m), 2.18-



2.23 (1H, m), 2.32 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 1.5, 7.6 



Hz), 2.96 (1H, m), 3.71 (1H, d, J = 12.0 Hz), 3.83 (1H, d, J = 



11.9 Hz), 4.84 (1H, dd, J = 4.9, 11.7 Hz), 5.05 (1H, m), 5.39 



(1H, dd, J = 5.2, 11.6 Hz), 6.42 (1H, s), 7.39 (1H, dd, J = 4.9, 



8.1 Hz), 8.02 (1H, s), 8.07 (1H, m), 8.68 (1H, d, J = 4.4 Hz), 



8.80-8.83 (1H, m), 8.97 (1H, m), 9.38 (1H, m)


254
0.91 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.39-1.46 (1H, m), 1.49 (3H, s), 1.63 (1H, d, J = 



2.7 Hz), 1.70-1.73 (2H, m), 1.85 (3H, s), 1.88-2.01 (2H, m), 



2.18-2.22 (1H, m), 2.32 (2H, q, J = 7.5 Hz), 2.41 (2H, dq, J = 



2.2, 7.6 Hz), 2.97 (1H, m), 3.68 (1H, d, J = 11.7 Hz), 3.83 (1H, 



d, J = 11.9 Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz), 5.04 (1H, m),



5.34 (1H, dd, J = 5.4, 11.5 Hz), 6.44 (1H, s), 7.39 (1H, dd, J = 



4.9, 8.0 Hz), 8.07 (1H, dt, J = 1.9, 6.3 Hz), 8.32 (1H, d, J = 2.0 



Hz), 8.67 (1H, d, J = 4.1 Hz), 8.92 (1H, d, J = 2.0 Hz), 8.98 



(1H, s)


255
0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.38-1.45 (1H, m), 1.49 (3H, s), 1.60 (1H, d, J = 



3.0 Hz), 1.68-1.70 (2H, m), 1.83 (3H, s), 1.75-1.98 (2H, m), 



2.17-2.21 (1H, m), 2.33 (2H, dq, J = 1.7, 7.5 Hz), 2.41 (2H, dq, 



J = 2.2, 7.5 Hz), 2.97 (1H, m), 3.67 (1H, d, J = 12.0 Hz), 3.87 



(1H, d, J = 11.9 Hz), 4.81 (1H, dd, J = 4.9, 11.7 Hz), 5.03 (1H, 



m), 5.23 (1H, dd, J = 5.1, 11.5 Hz), 6.46 (1H, s), 7.07 (1H, d, 



J = 5.2 Hz), 7.39 (1H, dd, J = 4.9, 8.1 Hz), 7.54 (1H, d, J = 5.3 



Hz), 8.08 (1H, dt, J = 2.2, 8.1 Hz), 8.67 (1H, dd, J = 1.4, 4.9 



Hz), 8.99 (1H, d, J = 2.2 Hz)

















TABLE 27





 
1H-NMR δ (ppm)







256
0.92 (3H, s), 1.12 (3H, t, J = 7.8 Hz), 1.15 (3H, t, J = 7.7 Hz), 



1.26 (1H, s), 1.39-1.47 (1H, m), 1.50 (3H, s), 1.61 (1H, d, J = 



2.4 Hz), 1.69-1.81 (2H, m), 1.85 (3H, s), 1.90-1.99 (2H, m), 



2.18-2.21 (1H, m), 2.33 (2H, dq, J = 1.2, 7.7 Hz), 2.41 (2H, dq, 



J = 2.7, 7.6 Hz), 2.66 (3H, s), 2.96 (1H, m), 3.72 (1H, d, J = 



11.7 Hz), 3.83 (1H, d, J = 12.0 Hz), 4.83 (1H, dd, J = 4.9, 11.4 



Hz), 5.04 (1H, m), 5.25 (1H, dd, J = 5.3, 11.7 Hz), 6.41 (1H, s), 



7.30 (1H, d, J = 8.0 Hz), 7.38 (1H, dd, J = 4.9, 8.1 Hz), 8.07 



(1H, dt, J = 2.2, 8.1 Hz), 8.24 (1H, dd, J = 2.2, 8.0 Hz), 8.67 



(1H, dd, J = 1.5, 4.9 Hz), 8.97 (1H, d, J = 2.2 Hz), 9.18 (1H, d, 



J = 2.2 Hz)


