# Patent

## Title
Pest control agents

## Abstract

There is provided a pest control agent comprising a compound represented by formula (I) as active ingredient.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to 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 Pub. No. 360895/1992) Publication 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, Japanese Patent Laid-Open Pub. No. 184158/1994, Japanese Patent Laid-Open Pub. No. 239385/1996, Japanese Patent Laid-Open Pub. No. 259569/1996, Japanese Patent Laid-Open Pub. No. 269062/1996, Japanese Patent Laid-Open Pub. No. 269063/1996, Japanese Patent Laid-Open Pub. No. 269064/1996, Japanese Patent Laid-Open Pub. No. 269065/1996, Japanese Patent Laid-Open Pub. No. 269066/1996, Japanese Patent Laid-Open Pub. 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 Publication (Japanese version) 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.
The present invention has been made based on such finding.
Accordingly, an object of the present invention is to provide 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.
And, the pest control agent according to the present invention comprises a compound represented by formula (I) as active ingredient:




[wherein

Het1 represents a saturated or unsaturated five- to six-membered heterocyclic ring,
R1 represents a hydroxyl group,
an optionally substituted C1-6 alkylcarbonyloxy group,
an optionally substituted C2-6 alkenylcarbonyloxy group,
an optionally substituted C2-6 alkynylcarbonyloxy group,
an optionally substituted C1-6 alkyloxy group,
an optionally substituted C2-6 alkenyloxy group,
an optionally substituted C2-6 alkynyloxy group,
an optionally substituted benzyloxy group, or
an oxo group 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 a hydroxyl group,
an optionally substituted C1-18 alkylcarbonyloxy group,
an optionally substituted C2-6 alkenylcarbonyloxy group,
an optionally substituted C2-6 alkynylcarbonyloxy group,
an optionally substituted benzoyloxy group,
an optionally substituted C1-6 alkylsulfonyloxy group,
an optionally substituted C1-6 alkyloxy group,
an optionally substituted C2-6 alkenyloxy group,
an optionally substituted C2-6 alkynyloxy group,
a C1-6 alkyloxy-C1-6 alkyloxy group,
a C1-6 aklylthio-C1-6 alkyloxy group,
an optionally substituted C1-6 alkyloxycarbonyloxy group,
an optionally substituted C1-6 alkylaminocarbonyloxy group, or
the bond between 1-position and 2-position represents a double bond in the absence of R2, and
R3 represents a hydrogen atom,
a hydroxyl group,
an optionally substituted C1-18 alkylcarbonyloxy group,
an optionally substituted C2-6 alkenylcarbonyloxy group,
an optionally substituted C2-6 alkynylcarbonyloxy group,
an optionally substituted benzoyloxy group,
an optionally substituted C1-6 alkylsulfonyloxy group,
an optionally substituted benzenesulfonyloxy group,
an optionally substituted C1-6 alkyloxy group,
an optionally substituted C2-6 alkenyloxy group,
an optionally substituted C2-6 alkynyloxy group,
an optionally substituted C1-6 alkyloxycarbonyloxy group,
an optionally substituted C1-6 alkylaminocarbonyloxy group, or
an optionally substituted five- to six-membered heterocyclic thiocarbonyloxy group, 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,
a hydroxyl group,
an optionally substituted C1-18 alkylcarbonyloxy group,
an optionally substituted C2-6 alkenylcarbonyloxy group,
an optionally substituted C2-6 alkynylcarbonyloxy group,
an optionally substituted benzoyloxy group,
an optionally substituted C1-6 alkylsulfonyloxy group,
an optionally substituted benzenesulfonyloxy group,
an optionally substituted benzyloxy group,
an optionally substituted C1-6 alkyloxy group,
an optionally substituted C2-6 alkenyloxy group,
an optionally substituted C2-6 alkynyloxy group,
a C1-6 alkyloxy-C1-6 alkyloxy group,
a C1-6 alkylthio-C1-6 alkyloxy group,
a C1-6 alkyloxy-C1-6 alkyloxy-C1-6 alkyloxy group,
an optionally substituted C1-6 alkyloxycarbonyloxy group,
an optionally substituted C1-6 alkylaminocarbonyloxy group,
an optionally substituted saturated or unsaturated five- to six-membered heterocyclic oxy group,
an optionally substituted saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group,
an optionally substituted saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group, or
an oxo group in the absence of a hydrogen atom at the 7-position, provided that
a compound wherein
Het1 represents a 3-pyridyl group,
R1 represents a hydroxyl group, and
all of R2, R3, and R4 represent an acetyloxy group, is excluded.]
Further, the hemipteran pest control agent according to the present invention comprises a compound represented by formula (Ia) as active ingredient:




