WO2004022546A1 - Substances inhibiting biosynthesis of jasmonic acid - Google Patents

Abstract

It is intended to provide heptyl 8-[1-(2,4-dichlorophenyl)-2-imidazolylethoxy]octanoate and compounds somewhat similar thereto. These compounds specifically inhibit the biosynthesis of jasmonic acid in plants and thus exert effects of inducing male sterility, inhibiting pollen tube elongation, keeping cut flowers fresh, extending flowering season, inhibiting pollen formation, promoting germination, controlling weeds, preventing pollen scattering and so on. Among all, the effects of inhibiting pollen formation and preventing pollen scattering are particularly noteworthy. This is because use of these effects would make it possible to prevent scattering of pollens of plants causative of pollen fever such as cedar to thereby suppress the onset of pollen fever.

Description

 Substances that inhibit acid biosynthesis

 The present invention relates to a substance that specifically inhibits plant jasmonic acid biosynthesis and its use, and a method for screening a substance that specifically inhibits jasmonic acid biosynthesis.

 Light

 Fine

Background art

 Jasmonic acid has been known for a long time, and its biological activity has been actively studied. It is a substance widely distributed in the plant kingdom from filamentous fungi to higher plants. In recent years, it has been discovered that it is a plant hormone that has various physiological effects on plant growth and growth (Annu. Rev. Plant Physiol. Plant Mol. Biol. 44, 569-589). In particular, it plays important roles in pollen formation (Proc Natl Acad Sci USA. 97, 10625-10630), germination control, and flower and fruit formation (Proc Natl Acad Sci USA. 92, 4114-4119). In addition, jasmonic acid may play a central role as a signaling substance in resistance to pathogens (Proc Natl Acad Sci USA. 87, 7713-7116) and injury response (Nature 383, 826-829). It has been revealed. In other words, it is suggested that suppressing the action of jasmonic acid leads to pollen formation, suppression of pollen tube elongation, male sterility, prolonged flowering period, promotion of germination, reduced disease resistance, and / or reduced stress response function. ing.

From these findings, it is considered that if the action of jasmonic acid in plants can be artificially controlled, plant growth can be regulated as desired. Jasmonic acid-deficient plants (jasmonic acid-deficient plants obtained by a method based on the disruption of the jasmonic acid biosynthesis gene) are obtained from Arabidopsis thaliana and other plants. Since the biological activity of all jasmonic acids during the entire growth period is blocked, it is impossible to inhibit only the desired activity among various biological activities of jasmonic acid. It is also conceivable. There is also the disadvantage that it is necessary to develop a defective line for each plant species, which takes time to develop, and that maintaining the defective line is costly.

 Gibberellin, one of the most well-studied plant hormones, has elucidated its physiological function in detail using studies with specific inhibitors of its biosynthesis. If a specific inhibitor of the biosynthesis of jasmonic acid is developed, the inhibitor is acted only during the growth stage of the biological activity of the target jasmonic acid. It is considered that only specific physiological activities can be suppressed. In addition, such inhibitors are very effective in knowing the physiological functions of endogenous physiologically active substances, and their development is expected as a new means for understanding the function of jasmonic acid.

 However, the jasmonic acid biosynthetic pathway (see Fig. 1) has been relatively recently found to be a cascade as shown in Fig. 1, and there is no knowledge about a method for specifically inhibiting the jasmonic acid biosynthetic pathway. It has not yet been reported that the inhibition of diasmonic acid biosynthesis can be specifically and effectively inhibited by inhibiting any of the enzymes involved in the pathway. At present, we must rely on experimental verification.

 An object of the present invention is to select an enzyme that is effective as a target for inhibiting jasmonic acid biosynthesis, and to specify a substance that specifically inhibits jasmonic acid biosynthesis. Disclosure of the invention

The present inventors have studied the jasmonic acid biosynthetic pathway (FIG. 1) in order to solve the above-mentioned problems. (Allene oxide synthetase, hereafter referred to as “A0S”). AOS is involved in the most important step in controlling jasmonic acid biosynthesis, as indicated by the results of functional analysis of enzymes involved in the biosynthetic pathway (Plant J. 15, 675-684). Furthermore, recent studies using knockouts of AOS have suggested that AOS is essential for jasmonic acid biosynthesis (Plant J. 31, 1-12). This has led to the development of specific inhibitors of AOS. Considered promising inhibitors of the jasmonate biosynthetic pathway.