257
0.91 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.38-1.46 (1H, m), 1.50 (3H, s), 1.63 (1H, d, J = 



2.4 Hz), 1.70-1.73 (2H, m), 1.86 (3H, s), 1.83-1.98 (2H, m), 



2.18-2.22 (1H, m), 2.32 (2H, dq, J = 1.5, 7.7 Hz), 2.41 (2H, dq, 



JJ = 2.2, 7.7 Hz), 2.96 (1H, d, J = 1.9 Hz), 3.68 (1H, d, = 11.9 



Hz), 3.84 (1H, d, J = 12.0 Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz),



5.05 (1H, m), 5.32 (1H, dd, J = 5.3, 11.7 Hz), 6.43 (1H, s), 7.39 



(1H, dd, J = 4.9, 8.0 Hz), 7.56 (1H, d, J = 8.1 Hz), 7.85 (1H, t, 



J = 7.8 Hz), 8.07 (2H, m), 8.67 (1H, dd, J = 1.7, 4.9 Hz), 8.98 



(1H, d, J = 2.0 Hz)


258
0.91 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.38-1.46 (1H, m), 1.50 (3H, s), 1.62 (1H, d, J = 



2.4 Hz), 1.69-1.72 (2H, m), 1.86 (3H, s), 1.80-1.96 (2H, m), 



2.18-2.22 (1H, m), 2.32 (2H, q, J = 7.5 Hz), 2.41 (2H, dq, J = 



2.2, 7.5 Hz), 2.93 (1H, d, J = 1.9 Hz), 3.68 (1H, d, J = 11.9 Hz),



3.83 (1H, d, J = 12.0 Hz), 4.83 (1H, dd, J = 4.9, 11.4 Hz), 5.04 



(1H, m), 5.33 (1H, dd, J = 5.3, 11.5 Hz), 6.42 (1H, s), 7.20 (1H, 



dd, J = 2.9, 8.0 Hz), 7.38 (1H, dd, J = 4.9, 8.3 Hz), 8.00 (1H, q, 



J = 7.8 Hz), 8.08 (2H, m), 8.67 (1H, dd, J = 1.4, 4.6 Hz), 8.97 



(1H, d, J = 2.2 Hz)


259
0.93 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.21 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.40-1.47 (1H, m), 1.51 (3H, s), 1.61 (1H, d, J = 



3.0 Hz), 1.70-1.83 (2H, m), 1.86 (3H, s), 1.92-1.98 (2H, m), 



2.17-2.22 (1H, m), 2.32 (2H, q, J = 7.3 Hz), 2.43 (2H, dq, J = 



1.4, 5.3 Hz), 2.97 (1H, d, J = 2.0 Hz), 3.74 (1H, d, J = 11.7 Hz),



3.83 (1H, d, J = 11.7 Hz), 4.13 (3H, s), 4.84 (1H, dd, J = 4.9,



11.4 Hz), 5.05 (1H, m), 5.24 (1H, dd, J = 5.3, 11.7 Hz), 6.43 



(1H, s), 7.16-7.20 (1H, m), 7.35-7.44 (4H, m), 7.70 (1H, d, J = 



8.1 Hz), 8.05 (1H, dt, J = 1.7, 8.3 Hz), 8.66 (1H, dd, J = 1.5, 4.9 



Hz), 8.96 (1H, d, J = 2.2 Hz)


260
0.93 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.40-1.46 (1H, m), 1.48 (3H, s), 1.63 (1H, d, J = 