[wherein

Het2 represents optionally substituted saturated or unsaturated five- to six-membered heterocyclic ring,
R11 represents a hydroxyl group,
an optionally substituted C1-6 alkylcarbonyloxy group,
an optionally substituted C2-6 alkenylcarbonyloxy group,
an optionally substituted C2-6 alkynylcarbonyloxy group,
an optionally substituted C1-6 alkyloxy group,
an optionally substituted C2-6 alkenyloxy group,
an optionally substituted C2-6 alkynyloxy group,
an optionally substituted benzyloxy, or
an oxo group 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 a hydroxyl group,
an optionally substituted C1-18 alkylcarbonyloxy group,
an optionally substituted C2-6 alkenylcarbonyloxy gorup,
an optionally substituted C2-6 alkynylcarbonyloxy group,
an optionally substituted benzoyloxy group, or
an optionally substituted C1-6 alkylsulfonyloxy group,
an optionally substituted C1-6 alkyloxy group,
an optionally substituted C2-6 alkenyloxy group,
an optionally substituted C2-6 alkynyloxy group,
a C1-6 alkyloxy-C1-6 alkyloxy group,
a C1-6 alkylthio-C1-6 alkyloxy group,
an optionally substituted C1-6 alkyloxycarbnyloxy group,
an optionally substituted C1-6 alkylaminocarbonyloxy group, or
the bond between 1-position and 2-position represents a double bond in the absence of R12, and
R13 represents a hydrogen atom,
a hydroxyl group,
an optionally substituted C1-18 alkylcarbonyloxy group,
an optionally substituted C2-6 alkenylcarbonyloxy group,
an optionally substituted C2-6 alkynylcarbonyloxy group,
an optionally substituted benzoyloxy group,
an optionally substituted C1-6 alkylsulfonyloxy group,
an optionally substituted benzenesulfonyloxy group, or
an optionally substituted C1-6 alkyloxy group,
an optionally substituted C2-6 alkenyloxy group,
an optionally substituted C2-6 alkynyloxy group,
an optionally substituted C1-6 alkyloxycarbonyloxy group,
an optionally substituted C1-6 alkylaminocabonyloxy group,
an optionally substituted five- to six-membered heterocyclic thiocarbonyloxy group, 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, a C1-6 alkyl group, a C1-6 alkyloxy, group, a C2-6 alkenyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R12′ and R13′ together represent an oxo group or a C2-6 alkylene group), and
R14 represents a hydrogen atom,
a hydroxyl group,
an optionally substituted C1-18 alkylcarbonyloxy group,
an optionally substituted C2-6 alkenylcarbonyloxy group,
an optionally substituted C2-6 alkynylcarbonyloxy group,
an optionally substituted benzoyloxy group,
an optionally substituted C1-6 alkylsulfonyloxy group,
an optionally substituted benzenesulfonyloxy group,
an optionally substituted benzyloxy,
an optionally substituted C1-6 alkyloxy group,
an optionally substituted C2-6 alkenyloxy group,
an optionally substituted C2-6 alkynyloxy group,
a C1-6 alkyloxy-C1-6 alkyloxy group,
a C1-6 alkylthio-C1-6 alkyloxy group,
a C1-6 alkyloxy-C1-6 alkyloxy-C1-6 alkyloxy group,
an optionally substituted C1-6 alkyloxycarbonyloxy group,
an optionally substituted C1-6 alkylaminocarbonyloxy group,
an optionally substituted saturated or unsaturated five- to six-membered heterocyclic oxy group,
an optionally substituted saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group,
an optionally substituted saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group, or
an oxo group in the absence of a hydrogen atom at the 7-position.]
The pyripyropene derivatives represented by formula (I) 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 as 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.
Further, the terms “alkyl,” “alkenyl,” and “alkynyl” as used in this specification 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 “C1-6alkyl” 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, the term “heterocyclic ring” as used in this specification 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 in this specification 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 also true for functional groups other than the alkyl group.
Examples of the “saturated or unsaturated five- to six-membered heterocyclic ring” represented by Het1 and Het2 include a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, an isothiazoyl group, an isoxazolyl group, a thiazolyl group, an oxazolyl group, a pyridynyo group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, and a pyridazinyl group, and more specific examples thereof include a (2- or 3-)thienyl group, a (2- or 3-)furyl group, a (1-, 2- or 3-)pyrrolyl group, a (1-, 2-, 4- or 5-)imidazolyl group, a (1-, 3-, 4- or 5-)pyrazolyl group, a (3-, 4- or 5-)isothiazolyl group, a (3-, 4- or 5-)isoxazolyl group, a (2-, 4- or 5-)thiazolyl group, a (2-, 4- or 5-)oxazolyl group, a 1-oxydopyridynio group, a 1-methylpyridynyo group, a (2-, 3- or 4-)pyridyl group or, a (2-, 4-, 5- or 6-)pyrimidinyl group, a (2- or 3-)pyrazinyl group, and a (3- or 4-)pyridazinyl group, preferred are a pyridyl group, a thiazolyl group, a pyrazolyl group, a pyrimidinyl group, and a pyrrolyl group, and more preferred are a 3-pyridyl group. Here, this saturated or unsaturated five- to six-membered heteriocyclic ring may be substituted, and substituents include halogen atoms, a C1-4 alkyl group, a C1-4 alkyloxy group, a nitro group, a cyano group, a formyl group, a trifluoromethyl group, a trifluoromethoxy group, a trifluoromethylthio group, a trifluoromethylsulfinyl group, a trifluoromethylsulfonyl group, an acetyl group, and an acetyloxy group, preferred are halogen atoms and a trifluoromethyl group, and more preferred are a chlorine atom and a trifluoromethyl group.
The “C1-6 alkylcarbonyloxy group” represented by R1 and R11 is optionally substituted, and substituents include halogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio groups.
The “C1-18 alkylcarbonyloxy group” represented by R2, R3 and R4, and R12, R13 and R14 is preferably a C1-6 alkylcarbonyloxy group. This C1-18 alkylcarbonyloxy group is optionally substituted, and substituents include halogen atoms and cyano, phenyl, trifluoromethoxy, and trifluoromethylthio groups.
The “C2-6 alkenylcarbonyloxy group” 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.
The “C2-6 alkynylcarbonyloxy group” represented by R1, R2, R3 and R4, and R11, R12, R13 and R14 is optionally substituted, and substituents include halogen atoms and cyano, phenyl, trifluoromethoxy, and trifluoromethylthio groups.
The “C1-6 alkyloxy group” represented by R1, R2, R3, R4, and R11, R12, R13, and R14 is optionally substituted, and substituents include halogen atoms; a cyano group; a phenyl group; a trifluoromethoxy group; a trifluoromethylthio group; a C1-6 alkylcarbonyl group optionally substituted by a halogen atom; and a C1-6 alkylcarbonyloxy group optionally substituted by a halogen atom.
The “C2-6 alkenyloxy group” represented by R1, R2, R3, R4, and R11, R12, R13 and R14 is optionally substituted, and substituents include halogen atoms; a cyano group; a phenyl group; a trifluoromethoxy group; a trifluoromethylthio group; a C1-6 alkylcarbonyl group optionally substituted by a halogen atom; and a C1-6 alkylcarbonyloxy group optionally substituted by a halogen atom.
The “C2-6 alkynyloxy group” represented by R1, R2 R3, R4, and R11, R12, R13 and R14 is optionally substituted, and substituents include halogen atoms; a cyano group; a phenyl group; a trifluoromethoxy group; a trifluoromethylthio group; a C1-6 alkylcarbonyl group optionally substituted by a halogen atom; and a C1-6 alkylcarbonyloxy group optionally substituted by a halogen atom.
The phenyl group in the “benzyloxy group” represented by R1 and R4, and R11 and R14 is optionally substituted, and substituents include halogen atoms; a C1-6 alkyloxy group optionally substituted by a halogen atom; a C1-6 alkyl group optionally substituted by a halogen atom; a C1-6 alkylcarbonyl group optionally substituted by a halogen atom; a C1-6 alkylcarbonyloxy group optionally substituted by a halogen atom; a C1-6 alkylcarbonylamino group optionally substituted by a halogen atom; a C1-6 alkylaminocarbonyloxy group optionally substituted by a halogen atom; a C1-6 alkylaminocarbonyl group optionally substituted by a halogen atom; a C1-6 alkylsulfonyloxy group optionally substituted by a halogen atom; a C1-6 alkylthio group optionally substituted by a halogen atom; a C1-6 alkylsulfinyl group optionally substituted by a halogen atom; a C1-6 alkylsulfonyl group optionally substituted by a halogen atom; a cyano group; formyl group; an azide group; a guanidyl group; group —C(═NH)—NH2; or group —CH═N—O—CH3.