 AOS has been shown to be a cytochrome P450 enzyme (Science 252, 781-784). However, no AOS inhibitor has been reported at present, and the present inventors have developed imidazole-based compounds, which are the most commonly used inhibitors of cytochrome P450 enzymes, based on the catalytic cycle of AOS. We designed inhibitors at the center, and intensively searched for compounds that inhibit AOS. As a result, a compound having AOS inhibitory activity was discovered, and the effect of diXCI sasmonic acid on physiological activity was examined using the compound.

 H

As a result, the present invention has been completed.

 That is, the present invention includes the following inventions.

 Three

1. The following formula (I):

(I)

Wherein the - (. Those該置substituent is a substituent selected from Substituent Group A) c ₈ alkyl group, an optionally substituted Bifue two drill group may off be substituted X represents an oxygen atom, a sulfur atom, an imino group, a methylene group, and a phenyl group (the substituent is a substituent selected from the following substituent group A).

R ₂ may be substituted (^-(: ₁₂ alkyl group (the substituent is a substituent selected from the following substituent group B)), and optionally substituted C ₂ -C ₁₂ Alkenyl group (the substituent is a substituent selected from Substituent Group B below), C ₃ -C _4, alkoxycarbylalkyl group, C ₃ _C _4, alkylaminocarbolalkyl group, substituted A substituent (the substituent is a substituent selected from Substituent Group A below).

Y represents an alkylene group of C _r C ₄ or that CH and 直接 are directly bonded without Y being present;

R ₃ is Imidazoriru group, 1, 2, 4-triazolyl group, a pyrimidyl group, substituent group A is a halogen atom, a nitro group, Shiano group, hydroxyl group, C ₄ Al kill groups, C厂C ₄ alkoxy Group, C Factory C ₄ haloalkyl group, and-^ haloalkoxy group Group consisting of

Substituent group B includes a phenyl group which may be substituted (the substituent is a substituent selected from the above-described substituent group A), a phenyl group which may be substituted (the substituent is And a pyridyl group which may be substituted (the substituent is a substituent selected from the above-mentioned substituent group A). ]

And a salt thereof.

 2. An agricultural chemical composition comprising the compound according to claim 1 as an active ingredient.

 3. A jasmonic acid biosynthesis inhibitor comprising the compound according to claim 1 as an active ingredient.

4. A male sterilizing agent comprising the compound according to claim 1 as an active ingredient.

 5. A pollen tube elongation inhibitor comprising the compound according to claim 1 as an active ingredient.

 6. A freshness-retaining agent for cut flowers, comprising the compound according to claim 1 as an active ingredient.

 7. A flowering period extender comprising the compound according to claim 1 as an active ingredient.

 8. A pollen formation inhibitor comprising the compound according to claim 1 as an active ingredient.

 9. A germination accelerator comprising the compound according to claim 1 as an active ingredient.

 10. A herbicide containing the compound according to claim 1 as an active ingredient.

 11. A herbicide comprising the compound according to claim 1 and another compound having herbicidal activity.

12. A pollen scattering inhibitor comprising the compound according to claim 1 as an active ingredient.

 13. A method for inhibiting the biosynthesis of jasmonic acid, comprising treating a plant with the compound according to claim 1.

 14. A method for male sterilization, comprising treating a plant with the compound according to claim 1.

15. A method for inhibiting pollen tube elongation, comprising treating pollen with the compound according to claim 1.

 16. A method for maintaining freshness, comprising treating cut flowers with the compound according to claim 1.

17. A method for extending a flowering period, comprising treating a plant with the compound according to claim 1.

 18. A method for suppressing pollen formation, comprising treating a plant with the compound according to claim 1.

19. A method for promoting germination, comprising treating a seed with the compound according to claim 1. 20. A herbicidal method comprising treating a plant with the compound according to claim 1.

 21. A herbicidal method comprising treating a plant with the compound according to claim 1 and another compound having herbicidal activity.

 22. A method for preventing pollen scattering, comprising treating a plant with the compound according to claim 1.

 23. Specificity for jasmonic acid biosynthesis, including a step of contacting a test substance with a plant-derived allenoxide synthase and a step of selecting a test substance that inhibits the activity of a plant-derived allenoxide synthase A screening method for the substance to be inhibited.