3.0 Hz), 1.71-1.74 (2H, m), 1.80 (3H, s), 1.83-1.95 (1H, m), 



2.02-2.06 (1H, m), 2.18-2.22 (1H, m), 2.32 (2H, dq, J = 1.7, 7.6 



Hz), 2.41 (2H, dq, J = 3.4, 7.5 Hz), 2.96 (1H, m), 3.70 (1H, d, 



J = 12.0 Hz), 3.87 (1H, d, J = 11.9 Hz), 4.83 (1H, dd, J = 4.8, 



11.5 Hz), 5.05 (1H, m), 5.37 (1H, dd, J = 4.9, 11.7 Hz), 6.46 



(1H, s), 7.39-7.45 (2H, m), 7.87 (1H, dd, J = 1.5, 8.3 Hz), 8.08 



(1H, dt, J = 1.5, 8.3 Hz), 8.64 (1H, dd, J = 1.2, 4.6 Hz), 8.69 



(1H, d, J = 4.9 Hz), 8.97 (1H, d, J = 2.2 Hz)


261
0.85-1.06 (8H, m), 0.92 (3H, s), 1.26 (1H, s), 1.30-1.40 (1H, m), 



1.42 (3H, s), 1.45-1.63 (5H, m), 1.67 (3H, s), 1.81-1.92 (2H, m), 



2.14-2.25 (2H, m), 2.88 (1H, d, J = 1.4 Hz), 3.75 (1H, d, J = 



11.9 Hz), 3.86 (1H, d, J = 11.6 Hz), 3.78-3.82 (1H, m), 4.82 



(1H, dd, J = 5.1, 11.4 Hz), 5.00 (1H, m), 6.52 (1H, s), 7.42 (1H, 



dd, J = 4.9, 8.0 Hz), 8.11 (1H, dt, J = 1.7, 8.0 Hz), 8.69 (1H, dd, 



J = 1.5, 4.9 Hz), 9.01 (1H, d, J = 1.9 Hz)

















TABLE 28





 
1H-NMR δ (ppm)







262
0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.20 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.39-1.47 (1H, m), 1.49 (3H, s), 1.61 (1H, d, J = 



2.7 Hz), 1.66-1.71 (2H, m), 1.84 (3H, s), 1.76-1.99 (2H, m), 



2.18-2.22 (1H, m), 2.32 (2H, dq, J = 1.0, 7.5 Hz), 2.42 (2H, dq, 



J = 2.7, 7.5 Hz), 2.96 (1H, m), 3.73 (1H, d, J = 11.9 Hz), 3.82 



(1H, d, J = 11.9 Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz), 5.04 (1H, 



m), 5.26 (1H, dd, J = 5.1, 11.7 Hz), 6.44 (1H, s), 7.35-7.41 (2H, 



m), 8.07 (1H, dt, J = 1.7, 8.0 Hz), 8.44-8.50 (2H, m), 8.67 (1H, 



d, J = 4.9 Hz), 8.98 (1H, d, J = 1.7 Hz)


263
0.92 (3H, s), 1.12 (3H, t, J = 7.5 Hz), 1.20 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.30-1.47 (1H, m), 1.50 (3H, s), 1.62 (1H, d, J = 



2.4 Hz), 1.69-1.71 (2H, m), 1.85 (3H, s), 1.75-1.97 (2H, m), 



2.18-2.22 (1H, m), 2.33 (2H, dq, J = 0.9, 7.6 Hz), 2.42 (2H, dq, 



J = 2.4, 7.6 Hz), 2.98 (1H, m), 3.73 (1H, d, J = 11.6 Hz), 3.81 



(1H, d, J = 11.9 Hz), 4.84 (1H, dd, J = 4.9, 11.7 Hz), 5.05 (1H, 



m), 5.26 (1H, dd, J = 5.1, 11.5 Hz), 6.40 (1H, s), 7.38 (1H, dd, 



J = 4.9, 8.0 Hz), 7.80 (2H, d, J = 8.8 Hz), 8.06 (1H, dt, J = 1.7, 



8.0 Hz), 8.21 (2H, d, J = 8.8 Hz), 8.67 (1H, dd, J = 1.5, 4.9 Hz), 



8.96 (1H, d, J = 1.7 Hz)


264
0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.20 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.39-1.47 (1H, m), 1.51 (3H, s), 1.62 (1H, d, J = 