The phenyl group in the “benzoyloxy group” represented by R2, R3 and R4, and R12, R13 and R14 is optionally substituted, and substituents include halogen atoms; a C1-6 alkyloxy group optionally substituted by a halogen atom; a C1-6 alkyl group optionally substituted by a halogen atom; a C1-6 alkylcarbonyl group optionally substituted by a halogen atom; a C1-6 alkylcarbonyloxy group optionally substituted by a halogen atom; a C1-6 alkylcarbonylamino group optionally substituted by a halogen atom; a C1-6 alkylaminocarbonyloxy group optionally substituted by a halogen atom; a C1-6 alkylaminocarbonyl group optionally substituted by a halogen atom; a C1-6 alkylsulfonyloxy group optionally substituted by a halogen atom; a C1-6 alkylthio group optionally substituted by a halogen atom; a C1-6 alkylsulfinyl group optionally substituted by a halogen atom; a C1-6 alkylsulfonyl group optionally substituted by a halogen atom; a cyano group; a formyl group; an azide group; a guanidyl group; group —C(═NH)—NH2; or group —CH═N—O—CH3.
The phenyl group in the “benzenesulfonyloxy group” represented by R3 and R4, and R13 and R14 is optionally substituted, and substituents include halogen atoms; a C1-6 alkyloxy group optionally substituted by a halogen atom; a C1-6 alkyl group optionally substituted by a halogen atom; a C1-6 alkylcarbonyl group optionally substituted by a halogen-atom; a C1-6 alkylcarbonyloxy group optionally substituted by a halogen atom; a C1-6 alkylcarbonylamino group optionally substituted by a halogen atom; a C1-6 alkylaminocarbonyloxy group optionally substituted by a halogen atom; a C1-6 alkylaminocarbonyl group optionally substituted by a halogen atom; a C1-6 alkylsulfonyloxy group optionally substituted by a halogen atom; a C1-6 alkylthio group optionally substituted by a halogen atom; a C1-6 alkylsulfinyl group optionally substituted by a halogen atom; a C1-6 alkylsulfonyl group optionally substituted by a halogen atom; a cyano group; a formyl group; an azide group; a guanidyl group; group —C(═NH)—NH2; or group —CH═N—O—CH3.
The “C1-6 alkylsulfonyloxy group” represented by R2, R3, and R4 and R12, R13 and R14 is optionally substituted, and substituents include halogen atoms, a cyano group, a phenyl group, a trifluoromethoxy group, or a trifluoromethylthio group.
The “C1-6 alkyloxycarbonyloxy group” represented by R2, R3, and R4 and R12, R13, and R14 is optionally substituted, and substituents include halogen atoms, a cyano group, a phenyl group, a trifluoromethyloxy group, or a trifluoromethylthio.
The “C1-6 alkylaminocarbonyloxy group” represented by R2, R3, and R4 and R12, R13, and R14 is optionally substituted, and substituents include halogen atoms, a cyano group, a phenyl group, a trifluoromethyloxy, or trifluoromethylthio.
The “phenyl group” and the phenyl group in the “benzyl group” represented by R2′ and R3′, and R12′ and R13′ is optionally substituted, and substituents include halogen atoms, a C1-4 alkyl group, a C1-4 alkyloxy group, a nitro group, a cyano group, a formyl group, a trifluoromethyloxy group, an acetyl group, or an acetyloxy group.
Examples of the saturated or unsaturated five- to six-membered oxy group, the saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, and the “saturated or unsaturated five- to six-membered heterocyclic ring” in the saturated or unsaturated five- to six-membered heterocyclic thiocabonyloxy group represented by R3 and R4, and R13, and R14 include a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, an isothiazoyl group, an isoxazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a tetrahydropyranyl group, a piperidinyl group, a piperadinyl group, a morpholynyl group, a tetrahydropyranyl group, or mannosyl group, preferably a pyridyl group, a furanyl group, a thiazolyl group, an imidazolyl group, a tetrahydropyranyl group, or a mannosyl group, and more specific examples thereof include a (2- or 3-)thienyl group, a (2- or 3-)furyl group, a (1-, 2- or 3-)pyrrolyl group, a (1-, 2-, 4- or 5-)imidazolyl group, a (1-, 3-, 4- or 5-)pyrazolyl group, a (3-, 4- or 5-)isothiazolyl group, a (3-, 4- or 5-)isoxazolyl group, a (2-, 4- or 5-)thiazolyl group, a (2-, 4- or 5-)oxazolyl group, a (2-, 3- or 4-)pyridyl group or, a (2-, 4-, 5- or 6-)pyrimidinyl group, a (2- or 3-)pyrazinyl group, a (3- or 4-)pyridazinyl group, (2-, 3- or 4-)tetrahydropyranyl group, (1-, 2-, 3- or 4-)piperidinyl group, (1-, 2- or 3-)piperadinyl group, and (2-, 3- or 4-) morpholinyl group, and preferred are a 3-pyridyl group, a 2-furanyl group, a 5-thiazolyl group, a 1-imidazolyl group, a 5-imidazolyl group, or a 2-tetrahydropyranyl group.
The above heterocyclic ring in the saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group and the saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group are optionally substituted, and substituents include halogen atoms, a C1-4 alkyl group, a C1-4 alkyloxy group, a nitro group, a cyano group, a formyl group, a trifluoromethyloxy group, a trifluoromethyl group, a trifluoromethylthio group, a trifluoromethylsulfinyl group, a trifluoromethylsulfonyl group, an acetyl group, and an acetyloxy group, and preferred are halogen atoms.
The heterocyclic ring in the above saturated or unsaturated five- to six-membered heterocyclic oxy group is optionally substituted, and substituents include a hydroxyl group, a benzyloxy group, a halogen atom, a C1-4 alkyl group, a C1-4 alkyloxy group, a nitro group, a cyano group, a formyl group, a trifluoromethoxy group, a trifluoromethyl group, a trifluoromethylthio group, a trifluoromethylsulfinyl group, a trifluoromethylsulfonyl group, an acetyl group, or an acetyloxy group, and preferred are a hydroxyl group or a benzyloxy group.
A composition represented by formula (I)
According to a preferred embodiment of the present invention, in the compound represented by formula (I), Het1 represents an optionally substituted pyridyl group, a 1-oxydopyridinyo group, a 1-methylpyridinyo group, an optionally substituted thiazolyl group, a pyrazolyl group, a pyrimidinyl group, or a pyrrolyl group.
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (I), R1 represents a hydroxyl group, a C1-6 alkylcarbonyloxy group, a C1-3 alkyloxy group, a benzyloxy group, or an oxo group 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, a hydroxyl group or a C1-6 alkylcarbonyloxy group 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 a hydroxyl group.
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (I), R2 represents a hydroxyl group, a C1-18 alkylcarbonyloxy group, an optionally substituted benzoyloxy group, a C1-3 alkylsulfonyloxy group, a C1-3 alkyloxy group, a C1-3 alkyloxy-C1-3 alkyloxy group, a C1-3 alkylthio-C1-3 alkyloxy group, C1-3 alkyloxycarbonyloxy group, a C1-3 alkylaminocarbonyloxy group, or the bond between 1-position and 2-position represents a double bond in the absence of R2, more preferably, a C1-8 alkylcarbonyloxy group, still more preferably, a C1-6 alkylcarbonyloxy group.
Further, in a preferred embodiment of the present invention, in the compound represented by formula (I), R3 represents a hydrogen atom, a hydroxyl group, a C1-18 alkylcarbonyloxy group, an optionally substituted benzoyloxy group, a C1-6 alkylsulfonyloxy group, an optionally substituted benzenesulfonyloxy group, a C1-6 alkyloxy group, a C1-3 alkyloxycarbonyloxy group, a C1-3 alkylaminocaronyloxy group, or a five- to six-membered heterocyclic thiocarbonyloxy group, more preferably, a C1-8 alkylcarbonyloxy group or a C1-6 alkylsulfonyloxy group, still more preferably, a C1-6 alkylcarbonyloxy group, particularly preferably, a C3-5 alkylcarbonyloxy group.
Further, 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, a C1-6 alkyl group, a C1-3 alkyloxy group, a C2-3 alkenyl group, a benzyl group, or an optionally substituted phenyl group, or R2′ and R3′ together represent an oxo group or a C2-6 alkylene group), more preferably, together represent —O—CR2′R3′—O— (wherein R2′ and R3′, which may be the same or different, represent a hydrogen atom, a C1-6 alkyl group, or an optionally substituted phenyl group, or R2′ and R3′ together represent an oxo group or a C2-6 alkylene group).