 Hereinafter, the present invention will be described in detail.

In the above formula (I), is a substituted C ₈ alkyl group, an optionally substituted biphenylyl group (the substituent is a substituent selected from the following substituent group A), and is substituted. X represents an oxygen atom, a sulfur atom, an imino group or a methylene group, and R ₂ represents a phenyl group which may be substituted (the substituent is a substituent selected from Substituent Group A below). -C ₁₂ alkyl group (the substituent is a substituent selected from Substituent Group B below), and optionally substituted C ₂ -C ₁₂ alkenyl group (the substituent is A substituent selected from group B.), C ₃ _C ₄ . Alkoxycarbonyl El alkyl group, C ₃ - C ₄₀ alkylaminocarbonyl group, represents an optionally substituted phenyl group (. The substituent is a substituent selected from the following substituent group A), Y is -Indicates that CH is directly bonded without the presence of an alkylene group of C ₄ or Y, and R ₃ indicates an imidazolyl group, 1,2,4-triazolyl group, or pyrimidyl group; A is a halogen atom, a nitro group, Shiano group, a hydroxyl group, ^c i_ ^c 4 alkyl group, Ji厂C ₄ alkoxy groups, C厂₍₄ C port alkyl group, and C厂C ₄ group consisting Haroaru Kokishi group And the substituent group B includes a phenyl group which may be substituted (the substituent is a substituent selected from the above-mentioned substituent group A), a phenoxy group which may be substituted (the substituent Is selected from the above substituent group A It is a substituent.), And optionally substituted pyridyl group (said substituent is a group consisting of a substituent Ru is selected from the substituent group A.).

In - the "C ₈ alkyl" is a straight-chain or branched alkyl Le group having 1 to 8 carbon atoms, for example, tert - heptyl, isopropyl Honoré, n - heptyl, n - heptyl, methylcarbamoyl And preferably tert-butyl, isopropyl and n-butyl, and more preferably tert-butyl and isopropyl.

The “optionally substituted biphenylyl group” in the above refers to a biphenylyl group (mainly 4-biphenylyl group), a halogen atom, a nitro group, a cyano group, a hydroxyyl group, and a “ _ (] ₄ alkyl group ”,“ -C ₄ alkoxy group ”described below,“ C Factory C ₄ haloalkyl group ”described below, and“ C Factory C ₄ haloalkoxy group ”described below, the same selected from the group consisting of Or a bifuryl group substituted by a different substituent, for example, 2,6-dichloro-4-bifuyulinole, 2-cyclohex-4-biphenylyl, and preferably 2,6-dichloro-4-biphenylyl. -Jikro mouth _4-It is bifeniril.

And "optionally substituted Fueeru group" in addition to phenyl group, c androgenic atom, a nitro group, Shiano group, arsenate Dorokishiru group, later "- C ₄ alkyl group", below "C _r C ₄ alkoxy group ", later the" C厂a mouth alkyl group ", and later" C厂C ₄ identical or different ivy phenylene Honoré group substituted with a substituent selected from the group consisting of haloalkoxy group ", For example, 2,4-dichlorophenol, 2,6-dichlorophenyl, 2,4-difluorophenyl, 4-chlorophenyl, and preferably 2,4-dichlorophenyl, , 4-difluorophenyl and 4-chloro feninole, and more preferably, 2, 4-diphenyl feninole and 2, 4-diphenol phenol.

The "C factory C ₁₂ alkyl group" for R ₂ is a linear or branched anoalkyl group having 1 to ₁₂ carbon atoms, for example, methyl, ethylenol, propyl, butyl, noel, heptyl, Pentyl, preferably methyl, ethyl, propyl, butyl, nonyl, and heptyl, and more preferably methyl, ethyl, propyl, butyl, and nonyl. .