2.4 Hz), 1.68-1.82 (2H, m), 1.86 (3H, s), 1.93-2.01 (2H, m), 



2.19-2.23 (1H, m), 2.32 (2H, dq, J = 1.0, 7.6 Hz), 2.42 (2H, dq, 



J = 2.4, 7.5 Hz), 2.97 (1H, m), 3.73 (1H, d, J = 11.9 Hz), 3.80 



(1H, d, J = 11.9 Hz), 4.84 (1H, dd, J = 4.9, 11.7 Hz), 5.05 (1H, 



m), 5.26 (1H, dd, J = 5.1, 11.5 Hz), 6.41 (1H, s), 7.38 (1H, dd, 



J = 4.1, 8.0 Hz), 7.65 (1H, m), 7.90 (1H, dt, J = 1.5, 7.8 Hz), 



8.07 (1H, dt, J = 2.2, 8.0 Hz), 8.34 (1H, dt, J = 1.5, 7.8 Hz), 8.38 



(1H, t, J = 1.5 Hz), 8.67 (1H, dd, J = 1.5, 4.9 Hz), 8.96 (1H, d, 



J = 2.4 Hz)


265
0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.21 (3H, t, J = 7.5 Hz), 



1.26 (1H, s), 1.39-1.48 (1H, m), 1.51 (3H, s), 1.63 (1H, d, J = 



2.7 Hz), 1.63-1.83 (2H, m), 1.86 (3H, s), 1.90-1.98 (2H, m), 



2.18-2.23 (1H, m), 2.33 (2H, q, J = 7.5 Hz), 2.43 (2H, dq, J = 



2.5, 7.6 Hz), 2.97 (1H, m), 3.72 (1H, d, J = 11.9 Hz), 3.82 (1H, 



d, J = 12.0 Hz), 4.84 (1H, dd, J = 4.9, 11.4 Hz), 5.05 (1H, d, J = 



4.1 Hz), 5.28 (1H, dd, J = 5.1, 11.5 Hz), 6.42 (1H, s), 7.38 (1H, 



dd, J = 4.9, 8.0 Hz), 7.65 (1H, t, J = 7.8 Hz), 7.88 (1H, d, J = 7.8 



Hz), 8.06 (1H, dt, J = 1.8, 8.0 Hz), 8.30 (1H, d, J = 8.1 Hz), 8.36 



(1H, s), 8.67 (1H, dd, J = 1.5, 4.9 Hz), 8.97 (1H, d, J = 2.2 Hz)


266
0.89 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.14 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.33-1.37 (1H, m), 1.42 (3H, s), 1.46-1.55 (1H, m), 



1.58 (3H, s), 1.60-1.70 (2H, m), 1.78-1.91 (2H, m), 2.13-2.17 



(1H, m), 2.32 (2H, dq, J = 1.7, 7.3 Hz), 2.35 (2H, q, J = 7.3 Hz), 



2.89 (1H, m), 3.66 (1H, d, J = 11.4 Hz), 3.81 (1H, d, J = 12.0 



Hz), 3.96 (2H, s), 4.76-4.82 (1H, m), 4.98-5.06 (2H, m), 6.38 



(1H, s), 7.17-7.25 (1H, m), 7.36-7.46 (2H, m), 7.69-7.73 (1H, 



m), 8.08-8.12 (1H, m), 8.60 (1H, dt, J = 1.0, 4.9 Hz), 8.70 (1H, 



dd, J = 1.7, 4.9 Hz), 9.00 (1H, d, J = 1.4 Hz)

















TABLE 29





 
1H-NMR δ (ppm)







267
0.89 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.15 (3H, t, J = 7.6 Hz), 