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (I), R4 represents a hydrogen atom, a hydroxyl group, an optionally substituted C1-18 alkylcarbonyloxy group, a C2-6 alkenylcarbonyloxy group, a C2-6 alkynylcarbonyloxy group, a C1-6 alkylsulfonyloxy group, a benzenesulfonyloxy group, a benzyloxy group, a C1-3 alkyloxy group, a C1-3 alkyloxy-C1-3 alkyloxy group, a C1-3 alkylthio-C1-3 alkyloxy group, a C1-3 alkyloxy-C1-3 alkyloxy-C1-3 alkyloxy-C1-3 alkyloxy group, an optionally substituted C1-3 alkyloxycarbonyloxy group, an optionally substituted C1-3 alkylaminocarbonyloxy group, an optionally substituted benzoyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, or saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group, or an oxo group in the absence of a hydrogen atom at the 7-position, more preferably, a hydroxyl group, a C1-18 alkylcarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, an optionally substituted benzoyloxy group, an optionally substituted C1-6 alkylaminocaronyloxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, a saturated or unsaturated five- to six-membered thiocarbonyloxy group, or an oxo group in the absence of a hydrogen atom at the 7-position, still more preferably, a C1-6 alkylcarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, or a benzoyloxy group, further more preferably, a C3-5 alkylcarbonyloxy group, a 2-tetrahydropyranyl group, or a benzoyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (I), Het1 represents a 3-pyridyl group, R1 represents a hydroxyl group or a C1-6 alkylcarbonyloxy group, 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 a C1-6 alkylcarbonyloxy group, R3 represents a C1-6 alkylcarbonyloxy group or a C1-6 alkylsulfonyloxy group, 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, a C1-6 alkyl group, or an optionally substituted phenyl group, or R2′ and R3′ together represent an oxo group or a C2-6 alkylene group), and R4 represents a hydroxyl group, a C1-6 alkylcarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, an optionally substituted benzoyloxy group, an optionally substituted C1-6 alkylaminocarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group, or an oxo group in the absence of a hydrogen atom at the 7-position.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (I), Het1 represents a 3-pyridyl group, R1 represents a hydroxyl group, R2 represents a C1-6 alkylcarbonyloxy group, and R3 and/or R4 represents a C3-5 alkylcarbonyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (I), Het represents a 3-pyridyl group, R1 represents a hydroxyl group, R2 represents a C1-6 alkylcarbonyloxy group, R3 represents a C1-6 alkylcarbonyloxy group or a C1-6 alkylsulfonyloxy group, and R4 represents a C1-6 alkylcarbonyloxy, an optionally substituted benzoyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, or a saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (I), R1 represents a hydroxyl group, and R2, R3, and R4 represent a C1-6 alkylcarbonyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (I), R1, R2, R3, and R4 represent a C1-6 alkylcarbonyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (I), R1 represents a hydroxyl group and R2 and R3 represent a C1-6 alkylcarbonyloxy group and R4 represents a saturated or unsaturated five- to six-membered heterocyclic oxy group.
A compound represented by formula (Ia)
According to a preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents an optionally substituted pyridyl group, a 1-oxydopyridinyo group, a 1-methylpyridinyo group, an optionally substituted thiazolyl group, a pyrazolyl group, a pyrimidinyl group, or a pyrrolyl group.
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (Ia), R11 represents a hydroxyl group, a C1-6 alkylcarbonyloxy group, a C1-3 alkyloxy group, a benzyloxy group, or an oxo group 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, a hydroxyl group or a C1-6 alkylcarbonyloxy group, 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 a hydroxyl group.
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (Ia), R12 represents a hydroxyl group, a C1-8 alkylcarbonyloxy group, an optionally substituted benzoyloxy group, a C1-3 alkylsulfonyloxy group, a C1-3 alkyloxy group, a C1-3 alkyloxy-C1-3 alkyloxy group, a C1-3 alkylthio-C1-3 alkyloxy group, a C1-3 alkyloxycarbonyloxy group, or a C1-3 alkylaminocarbonyloxy group, or the bond between 1-position and 2-position represents a double bond in the absence of R2, more preferably, a C1-8 alkylcarbonyloxy group, still more preferably, a C1-6 alkylcarbonyloxy group.
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (Ia), R13 represents a hydrogen atom, a hydroxyl group, a C1-18 alkylcarbonyloxy group, an optionally substituted benzoyloxy group, a C1-6 alkylsulfonyloxy group, an optionally substituted benzenesulfonyloxy group, a C1-6 alkyloxy group, a C1-3 alkyloxycarbonyloxy group, a C1-3 alkylaminocabonyloxy group, or a five- to six-membered thiocarbonyloxy group, more preferebly, a C1-18 alkylcarbonyloxy group or C1-6 alkylsulfonyloxy group, still more preferably, a C1-6 alkylcabonyloxy group, particularly preferably, a C3-5 alkylcaronyloxy group.
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, a C1-6 alkyl group, a C1-3 alkyloxy group, a C2-3 alkenyl group, a benzyl group, or an optionally substituted phenyl group, or R12′ and R13′ together represent an oxo group or a C2-6 alkylene group), more preferably, together represent —O—CR12′R13′—O— (wherein R12′ and R13′, which may be the same or different, represent a hydrogen atom, a C1-6 alkyl group, or an optionally substituted phenyl group, or R12′ and R13′ together represent an oxo group or a C2-6 alkylene group).
Further, according to a preferred embodiment of the present invention, in the compound represented by formula (Ia), R14 represents a hydrogen atom, a hydroxyl group, an optionally substituted C1-18 alkylcarbonyloxy group, a C2-6 alkenylcarbonyloxy group, a C2-6 alkynylcarbonyloxy group, a C1-6 alkylsulfonyloxy group, a benzenesulfonyloxy group, a benzyloxy group, a C1-3 alkyloxy group, a C1-3 alkyloxy-C1-3 alkyloxy group, a C1-3 alkylthio-C1-3 alkyloxy group, a C1-3 alkyloxy-C1-3 alkyloxy-C1-3 alkyloxy group, an optionally substituted C1-3 alkyloxycarbonyloxy group, an optionaly substituted C1-3 alkylaminocarbonyloxy group, an optionally substituted benzoyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, or saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group, or an oxo group in the absence of a hydrogen atom at the 7-position, more preferably, a hydroxyl group, a C1-18 alkylcarbonyloxy group, an optionally substituted benzoyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, a C1-6 alkylaminocarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group, or an oxo group in the absence of a hydrogen atom at the 7-position, still more preferably, a C1-6 alkylcarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, or benzoyloxy group, still more preferably, a C3-5 alkylcarbonyloxy group, a 2-tetrahydropyranyl group, or a benzoyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents a 3-pyridyl group, R11 represents a hydroxyl group, a C1-6 alkylcarbonyloxy group, 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 a C1-6 alkylcarbonyloxy group, and R13 represents a C1-6 alkylcarbonyloxy group, a C1-6 alkylsulfonyloxy group, 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, a C1-6 alkyl group, or an optionally substituted phenyl group, or R12′ and R13′ together represent an oxo group or a C2-6 alkylene group), and R14 represents a hydroxyl group, a C1-6 alkylcarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, an optionally substituted benzoyloxy group, an optionally substituted C1-6 alkylaminocarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic thiocarbonyloxy group, or, an oxo group in the absence of a hydrogen atom at the 7-position.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents a 3-pyridyl group, R11 represents a hydroxyl group, R12 represents a C1-6 alkylcarbonyloxy group, R13 and/or R14 represents a C3-5 alkylcarbonyloxy group.
Further, according to still another preferred embodiment of the present invention, in the compound represented by formula (Ia), Het2 represents a 3-pyridyl group, R11 represents a hydroxyl group, R12 represents a C1-6 alkylcarbonyloxy group, R13 represents a C1-6 alkylcarbonyloxy group, or C1-6 alkylsulfonyloxy group, and R14 represents a C1-6 alkylcarbonyloxy group, an optionally substituted benzoyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, or a saturated or unsaturated five- to six-membered thiocarbonyloxy group, and R14 represents a C1-6 alkylcarbonyloxy group, a saturated or unsaturated five- to six-membered heterocyclic oxy group, an optionally substituted benzoyloxy group, a saturated or unsaturated five- to six-membered heterocyclic carbonyloxy group, or a saturated or unsaturated five- to six-membered heterocyclic thiocabonyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (Ia), R11 represents a hydroxyl group, and R12, R13, and R14 represent a C1-6 alkylcarbonyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (Ia), R11, R12, R13, and R14 represent a C1-6 alkylcarbonyloxy group.
Further, according to another preferred embodiment of the present invention, in the compound represented by formula (Ia), R11 represents a hydroxyl group, R12 and R13 represent C1-6 alkylcarbonyloxy group, and R14 represents a saturated or unsaturated five- to six-membered heterocyclic oxy group.
Specific examples of the compounds represented by formula (I) or (Ia) above include compounds shown in Tables 1 to 14 below. In addition, in the following tables, H(═) means that the bond between 5-position and 13-position represents a double bond in the absence of R1 and a hydrogen atom at the 5-position.