In R ₂ "which may be substituted - C ₁₂ alkyl group" and, in the aforementioned '^ - C ₁₂ alkyl group "other," optionally substituted phenyl group "described later, below" location substitution which may Fuyunokishi group optionally ", and was substituted by the same or different substituents selected from the group consisting of" an optionally substituted pyrid-Le group "below" - a C ₁₂ Anorekinore group ", for example, , Hue-noremethinole, 3_phenylpropinole, 2-phenoxechityl, 2-black pheninolemethinole, 4-black-mouth feninolemethinole, 6-black-mouth (3-pyridyl) methyl, 2,3-dic Oral phenylmethyl, 2,4-dioctal phenylmethyl, 2,6-dichlorophenylphenyl, 3,5-difluoropheninolemethyl, 2,6-diphenolenophenyleninomethyl, 2,5-dichloropheninolemethyl, preferably phenylenomethyl, Enylpropyl, 2-phenyloxethyl, 2-chlorophenylmethyl, 4-chlorophenylenomethyl, 6-chloro (3-pyridyl) methyl, 2,3-diphenylphenyl, 2,4-dimethyl Mouth phenylmethyl, 2,6-di-mouth Mouth phenylenomethine, 3,5-difluoro Mouth phenylenomethyl, 2,6-difluorophenylmethyl, more preferably pheninolemethinole, 3-phenylpropyl, 2-phenoxicetyl , 2-chlorophenylmethyl, 4-chlorophenylmethyl, 6-chloro (3-pyridyl) methyl, 2,3-dichlorophenylmethyl, 2,4-dichlorophenylmethyl Le, 2, 6-dichlorophenyl methyl, 3, 5-Jifunoreo port Hue Nino les methylate Honoré.

The “C ₂ -C ₁₂ alkenyl group” for R ₂ is a linear or branched alkenyl group having 1 to ₁₂ carbon atoms, for example, aryl, 3-methyl-2-butenyl, heptenyl, otatyl And are preferably aryl, 3-methyl-2-butenyl and octenyl, and more preferably 3-methyl-2-butenyl and octiel.

"Optionally substituted C ₂ - C ₁₂ alkenyl group" in R ₂ and, in the aforementioned "C ₂ - C ₁₂ alkenyl group" other, "optionally substituted phenyl group" described later, below A `` C <sub>2</sub> -C <sub>12</sub> anorecenyl group substituted by the same or different substituents selected from the group consisting of `` optionally substituted phenoxy group '' and `` optionally substituted pyridyl group '' And, for example, pheninolebininole, 2-hexopeninylvinyl, 4-chloroopeninolevininole, 2,4-dichloropheninolebininole, phenoxybininole, 3-phenylenylinyl, 3- (2-inn) 3- (4-chloro-2-phenyl) aryl, 3- (2,4-dichlorophenyl) yl, 3-phenyloxy, preferably 3-phenyloxy, preferably 2-phenyl-2-yl Mouth mouth feninorebininore, 4 Black hole Fueninorebi two Honoré, 2, 4-dicumyl every mouth phenylene Honoré vinyl, Fuenokishibiniru, more preferably a phenylene Rubiniru.

The “C ₃ -C ₄ .alkoxycarbonylalkyl group” for R ₂ is a straight-chain or branched alkoxycarbonylalkyl group having 3 to 40 carbon atoms, for example, ethoxy canoleponyl butyl, ethoxy carbonyl Rupentyl, methoxycarbonyl heptinole, propoxycarbonylheptyl, butoxycarbolheptyl, 3-methylbutoxycarponylheptyl, heptoxycarbonylheptyl, ethoxycarponyl Ndecanyl, hexoxycarbinol heptinole, heptoxycarbonylheptinole, heptoxycarponyloctyl, and preferably propoxycarbonylheptyl, butoxycarbuelheptyl, 3-methylbutoxycarbonylheptyl, heptoxycarbonyl Heptyl, ethoxycanoleponinolendene, hexoxycarbonyl heptinole, heptoxycanoleponinoleheptyl, heptoxycanoleponinoleoctyl, and more preferably heptocarboleheptyl, ethoxycarbonyl undecanyl, hexonole. Xycarbonylheptyl, heptoxycarbonylheptyl, heptoxyforce / leponinoleotectinole.

“C ₃ _C _4. Alkylaminocarbonylalkyl group” in R ₂ is a straight-chain or branched-chain alkylaminocarbonylalkyl group having 3 to 40 carbon atoms, for example, ethylaminocarboninolemethyl Heptylaminocarbonelecinole, heptinolea mininocarbo-octyl, preferably heptylaminocapillonileptyl, heptylaminocarbonylcarbonyl, and more preferably heptylaminocarbonoleoctyl / re.