1.26 (1H, s), 1.43 (3H, s), 1.50 (3H, d, J = 3.0 Hz), 1.61 (3H, s), 



1.58-1.70 (2H, m), 1.75-1.93 (2H, m), 2.14-2.18 (1H, m), 2.32 



(2H, q, J = 7.6 Hz), 2.36 (2H, q, J = 7.6 Hz), 2.90 (1H, d, J = 1.9 



Hz), 3.70 (1H, d, J = 12.0 Hz), 3.74 (2H, s), 3.77 (1H, d, J = 



11.9 Hz), 4.79 (1H, dd, J = 4.9, 11.4 Hz), 4.96-5.00 (2H, m), 



6.37 (1H, s), 7.32 (1H, dd, J = 4.8, 7.6 Hz), 7.42 (1H, dd, J = 



4.9, 8.1 Hz), 7.71 (1H, d, J = 7.8 Hz), 8.12 (1H, dt, J = 1.9, 8.1 



Hz), 8.57 (1H, dd, J = 1.6, 4.8 Hz), 8.65 (1H, d, J = 1.9 Hz), 



8.70 (1H, dd, J = 1.6, 4.7 Hz), 9.04 (1H, d, J = 4.2 Hz)


269
0.85-1.11 (8H, m), 0.93 (3H, s), 1.26 (1H, s), 1.39-1.47 (1H, m), 



1.50 (3H, s), 1.55-1.68 (5H, m), 1.87 (3H, s), 1.83-2.02 (2H, m), 



2.17-2.22 (1H, m), 2.96 (1H, s), 3.79 (1H, d, J = 12.2 Hz), 3.83 



(1H, d, J = 12.1 Hz), 4.85 (1H, dd, J = 4.9, 11.5 Hz), 5.04 (1H, 



m), 5.38 (1H, dd, J = 5.12, 11.6 Hz), 6.46 (1H, s), 7.38 (1H, dd, 



J = 4.8, 8.2 Hz), 7.69-7.80 (2H, m), 7.87 (1H, m), 8.08 (1H, dt, 



J = 2.2, 8.0 Hz), 8.22 (1H, dd, J = 1.7, 7.5 Hz), 8.67 (1H, dd, J =



1.5, 4.9 Hz), 8.98 (1H, d, J = 2.4 Hz)


270
0.86-1.10 (8H, m), 0.94 (3H, s), 1.26 (1H, s), 1.38-1.46 (1H, m), 



1.49 (3H, s), 1.57-1.69 (5H, m), 1.75 (3H, s), 1.78-2.05 (2H, m), 



2.18-2.21 (1H, m), 2.93 (1H, m), 3.80 (1H, d, J = 11.9 Hz), 3.84 



(1H, d, J = 11.9 Hz), 4.84 (1H, dd, J = 5.0, 11.6 Hz), 5.04 (1H, 



m), 5.31 (1H, dd, J = 5.0, 11.8 Hz), 6.42 (1H, s), 7.40 (1H, dd, 



J = 4.9, 8.3 Hz), 7.70 (1H, d, J = 5.3 Hz), 8.09 (1H, dt, J = 1.7, 



8.1 Hz), 8.69 (1H, dd, J = 1.6, 4.7 Hz), 8.97 (1H, d, J = 5.1 Hz),



9.00 (1H, d, J = 2.2 Hz), 9.17 (1H, s)


271
0.85-1.08 (8H, m), 0.92 (3H, s), 1.26 (1H, s), 1.38-1.46 (1H, m), 



1.48 (3H, s), 1.56-1.68 (5H, m), 1.79 (3H, s), 1.83-2.08 (2H, m), 



2.18-2.21 (1H, m), 2.95 (1H, m), 3.76 (1H, d, J = 11.9 Hz), 3.86 



(1H, d, J = 11.9 Hz), 4.83 (1H, dd, J = 4.9, 11.5 Hz), 5.04 (1H, 



m), 5.39 (1H, dd, J = 5.1, 11.9 Hz), 646 (1H, s), 7.34-7.45 (2H, 



m), 7.86 (1H, dd, J = 1.3, 8.0 Hz), 8.08 (1H, dt, J = 2.0, 8.0 Hz), 



8.64 (1H, dd, J = 1.2, 4.7 Hz), 8.68 (1H, dd, J = 1.5, 4.9 Hz), 



9.00 (1H, d, J = 2.2 Hz)









Example 11
Preparation Example 1
Wettable Powder
Compound According to the Present Invention















(Compound No. 82)
30 wt %



Clay
30 wt %



Diatomaceous earth
35 wt %



Calcium lignin sulfonate
 4 wt %



Sodium laurylsulfate
 1 wt %









The above ingredients were homogeneously mixed together, and the mixture was ground to prepare wettable powder.