TABLE 1





Compound No.
R1
R2
R3
R4
Het1




















1
OH
OCOCH3
OCOCH3
OCOCH2CH3
3-pyridyl


2
OH
OCOCH3
OCOCH3
OCOCH2CF3
3-pyridyl


3
OH
OCOCH3
OCOCH3
OCOCH2OCH3
3-pyridyl


4
OH
OCOCH3
OCOCH3
OCOCH2OCOCH3
3-pyridyl


5
OH
OCOCH3
OCOCH3
OCOCH2CH2CN
3-pyridyl


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


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


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


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


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


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


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


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


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


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


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


17
OH
OCOCH3
OCOCH3
OCOCH2C≡CCH3
3-pyridyl


18
OH
OCOCH3
OCOCH3
OCOC≡CCH2CH3
3-pyridyl


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





















TABLE 2





Compound No.
R1
R2
R3
R4
Het1







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


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-(p-Br—C6H4)
3-pyridyl


25
OH
OCOCH3
OCOCH3
OCO-(p-N3-C6H4)
3-pyridyl


26
OH
OCOCH3
OCOCH3
OCO-(p-OCF3-C6H4)
3-pyridyl


27
OH
OCOCH3
OCOCH3
OCO-(p-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





















TABLE 3





Compound No.
R1
R2
R3
R4
Het1







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


40
OH
OCOCH3
OCOCH3
OCONHCH2C6H5
3-pyridyl


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





















TABLE 4





Compound No.
R1
R2
R3
R4
Het1







59
OH
OCOCH3
OCOC6H5
OH
3-pyridyl


60
OH
OCOCH3
OCS-(1-imidazolyl)
OCOCH3
3-pyridyl


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
OCH2CH3
OCOCH3
3-pyridyl


67
OH
OCOCH3
C(H2)3CH3
OCOCH3
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





















TABLE 5





Compound No.
R1
R2
R3
R4
Het1







79
OH
OCOCH2CH3
H
H
3-pyridyl


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


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-p-Br—C6H4
OCO-p-Br—C6H4
OCO-p-Br—C6H4
3-pyridyl


97
OH
OCO-p-N3-C6H4
OSO2CH3
OCOCH3
3-pyridyl





















TABLE 6





Compound No.
R1
R2
R3
R4
Het1




















98
OH
OSO2CH3
OSO2CH3
OH
3-pyridyl


99
OH
OSO2CH3
OSO2CH3
OSO2CH3
3-pyridyl


100
OH
OSO2CH3
OSO2CH3
OCOCH3
3-pyridyl


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-(p-CH3-C6H5)
OH
3-pyridyl





















TABLE 7





Compound No.
R1
R2
R3
R4
Het1







117
OH
OH
OCO-p-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


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(i-Pr)—O—
OH
3-pyridyl


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


132
OH
—O—CH(OCH3)-O—
OH
3-pyridyl


133
OH
—O—CH(t-Bu)—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





















TABLE 8





Compound No.
R1
R2
R3
R4
Het1



















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


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(m-CH3-C6H4)-O—
OH
3-pyridyl


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


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


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


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


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


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


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


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


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


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





















TABLE 9





Compound No.
R1
R2
R3
R4
Het1



















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


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


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


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


159
OH
—O—CO—O—
OH
3-pyridyl


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


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





















TABLE 10





Compound No.
R1
R2
R3
R4
Het1







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(i-Pr)—O—
OH
3-pyridyl


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












180
H(═)
OCOCH3
OCOCH3
OCOCH3
3-pyridyl


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





















TABLE 11





Compound No.
R1
R2
R3
R4
Het1



















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(p-OCH3—C6H4)—O—
OH
3-pyridyl