The “phenyl group which may be substituted” for R ₂ includes, in addition to a phenyl group, a nitrogen atom, a nitro group, a cyano group, a hydroxyl group, a “C _r C ₄ alkyl group” described below, and a “c _r c ₄ alkoxy group "," c厂c ₄ haloalkyl group below ", and a phenyl group substituted by the same or different substituents selected from the rc c ₄ group consisting haloalkoxy group" described later, for example, And phenylbutyl, phenylpropyl and phenylethyl, preferably phenylbutyl and phenylpropyl, and more preferably phenylbutynole.

The “C factory C ₄ alkylene group” in Y is a linear or branched alkylene group having 1 to 4 carbon atoms, for example, methylene, ethylene, trimethylene, tetramethylene, and preferably methylene And ethylene, and more preferably methylene. The “halogen atom” in the substituent group A is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, preferably a fluorine atom, a chlorine atom, and more preferably a chlorine atom. .

The “C _r C ₄ alkyl group” in the substituent group A is a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, for example, butyl, propyl, isopropyl, ethyl, methyl And preferably butyl, propyl, isopropyl and ethyl, and more preferably butyl, propyl and isopropyl.

The “-C ₄ alkoxy group” in the substituent group A is a linear or branched alkoxy group having 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, and Are ethoxy, propoxy, isopropoxy and butoxy, more preferably ethoxy, propoxy and butoxy.

The “-C ₄ haloalkyl group” in the substituent group A is a straight-chain or branched-chain haloalkyl group having 1 to 4 carbon atoms, for example, chloromethyl, 1-chloroethyl, 2-chlorobutyl, 2-chlorobutyl. Propinole, preferably 1-chloroethynole, 2-chlorobutynole, and 2-chlorobutynole, and more preferably 2-chlorobutynole and 2-chlorobutynole.

The “C _r C ₄ haloalkoxy group” in the substituent group A is a straight-chain or branched-chain haloalkoxy group having 1 to 4 carbon atoms, such as 1-chloroethoxy, 2-chlorobutoxy, 3-chlorobutoxy, 1-chloropropoxy, 2-chloropropoxy, preferably 2-chlorobutoxy, 3-chlorobutoxy, 1-chloroethoxy, 2-propoxy, and more preferably There are 2-chlorobutoxy, 3-chlorobutoxy and 2-chloropropoxy.

The “phenyl group which may be substituted” in the substituent group B includes, in addition to a phenyl group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, the above-mentioned “C Factory C ₄ alkyl group”, Phenyl substituted by the same or different substituents selected from the group consisting of the aforementioned “C _r C ₄ alkoxy group”, the aforementioned “(Factory C ₄ haloalkyl group)”, and the aforementioned “-haloalkoxy group” For example, 2-chloro phenyl, 4-chloro phenyl, 2,3-dichloro phenyl, 2,4-dichloro phenyl, 2,6-dichloro phenyl , 3,5-diphnolenophenyl, 412-phenyl, 3-cyanophenyl, preferably 4-chlorophenyl, 2,3-dichlorophenyl, 2,4- Dichloropheninole, 2,6-dioctanol feninole, 3,5-diphnoleolophenino , 4-212 phenyl, 3-cyanophenyl, and more preferably, 4-chlorophenyl, 2,4-dichlorophenol, 2,6-dichlorophenyl, 3,5- Diphnoleolofeninole, 412 trofueninore, and 3-cyanofuer. The “optionally substituted phenoxy group” in the substituent group B includes, in addition to the phenoxy group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, the aforementioned “(^ -C ₄ alkyl group”, the aforementioned A phenoxy group substituted with the same or different substituent (s) selected from the group consisting of “C ₄ alkoxy group”, “C ₄ alkyl group”, and “-alkoxy group” described above. For example, 2-chlorophenoxy, 4-chlorophenoxy, 2,3-dichlorophenoxy, 2,4-dichlorophenoxy, 2,6-dichlorophenoxy, 3,5-diphenyl Orofuenoxy, 4-nitrophenoxy, and 3-cyanofenoxy, preferably 4-clofenoxy, 2,3-dichlorophenoxy, 2,4-dichlorophenoxy, 2,6-dichlorophenoxy Si, 3, 5-Jiff / Orophenoxy, 4_nitrophenoxy, 3-cyanophenoxy, more preferably 4-chlorophenoxy, 2,4-dichlorophenoxy, 2,6-dichlorophenoxy, 3,5-difluorophenoxy, 412 Trophenoxy, 3-cyanophenoxy.