Preparation Example 2
Dust
Compound According to the Present Invention















(Compound No. 82)
 2 wt %



Clay
60 wt %



Talc
37 wt %



Calcium stearate
 1 wt %









The above ingredients were homogeneously mixed together to prepare dust.

Preparation Example 3
Emulsifiable Concentrate
Compound According to the Present Invention















(Compound No. 82)
20 wt %



N,N-Dimethylformamide
20 wt %



Solvesso 150 (Exxon Mobil Corporation)
50 wt %



Polyoxyethylene alkylaryl ether
10 wt %









The above ingredients were homogeneously mixed and dissolved to prepare emulsifiable concentrate.

Preparation Example 4
Granules
Compound According to the Present Invention















(Compound No. 28)
5 wt %



Bentonite
40 wt %



Talc
10 wt %



Clay
43 wt %



Calcium lignin sulfonate
 2 wt %









The above ingredients were homogeneously ground and homogeneously 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 5
Floables
Compound According to the Present Invention
















(Compound No. 28)
25
wt %



POE polystyrylphenyl 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.

Test Example 1
Pesticidal Effect Against Mvzus Persicae 
Among the compounds of formula (I) produced by the conventional method described above, the compounds shown in Tables 1 to 14 and pyripyropene A were tested for pesticidal effect.
A leaf disk having a diameter of 2.8 cmφ was cut out from a cabbage grown in a pot and was placed in a 5.0 cm-Schale. Four adult aphids of Myzus persicae were released in the Schale. One day after the release of the adult aphids, the adult aphids were removed. The number of larvae at the first instar born in the leaf disk was adjusted to 10, and a test solution, which had been adjusted to a concentration of 20 ppm by the addition of a 50% aqueous acetone solution (0.05% Tween 20 added) was spread over the cabbage leaf disk. The cabbage leaf disk was then air dried. Thereafter, the Schale was lidded and was allowed to stand in a temperature-controlled room (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.