197
H(═)
—O—CH(C2H5)—O—
OH
3-pyridyl


198
H(═)
—O—CH(t-Bu)—O—
OH
3-pyridyl


199
H(═)
—O—CH(CH2.C6H5)—O—
OH
3-pyridyl












200
═O
OH
OH
OH
3-pyridyl


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
1-CH3-3


205
OH
OCOCH3
OCOCH3
OCOCH3
1-CH3-pyridynio


206
OH
OCOCH3
OCOCH3
OCOCH3
1-oxydo-3-pyridynio


207
OH
OCOCH3
OCOCH3
OH
1-oxydo-3-pyridynio


208
OH
OCOCH3
OCOCH3
OCOH2C6H5
1-oxydo-3-pyridynio


209
OCH3
OCOCH3
OCOCH3
OCH3
1-oxydo-3-pyridynio


210
OCH3
OCOCH3
OCOCH3
OCOCH3
1-oxydo-3-pyridynio


211
OCH2C6H5
OCOCH3
OCOCH3
OCH2C6H5
l-oxydo-3-pyridynio





















TABLE 12





Compound No.
R1
R2
R3
R4
Het1







212
═O
OCOCH3
OCOCH3
OCOC3
1-oxydo-pyridynio


213
OH
OCOCH3
OCOCH3
OCOC3
4-pyridyl


214
OH
OCOCH3
OCOCH3
OH
4-pyridyl


215
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
4-pyridyl


216
OH
OCOCH3
OCOCH3
OCOC6H5
4-pyridyl


217
OH
OCO(CH2)3CH3
OSOCH3
OCO(CH2)3CH3
4-pyridyl


218
═O
OH
OH
OH
4-pyridyl


219
═O
OCOCH3
OCOCH3
OCOCH3
4-pyridyl


220
OH
OCOCH3
OCOCH3
OCOCH3
2-pyridyl


221
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
2-pyridyl


222
OH
OCOCH2CH3
OCOCH2CH3
OH
2-pyridyl


223
OH
OCO(CH2)3CF3
OSO2CH3
OCO(CH2)3CH3
2-pyridyl


224
OH
OCOCH3
OCOCH3
OCH2SCH3
2-pyridyl


225
═O
OCOCH3
OCOCH3
OCOH3
6-Cl-3-pyridyl


226
OH
OCOCH3
OCOCH3
OH
6-Cl-3-pyridyl


227
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
6-Cl-3-pyridyl


228
OH
OCOCH2CH3
OCOCH2CH3
OH
6-Cl-3-pyridyl


229
OH
DCOCH3
OCOCH3
OCO-(3-pyridyl)
6-Cl-3-pyridyl


230
OH
OCOCH3
OCOCH3
OCH2SCH3
6-Cl-3-pyridyl





















TABLE 13





Compound No.
R1
R2
R3
R4
Het1







231
OCOCH3
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
6-Cl-3-pyridyl


232
OH
OCO(CH2)3CH3
OSO2CH3
OH
6-Cl-3-pyridyl


233
H(═)
OCOCH3
OCOCH3
OCOCH3
6-Cl-3-pyridyl


234
H(═)
OCOCH2CH3
OCOCH2CH3
OH
6-Cl-3-pyridyl


235
═O
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
6-Cl-3-pyridyl


236
OH
OCOCH3
OCOCH3
OCOCH3
4-CF3-3-pyridyl


237
OH
OCOCH3
OCOCH3
OH
4-CF3-3-pyridyl


238
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
4-CF3-3-pyridyl


239
OH
OCOCH2CH3
OCOCH2CH3
OH
4-CF3-3-pyridyl


240
OH
OCOCH3
OCOCH3
OCOC6H5
4-CF3-3-pyridyl


241
OH
OCO(CH2)3CH3
OSO2CH3
OCO(CH2)3CH3
4-CF3-3-pyridyl


242
OCOCH3
OCOCH2CH3
OCOCH2CH3
OCH2SCH3
4-CF3-3-pyridyl


243
H(═)
OCOCH3
OCOCH3
OCOCH3
4-CF3-3-pyridyl


244
═O
OCOCH2CH3
OCOCH2CH3
OCOH2CH3
4-CF3-3-pyridyl


245
OH
OCOCH3
OCOCH3
OCOCH3
2-Ci-5-thiazolyl


246
OH
OCOCH3
OCOCH3
OH
2-Ci-5-thiazolyl


247
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
2-Ci-5-thiazolyl


248
OH
OCOCH2CH3
OCOCH2CH3
OH
2-Ci-5-thiazolyl


249
OH
OCOCH3
OCOCH3
OCOC6H5
2-Ci-5-thiazolyl


250
OH
OCOCH3
OCOCH3
OCH2SCH3
2-Ci-5-thiazolyl





















TABLE 14





Compound No.
R1
R2
R3
R4
Het1







251
H(═)
OCOCH3
OCOCH3
OCOCH3
2-Ci-5-thiazolyl


252
H(═)
OCOCH2CH3
OCOCH2CH3
OH
2-Ci-5-thiazolyl


253
═O
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
2-Ci-5-thiazolyl


254
OH
OCOCH3
OCOCH3
OCOCH3
3-pyrazolyl


255
OH
OCOCH3
OCOCH3
OCOC6H5
3-pyrazolyl


256
OH
OCOCH3
OCOCH3
OCH2SCH3
3-pyrazolyl


257
═O
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
3-pyrazolyl


258
OH
OCOCH3
OCOCH3
OCOCH3
4-pyrimidinyl


259
OH
OCOCH2CH3
OCOCH2CH3
OCOCH2CH3
4-pyrimidinyl


260
OH
OCOCH2CH3
OCOCH2CH3
OH
4-pyrimidinyl


261
OH
OCOCH3
OCOCH3
OCOC6H5
4-pyrimidinyl


262
OH
OCO(CH2)3CH3
OSO2CH3
OCO(CH2)3CH3
4-pyrimidinyl


263
OH
OCOCH3
OCOCH3
OCOH2CH3
4-pyrimidinyl


264
H(═)
OCOCH3
OCOCH3
OCOCH3
4-pyrimidinyl


265
OH
OCOCH3
OCOCH3
OCOCH3
3-pyrrolyl


266
OH
OCOCH3
OCOCH3
OH
3-pyrrolyl









Production Process

The compound represented by formula (I) or (Ia) 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 Pub. No. 259569/1996, Japanese Patent Laid-Open Pub. No. 269062/1996, or Japanese Patent Laid-Open Pub. No. 269065/1996.




[wherein

R1 represents a hydroxyl group, an optionally substituted C1-6 alkylcarbonyloxy group, an optionally substituted C2-6 alkenylcarbonyloxy group, an optionally substituted C2-6 alkynylcarbonyloxy group, an optionally substituted C1-6 alkyloxy group, an optionally substituted C2-6 alkenyloxy group, an optionally substituted C2-6 alkynyloxy group, an optionally substituted benzyloxy group, or an oxo group 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 Pub. No. 269063/1996, or Japanese Patent Laid-Open Pub. No. 269066/1996.




[wherein R2, R3 and R4 are as defined in formula (I).]

Further, among the compounds according to the present invention, the compounds represented by formula (IV) can be synthesized by those skilled in the art by combining the method described in Journal of Antibiotics (1997), Vol. 50, pp. 229-36 and the synthesizing methods represented by formulae (II) and (III) above.




[wherein Het1, R1, R2, R3, and R4 are as defined in formula (I), however, a compound wherein Het1 represents a 3-pyridyl group is excluded.]