The “pyridyl group which may be substituted” in the substituent group B includes, in addition to the pyridyl group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, the above-mentioned “C Factory C ₄ alkyl group”, the above-mentioned "- C ₄ alkoxy group", the aforementioned "- C ₄ haloalkyl group", in及beauty aforementioned phenoxy group substituted by the same or different location substituent selected from the group consisting of "C厂Ha port alkoxy group" There are, for example, 6-clo mouth (3-pyridyl), 21-clo mouth (4-pyridyl), 3-clo mouth (4-pyridyl), preferably 6-clo mouth (3-pyridyl), It is a 3-clo (4-pyridyl), and more preferably a 6-clo (3-pyridyl).

 The present invention includes not only the compound represented by the formula (I) but also a salt thereof. Examples of such salts include sodium salts and potassium salts.

In the present invention, is preferably a C ₂ -C ₆ alkyl group, a biphenyl group, a phenyl group which may be substituted with a chlorine atom, and more preferably a tert-butyl group, a biphenyl group. They are a dilyl group, a phenyl group and a 2,4-dichlorophenyl group, and particularly preferably a 2,4-diphenyl phenyl group.

 In the present invention, X is preferably an oxygen atom.

In the present invention, is preferably C ₂ −. Alkyl group, C ₂ -C ₆ alkenyl group, c ₅ -c ₁₆ alkoxycarbonylalkyl group, phenyl which may be substituted with a halogen atom (Substituted with an alkyl group, a phenoxy group optionally substituted with a halogen atom) c _{4 An} alkyl group, a c substituted with a pyridyl group optionally substituted with a halogen atom a _r c ₄ alkyl group, more preferably a heptyl group, pentyl group, a hexyl group, a heptyl group, Okuchiru group, Noel group, Ariru group, 2-butene group, 3-methyl-2-butenyl Group, ethoxycarbonylbutyl group, ethoxycarbonylpentyl group, methoxycanolepodinoleheptyl group, propoxycarbinoleheptyl group, butoxycarbonylheptyl group, 3-methylbutoxycarbonylheptyl group, heptoxycarboheptyl group , Ethoxy carbonyl benzoyl group, hexoxycarbonylheptyl group, phenylmethyl group, 3-phenylpropyl Group, 2-phenoxhetinole group, 2-chlorophenymethylinole group, 4-chloropheninolemethinole group, 6-chloro (3-pyridyl) methyl group, 2,3-dichlorophenylmethyl group, 2,4 -Dichloromethylphenyl, 2,6-dichlorophenylmethyl, 3,5-difluorophenylmethyl, particularly preferably butyl, noninole, aryl, 3-methyl-2-butenyl, ethoxy Carbonylbutyl group, ethoxycarbonylpentyl group, methoxyl heptyl group, propoxyl heptyl group, butoxycarbonyl heptyl group, 3-methylbutoxycarbonyl heptyl group, heptoxycarbonylheptyl group, ethoxycarbonyl Ndecanyl, hexoxycarbonylheptyl, phenylmethyl, 3-phenylpropyl, 2-phenyl Noxityl group, 2-chlorophenylmethyl group, 4-chlorophenylmethyl group, 6-chloro (3-pyridyl) methyl group, 2,3-dichlorophenylinolemethy / re, 2,4-dichlorophenyl / remeth / le A 2,6-dichlorophenylmethyl group and a 3,5-difluorophenylmethyl group, and most preferably a heptoxycarponinoleheptyl group.

In the present invention, Y is preferably a methylene group or a direct bond between CH and R ₃ without Y, and more preferably a methylene group.

In the present invention, R ₃ is preferably an imidazolyl group.