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

As result, it was found that the death rate was not less than 80% for compounds of Nos. 1, 6, 8, 9, 10, 12, 14, 16, 18, 20, 23, 25, 28, 34, 35, 36, 37, 38, 39, 40, 44, 45, 49, 54, 56, 57, 61, 69, 76, 82, 85, 86, 88, 90, 91, 98, 103, 106, 107, 108, 109, 111, 125, 128, 133, 135, 137, 139, 142, 153, 160, 161, 162, 164, 167, 169, 170, 171, 172, 176, 180, 182, 183, 186, 187, 190, 196, 201, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 226, 227, 228, 229, 230, 231, 232, 233, 236, 237, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, and 274 and pyripyropene A.
Test Example 2
Pesticidal Effect Against Mvzus Persicae 
Among the compounds of formula (I) produced by the conventional method described above, the compounds shown in Tables 1 to 14 and pyripyropene A were tested for pesticidal effect.
A leaf disk having a diameter of 2.8 cmφ was cut out from a cabbage grown in a pot and was placed in a 5.0 cm-Schale. Four adult aphids of Myzus persicae were released in the Schale. One day after the release of the adult aphids, the adult aphids were removed. The number of larvae at the first instar born in the leaf disk was adjusted to 10, and a test solution, which had been adjusted to a concentration of 0.156 ppm by the addition of a 50% aqueous acetone solution (0.05% Tween 20 added) was spread over the cabbage leaf disk. The cabbage leaf disk was then air dried. Thereafter, the Schale was lidded and was allowed to stand in a temperature-controlled room (light period 16 hr-dark period 8 hr) (25° C.). Three days after the initiation of standing, the larvae were observed for survival or death, and the death rate of larvae was calculated in the same manner as in Test Example 1.
As result, it was found that the death rate was not less than 80% for compounds of Nos. 12, 23, 28, 45, 54, 56, 76, 82, 85, 86, 90, 164, 201, 205, 206, 207, 212, 213, 217, 218, 219, 222, 227, 228, 229, 231, 232, 233, 237, 239, 240, 242, 246, 247, 249, 250, 252, 253, 256, 258, 261, 262, 264, 265, 266, 267, 269, 270, and 271.
Test Example 3
Pesticidal Effect Against Plutella Xylostella 
A cabbage leaf disk having a diameter of 5 cm was placed in a plastic cup. Test compounds, which had been diluted to a predetermined concentration by the addition of a 50% aqueous acetone solution (Tween 20, 0.05% added), were spreaded over the cabbage leaf disk by means of a spray gun, and the cabbage leaf disk was then air dried. Five larvae at the second instar of Plutella xylostella were released in the cup. The cup was then lidded, and the larvae were reared in the temperature-controlled room (25° C.). Three days after the treatment, the larvae were observed for survival or death, and the death rate of the larvae was calculated in the same manner as in Test Example 1.
As a results, it was found that the death rate was not less than 80% for compounds of Nos. 76, 213, 218, 237 and 250 at a concentration of 500 ppm.
Test Example 4
Pesticidal Effect Against Helicoverpa Armigera 
A cabbage leaf disk having a diameter of 2.8 cm was placed is in a plastic cup. Test compounds, which had been diluted to a predetermined concentration by the addition of a 50% aqueous acetone solution (Tween 20, 0.05% added), were spreaded over the cabbage leaf disk by means of a spray gun, and the cabbage leaf disk was then air dried. A larva at the third instar of Helicoverpa armigera was released in the cup. The cup was then lidded, and the larva was reared in the temperature-controlled room (25° C.). Three days after the treatment, the larva was observed for survival or death. The test was repeated 5 times. Further, the death rate of the larvae were calculated in the same manner as in Test Example 1.
As a result, it was found that the death rate was not less than 80% for the compound of No. 219 at a concentration of 100 ppm.
Test Example 5
Pesticidal Effect Against Trigonotylus Caelestialium 
A wheat seedling was immersed for 30 seconds in a solution, in which each test compound had been diluted to a predetermined concentration by the addition of a 50% aqueous acetone solution (Tween 20, 0.05% added). The wheat seedling was air dried, and then placed in a glass cylinder. Further, two larvae at the second instar of Trigonotylus caelestialium were released in the glass cylinder. The glass cylinder was then lidded, and the larvae were reared in the temperature-controlled room (25° C.). During the test, the wheat seedling was supplied with water from the bottom of the glass cylinder. Three days after the treatment, the larvae were observed for survival or death, and the death rate of the larvae were calculated in the same manner as in Test Example 1.
As a result, it was found that the death rate was not less than 80% for compound of Nos. 218 and 261 at a concentration of 100 ppm.

## Claims

1. A compound represented by formula (Ib) or an agriculturally and horticulturally acceptable salt thereof:



wherein
Het1 represents 3-pyridyl,
R1 represents hydroxyl,
R2 and R3 represent propionyloxy or optionally substituted cyclic C3-6 alkylcarbonyloxy, and
R4 represents hydroxyl,
optionally substituted cyclic C3-6 alkylcarbonyloxy,
optionally substituted benzoyloxy, or
optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy, provided that
a compound wherein
Het1 represents 3-pyridyl,

R1 represents hydroxyl,
R2 and R3 represent propionyloxy, and
R4 represents hydroxyl,
is excluded.

2. The compound according to claim 1 or an agriculturally and horticulturally acceptable salt thereof, wherein
R2 and R3 represent optionally substituted cyclic C3-6 alkylcarbonyloxy, and
R4 represents hydroxyl, optionally substituted cyclic C3-6 alkylcarbonyloxy, or optionally substituted benzoyloxy.

3. The compound according to claim 1 or an agriculturally and horticulturally acceptable salt thereof, wherein
R2 and R3 represent propionyloxy, and
R4 represents optionally substituted cyclic C3-6 alkylcarbonyloxy or optionally substituted saturated or unsaturated five- or six-membered heterocyclic carbonyloxy.

4. An agricultural and horticultural composition comprising the compound according to claim 1 or an agriculturally and horticulturally acceptable salt thereof as active ingredient and an agriculturally and horticulturally acceptable carrier.