Use

Insect species against which pyripyropene derivatives of formula (I) 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, Aphididae such as Myzus persicae, Aphis gossypii, Aphis fabae, Aphis maidis, Acyrthosiphon pisum, Aulacorthum solani, Aphis craccivora, Macrosiphum euphorbiae, Macrosiphum avenae, Metopolophium dirhodum, Rhopalosiphum padi, Schizaphis graminum, Brevicoryne brassicae, Lipaphis erysimi, Aphis citricola, Apple aphid, Rosy apple aphid, Apple cotton aphid, Eriosoma lanigerum, Toxoptera aurantii, and Toxoptera citricidus; Deltocephalidae such as Nephotettix cincticeps; Delphacidae such as Laodelphax striatellus, Nilaparvata lugens, and Sogatella furcifera; Pentatornidae such as Eysarcoris ventralis, Nezara viridula, and Trigonotylus coelestialium; Aleyrodidae such as Bemisia argentifolii, Bemisia tabaci, and Trialeurodes vaporariorum; Cerococcidae, such as Pseudococcus comstocki and Planococcus citri Risso); Coleoptera pests (for example, Lissorhoptrus oryzophilus, Callosobruchuys chienensis, Tenebrio molitor, Diabrotica 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 (Boophilus microplus, Haemaphysalis longicomis, Rhipicephalus sanguineus, and Scarcoptes scabiei), and preferred are hemipteran pests.
Further, the compound represented by formula (Ia) according to the present invention has significant control effect against hemipteran pests. And, preferred hemipteran pests are preferably selected from Aphidoidea, Coccoidea and Aleyrodidae. More preferred are Myzus persicae, Aphis gossypii, Aphis fabae, Aphis maidis, Acyrthosiphon pisum, Aulacorthum solani, Aphis craccivora, Macrosiphum euphorbiae, Macrosiphum avenae, Metopolophium dirhodum, Rhopalosiphum padi, Schizaphis graminum, Brevicoryne brassicae, Lipaphis erysimi, Aphis citricola, Apple aphid, Rosy apple aphid, Apple cotton aphid, Eriosoma lanigerum, Toxoptera aurantii, Toxoptera citricidus, or Pseudococcus comstocki. 
When the compound according to formula (I) and (Ia) can be used as an effective ingredient of a pest control agent, the above compound can be used as such, however, the compound is usually used 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 carriers including 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 and the like.
Examples of liquid carriers include, for example: alcohols, such as methanol, n-hexanol, and ethylene glycol; ketones, such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons, such as n-hexane, kerosine, and kerosene; aromatic hydrocarbons, such as toluene, xylene, and methylnaphthalene; ethers, such as diethyl ether, dioxane, and tetrahydrofuran; esters, such as ethyl acetate; nitriles, such as acetonitrile and isobutyronitrile; acid amides, such as dimethylformamide and dimethylacetamide; vegetable oils, such as soy bean oil and cotton seed oil; dimethylsulfoxide; and water.
Further, gaseous carriers include, for example, LPQ 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.
Further, 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, however, in general, 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), or the above formualtions 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) to a plant or soil. Further, 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) to a plant or soil. Preferred methods usable for applying the above compound and formulation to plants or soil include spreading treatment, soil treatment, surface treatment, or fumigation treatment.
Spreading treatments include, for example, spreading, spraying, misting, atomizing, granule application, and submerged application. Further, soil treatments include, soil effusion and soil mixing. Further, examples of surface treatments include, for example, coating, dust coating, and covering. Further, 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) or (Ia) 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, fungicides, insecticides, 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 (9th edition, 2002, published by SHIBUYA INDEX RESEARCH GROUP). More specifically, insecticides, miticides, or nematocides include, for example: organic ester phosphate compounds such as O-(4-boromo-2-chlorophenyl) O-ethyl S-propylfosphorothioate (general name: profenofos), O-(2,2-dichlorovinyl) O,O-dimethylphosphate (general name: dichlorovos), O-ethyl O-[3-methyl-4-(methylthio)phenyl] N-isopropylphosphoroamidate (general name: fanamifos), O,O-dimethyl O-(4-nirto-m-tryl)phosphorothioate (general name: fenitrothion), O-ethyl O-(4-nitrophenyl)phosphorothioate (general name: EPN), O,O-diethyl O-(2-isopropyl-6-methylpyrimidin-4-yl)phosphoroate (general name: diazinon), O,O-dimethyl O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (general name: chloropyrifosmethyl), O,S-dimenylN-acetylphosphoroamidethioate (general name: acephate), and O-(2,4-dichlorophenyl) O-ethyl S-propylphosphorodioate (general name: prothiophos); carbamate compounds such as 1-naphthyl N-methylcarbamate (general name: carbaryl), 2-isopropoxyphenyl N-methylcarbamate (general name: propoxur), 2-methyl-2-(methylthio) propyonaldehyde O-methylcarbamoyloxym (general name: Aldicarb), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate (general name: carbofuran), dimethylN,N′-[thiobis{(methylimino) carbonyloxy}] gisetahneimidothiate (general name: thiodicarb), S-methyl N-(methylcarbamoyloxy) thioacetoimidate (general name: methomyl), N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio) acetoamide (general name: Oxamyl), 2(ethylthiomethyl) phenyl N-methylcarbamate (general name: ethyofencarb), and 2-dimethylamino-5,6-dimethylpyrimidin-4-yl N,N-dimethylcarbamate (general name: fenothiocarb); 2-sec-butylphenyl N-methylcarbamate (general name: fenobucarb); nereistoxin derivatives such as S,S′-2-dimethylaminotrimethylenebis (thiocarbamate) (general name: cartap) and N,N-dimethyl-1,2,3-trithian-5-ylamine (general name: thiocyclam); organochlorine compounds such as 2,2,2-trichloro-1,1-bis(4-chlorophenyl) ethanol (general name: dicofol) and 4-chlorophenyl-2,4,5-trichlorophenylsulfon (general name: tetradifon); organometallic compounds such as bis[tris(2-methyl-2-phenylpropyl) thin] oxyde (general name: phenbutatin oxide); pyrethoroid compounds such as (RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutylate (general name: fenvalerate), 3-phenoxybenzyl (1RS)-sys, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopopanecarboxylate (general name: permethrin), (RS)-α-cyano-3-phenxybenzyl (1RS)-sys, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (general name: cypermethrin), (S)-α-cyano-3-phenoxybenzyl (1R)-sys-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropnecarboxylate (general name: deltamethorin), (RS)-α-cyano-3-phenoxybenzyl (1RS)-sys, trans-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylchloropropanecarboxylate (general name: cyhalothrin), 4-methyl-2,3,5,6-tetrafluorobenzyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimet hylchloropropanecarboxylate (general name: tefluthrin), and 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzylether (general name: ethofenprox); benzoylurea compounds such as 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (general name: diflubenzuron), 1-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-3-2,6-difluorobenzoyl)-urea (general name: chlorofluazuron), and 1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea (general name: teflubenzuron); juvenile hormone-like compounds such as isopropyl(2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dotecadienoate (general name: methoprene); pyridadinone compounds such as 2-t-butyl-5-(4-t-butylbenzylthio)-4-chloro-3(2H)-pyridadinone (general name: pyridaben); pyrazole compounds such as t-butyl 4-[(1,3-dimethyl-5-phenoxypyrazole-4-yl) methyleneaminooxymethyl] benzoate (general name: fenpyroxymate); nitro compounds such as 1-(6-chloro-3-pyridylmethyl)-N-nitro-imidazoridin-2-iridenamine (general name: imidachloprid); or dinitro compounds, organosulfur compounds, urea compounds, triazine compounds, hydrazine compounds, and other compounds include compounds such as 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazine-4-on (general name: buprofezin), trans-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazoridinone-3-carboxamide (general name: hexythiazox), N-methylbis(2,4-xyryliminomethyl) amine (general name: amitraz), N′-(4-chloro-o-tryl)-N,N-dimethylfomramidine (general name: chlorodimeform), and (4-ethyxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl) propyl](dimethyl) silane (general name: silafluofen).
Furthermore, the control agent 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, and antibiotic agents such as avermectin and milbemycin.
Fungicides usable herein include, for example, anilinopyrimidine compounds such as 2-anilino-4-methyl-6-(1-propynyl) pyrimidine (general name: mepanipyrim) and 4,6-dimethyl-N-phenyl-2-pyrimidinamine (general name: pyrimethanil); azole compounds such as 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl) butanone (general name: triadimefon), 1-(biphenyl-4-yloxy)-3,3-dimethyl-1-(1H,1,2,4-triazole-1-yl) butane-2-ol (general name: bitertanol), 1-[N-(4-chloro-2-trifluoromethylphenyl)-2-propoxyacetoimidoyl] imidazole (general name: triflumizole), 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxoran-2-ylmethyl]-1H-1,2,4-triazole (general name: etaconazole), 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxoran-2-ylmethyl]-1H-1,2,4-triazole (general name: propiconazole), 1-[2-(2,4-dichlorophenyl) pentyl]-1H-1,2,4-triazole (general name: penconazole), bis (4-fluorophenyl) (methyl) (1H-1,2,4-triazole-1-ylmethyl) silane (general name: flusilazole), 2-(4-chlorphenyl)-2-(1H-1,2,4-triazole-1-ylmethyl) hexanenitryl (general name: myclobutanil), (2RS,3RS-2-4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazole-1-yl) butane-2-ol (general name: cyproconazole), (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazole-1-ylmethyl) pentane-3-ol (general name: tebuconazole), (RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazole-1-yl) hexane-2-ol (general name: hexaconazole), (2RS,5RS)-5-(2,4-dichlorophenyl) tetrahydro-5-(1H-1,2,4-triazole-1-ylmethyl)-2-furyl 2,2,2-trifluoroethylether (general name: farconazolesys), N-propyl-N-[2-(2,4,6-trichlorophenoxy) ethyl] imidazole-1-carboxamide (general name: prochloraz), and 2-(4-fluorophenyl-1-(1H-1,2,4 triazole-1-yl)-3-trimethylsilylpropane-2-ol (general name: simeconazole; quinoxaline compounds such as 6-methyl-1,3-dithiolo [4,5-b] quinoxaline-2-on (general name: quinomethonate); manganezeethylenebis (dithiocabamate) compounds (general name: maneb), zincethylenebis (dimethyldiocarbamate) compounds (general name: zineb), complex compounds of zinc and manganeseethylenebis(dithiocarbamate) (maneb) (general name: manzeb); ditiocarbamate compounds such as dizincbis (dimethylditiocarbamate) ethylenebis (diocarbamate) (general name: propineb); organochlorine compounds such as 4,5,6,7-tetrachlorofutharide (general name: futharide), tetrachloroisofuitharonitril (general name: chlorothalonil), and pentachloronitrobenzene (general name: quitozene); benzimidazole compounds such as methyl 1-(butylcarbamoyl) benzimidazole-2-ylcarbamate (general name: benomyl), dimetyl 4,4′-(o-phenylene) bis (3-thioarophanete) (general name: thiophanate-methyl), and methylbenzimidazole-2-ylcarbamate (general name: carbendazym); pyridinamine compounds such as 3-chloro-N-(3-chloro-2,6-dinitro-4-α,α,α-trifluorotryl)-5-trifluoromethyl-2-pyridinamine (general name: fluazinam); cyanoacetoamide compounds such as 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (general name: cymoxanil); phenylamide compounds such as methyl N-(2-methoxyacetyl)-N-5(2,6-xylyl)-DL-araninate (general name: metalaxyl), 2-methoxy-N-(2-oxo-1,3-oxazolyzine-3-yl) aceto-2′,6′-xylidide (general name: oxadixyl), (±)-α-2-chloro-N-(2,6-xylylacetoamide)-γ-butyloractone (general name: ofurace), methyl N-phenylacetyl-N-(2,6-xylyl)-DL-araninate (general name: benalaxyl), methyl N-(2-floyl)-N-(2,6-xylyl)-DL-araninate (general name: furalaxyl), and (±)-α-[N-(3-chlorophenyl) cyclopropnecarboxamide]-γ-butyloractone (general name: cyprofuran); sulfenic acid compounds such as N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfamide (general name: dichlofluanid); copper compounds such as copper hydroxide (general name: copper hydroxide) and copper-8-quinolynolate (general name: organocopper); isoxazole compounds such as 5-methylisoxazole-3-ol (general name: hydroxyisoxazole); organophosphorous compounds such as aluminumtris (ethylphosphnate) (general name: fosetylaluminum), O-2,6-dichloro-p-tril-O,O-dimethylphosphorothioate (general name: tolclofos-methyl), S-benzyl O,O-diisopropylphosphorothioate, O-ethyl S,S-diphenylphosphorodithioate, and aluminumethylhydrogenphosphonate; N-halogenothioalkyl compounds such as N-(trichloromethylthio) cyclohexy-4-en-1,2-dicarboxyimide (general name: captan), N-(1,1,2,2-tetrachloroethylthio) cyclohexy-4-en-1,2-dicarboxyimide (general name: captafol), and dicarboxyimide compounds such as N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxyimide (general name: procymidone), 3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-caroxamide (general name: iprodione), and (RS)-3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione (general name: vinchlozolin); benzoanilide compounds such as α,α,α-trifluoro-3′-isopropoxy-o-tolualynide (general name: flutolanil), and 3′-isopropoxy-o-tolanilide (general name: mepronil); piperadine compounds such as N,N′-[piperadine-1,4-diylbis [(trichloromethyl) methylene]] diformamide (general name: triforine); pyridine compounds such as 2′,4′-dichloro-2-(3-pyridyl) acetophenone O-methyloxym (general name: pyrifenox); carbinol compounds such as (±)-2,4′-dichloro-α-(pyrimidine-5-yl) benzhydrylalcohol (general name: fenarimol) and (±)-2,4′-difluoro-α-(1H-1,2,4-triazole-1-ylmethyl) benzhydrylalcohol (general name: flutoliafol); piperidine compounds such as (RS)-1-[3-(4-tertiallybutylphenyl)-2-methylpropyl] piperidine (general name: fenpropidin); morpholine compounds such as (±)-sys-4-[3-(4-tertiallybutylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (general name: fenpropimorf); organotin compounds such as triphenylthinhydroxyde (general name: phenthinhydroxide), and triphenylthinacetate (genral name: phenthinacetate); urea compounds such as 1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea (general name: pencycuron); cynnamic acid compounds such as (E,Z)4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl) acryloyl] morpholine (general name: dimethomorph); phenylcarbamate compounds such as isopropyl 3,4-diethoxycarbanilate (general name: diethofencarb); or cyanopyrrole compounds such as 3-cyano-4-(2,2-difluoro-1,3-benzooxol-4-yl) pyrrol (general name: fludioxonil), 3-(2′,3′-dichlorophenyl)-4-cyano-pyrrol (general name: fenpiclonyl).
According to another aspect of the present invention, there is provided use of a compound represented by formula (I). Further, according to still another aspect of the present invention, there is provided use of a compound represented by formula (Ia) as a hemipteran pest control agent.
EXAMPLES
The present invention will be specifically described hereunder with reference to examples, however, the present invention is not limited to these examples.
Preparation Example 1 [Wettable Powder]
