Examples of the compound represented by the formula (I) include 1- [2-aryloxy-2- (2,4-dicopenethyl) -ethyl] -1-imidazole (compound 1), 1-imidazole [2- (2,4-Diclobutenyl) -2- (3-methyl-2-butenyloxy) -ethyl imidazole (Compound 2), 1- [2- (2,4_dichlorofuunyl) -2-Noe Xy-ethyl] _1 ^ imidazole (compound 3), 1- [2- Butoxy-2- (2,4-dioctanol) -ethyl] -1 Imidazole (compound 4), 5- [1- (2,4_dioctanol) -2-imidazoli [Rethoxy] ethyl ester pentanoate (Compound 5), 6- [1- (2,4-dichlorophenyl) -2-imidazolylethoxy] hexanoate (Compound 6), 8_ [1- Methyl (2,4-dioctylphenyl) -2-imidazolylethoxy] octanoate (Compound 7), 8_ [1- (2,4-dichlorophenyl) -2-imidazolylethoxy] Propyl octanoate (compound 8), butyl 8- [1- (2,4-diphenyl) -2-imidazolylethoxy] butanetansate (compound 9), 8- [1- (2,4-dichlorobutane) Phenyl) -2-Methylazolylethoxy] octanesanoic acid 3-methylbutyl (compound 10), 8- [1- (2,4-dichlorophenyl) -2-imidazolylethoxy] octanoic acid heptyl ( Compound 1 1), 11- [1- (2,4-diphenyl ) -2 - I formidacillin sledding Rue butoxy] Undekan acid Echiru

(Compound 12), 1- (2,4-dichlorophenyl) -2-imidazolyl-1- (phenylmethoxy) ethane (Compound 13), 1- (2,4-dichlorophenyl) -2-imidazolyl- 1- (3-phenylpropoxy) ethane (compound 14), [1_ (2,4-dichlorophenyl) -2-imidazolyl] (2-phenoxhetoxy) methane (compound 15), 1- ( 2,4-Dichlorophenyl) -1-[(2-chlorophenyl) methoxy] -2-imidazolylethane (compound 16), 1- (2,4-dichlorophenyl)レ) -1-[(4- ク 口 口 フ 二 甲基) 甲 キ シ] -2- imidazolinoleethane (compound 17), 1- (2,4-dioctanol phenyl) -1-[(6 -C-mouth (3-pyridyl) methoxy] -2 -imidazolylethane (compound 18), 1- (2,4-diclo-phenyl)-1-[(2,3-dic-mouth Mouth phenol-methoxy) -2-imidazolylethane (compound 19), 1- (2,4-dichloromethane phenol) Ninore) — 1-[(2,4-Jik mouth mouth feninole) methoxy] — 2—Imidazolinoleethane

(Compound 20), 1- (2,4-Dimethyl phenyl) -1-[(2,6-Dimethyl phenyl) methoxy] -2-imidazolylethane (Compound 21), 1- ( 2,4-dic-open-phenyl) -1-[(3,5-difluorophenyl) methoxy] -2-imidazolylethane (compound 22), 8- (1-biphenyl-4-yl) 2- [1,2,4] -Triazole-1-ylethoxy) -octyl acid heptyl

(Compound 23), Methyl 8- (1-biphenyl-4-yl-2_ [1,2,4] -triazole-1-yl-ethoxy) -octanoate (Compound 24), 8_ (1 -Biphenyl-4-yl-2-imidazole-1-yl-ethoxy) -heptyl octanoate (compound 25), 8- (2-imidazole-1-yl-1-phenyl-ethoxy) -Heptinole octanoate (Compound 26), 8- (2-imidazole-1-yl-1-pheninoethoxy) -Metizole octanoate (Compound 27), 8-[(2,4-dichloro- Phenyl) -pyrimidine-5-yl-methoxy] -heptyl octanoate (compound 28), 8- (1-imidazole-1-ylmethyl-2,2-dimethyl-propoxy) -hexanole octanoate (compound 29), 8- [1- (2,4-dichro-phenyl) -2-pyrimidine-5-yl-ethoxy] -heptyl octanoate and the like. Among these compounds, 1- [2- (2,4-dichloromethyl) -2- (nonyloxy-ethyl) -1 / ^ imidazole (compound 3), 1- [2-butoxy-2- (2 , 4-Dichlorophenyl) -ethyl imidazole (Compound 4), 6- [1- (2,4-Dic-mouth phenyl) -2-imidazolylethoxy] hexyl hexate (Compound 6) , 8_ [1- (2,4-Dichrophthyl) -2-methylimidazolylethoxy] octanoate (Compound 7), 8- [1- (2,4_Dichrophthyl phenyl) ) -Propyl-2-imidazolylethoxy] octanoate (compound 8), 8- [1- (2,4-dichlorophenyl) -2-imidazolylethoxy] butyl octanoate (compound 9), 8- [1- (2,4-Dic-mouth phenyl) -2-imidazolylethoxy] 3-methylbutyl octanesate (Compound 10), 8- [1- (2,4-Dichlorophenyl) -2-imidazolylethoxy ] Heptyl octanoate (Compound 11) 1- (2,4-Dicyclohexyl) -2-imidazolyl-1- (phenylmethoxy) ethane (Compound 13), 1- (2,4-dichlorophenyl) -2-imidazolinole-1 -(3-phenylpropoxy) ethane (compound 14) is preferred, and heptyl 8- [1- (2,4-dichlorophenyl) -2_imidazolylethoxy] octanoate (compound 11) is most preferred .