Compound according to the present invention
30 wt %



(Compound No. 82)



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
 2 wt %



(Compound No. 82)



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
20 wt %



(Compound No. 82)



N,N-Dimethylformamide
20 wt %



Solvesso 150 (Exxon Mobil Corporation)
50 wt %



Polyoxyethylenealkylarylether
10 wt %










The above ingredients were homogeneously mixed and dissolved to prepare emulsifiable concentrate.
Preparation Example 4 [Granules]
















Compound according to the present invention
 5 wt %



(Compound No. 28)



Bentonite
40 wt %



Talc
10 wt %



Clay
43 wt %



Calcium lignin sulfonate
 2 wt %










The above ingredients were homogeneously ground and homogeneously mixed together and water was added to the mixture, followed by thorough kneading, then the kneaded product was granulated and dried to prepare granules.
Preparation Example 5 [Floables]














Compound according to the present invention
25
wt %


(Compound No. 28)


POE polystyrylphenyl ether sulfate
5
wt %


Propyleneglycol
6
wt %


Bentonite
1
wt %


1% aqueous xanthan gum solution
3
wt %


PRONAL EX-300 (Toho Chemical Industry Co., Ltd.)
0.05
wt %


ADDAC 827 (K.I. Chemical Industry Co., Ltd.)
0.02
wt %


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 Myzus persicae 
Among the compounds of formula (I) produced by the conventional method described above, the compounds shown in Tables 1 to 14 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 this 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 and 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, 207.

## 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 cyclopropylcarbonyloxy, and
R4 represents hydroxyl, cyclopropylcarbonyloxy, or 2-cyanobenzoyloxy.

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