The compound represented by the formula (I) can be produced, for example, by the following method.

 (II) (ΠΙ)

In the above formula,, R ₂ , R ₃ , X and Y have the same meanings as described above, and Ζ represents a halogen atom. The compound represented by the formula (I) is produced by reacting a compound represented by the formula (II) with a compound represented by the formula (III) in the presence of a solvent and a base. The base used is not particularly limited, and for example, sodium hydride, butyllithium, and the like can be used. The amount of the base used is not particularly limited, but is usually about 1.0 to 1.2 mol per 1 mol of the compound represented by the formula (Π).

 The solvent used is not particularly limited as long as it does not inhibit the reaction and can dissolve the compounds represented by the formulas (III) and (III) to some extent. For example, DMF, THF, and ethyl ether are used. can do.

 The amount of the solvent used is not particularly limited, but is usually about 0.2 to 1 liter per 1 raol of the compound represented by the formula (II).

 The reaction temperature is not particularly limited, but is usually 0 to 40 ° C, preferably 0 to 25 ° C.

 The reaction time is not particularly limited, but is usually 2 to 24 hours, and preferably 2 to 4 hours.

 The compound represented by the formula (II) can be produced by using a commercially available compound or according to the method of Godefroi, EF, et al. (J. Med. Chem., 784-791).

Compounds of formula (ΙΠ) can be prepared by reacting a force using a commercially available, or the alcohol of compound Chioeru chloride, or with PC1 _5. After completion of the above reaction, the compound represented by the formula (I) can be collected from the reaction mixture according to a conventional method. For example, the compound represented by the formula (I) can be obtained by distilling off the solvent under reduced pressure, adding an organic solvent immiscible with water, washing with water and drying. Further, the obtained compound represented by the formula (I) may be further purified by chromatography or the like.

 The compound of the present invention (the compound represented by the formula (I) and a salt thereof) can be used as an agricultural chemical composition. As used herein, the term "pesticide composition" refers to a composition that gives some effect to plants (including seeds, pollen, cut flowers, etc.).

 The pesticidal composition of the present invention is used for the purpose of inhibiting the biosynthesis of jasmonic acid. More specifically, for example, (1) male sterilization, (2) pollen tube elongation inhibition, and (3) cut flower It is used for purposes such as maintaining freshness, (4) extending flowering period, (5) suppressing pollen formation, (6) promoting germination, (7) weeding, and (8) preventing pollen scattering.

Plants targeted by the pesticidal composition of the present invention include all plants that biosynthesize jasmonic acid, but higher plants are particularly preferred, irrespective of monocots or dicots. Furthermore, in order to produce a first-generation hybrid (F1) plant of a plant having an amphoteric flower (including, but not limited to, rice and soybean), the pesticide composition of the present invention is administered to a plant to inhibit pollen formation and / or Alternatively, pollen obtained from another plant that induces male sterility and is to be crossed may be pollinated to the plant. In the past, efficient work to obtain amphoteric F1 plants required a great deal of work to remove the stamens of the flowers before maturity. However, it was extremely difficult to implement the method, and it was actually difficult to implement the method. By administering the pesticidal composition of the present invention, pollen formation and / or male sterilization can be reliably and simply suppressed, so that F1 plants can be obtained very simply and efficiently. The composition can be conveniently and widely administered by spraying or spraying. Then, by simply spraying pollen obtained from a plant to be crossed on the obtained male sterile plant on a large scale, an F1 plant of a plant having an amphoteric flower can be produced on a field scale.

 Further, by administering the pesticidal composition of the present invention to a plant (such as cedar) that causes pollinosis of an animal, pollen formation of the plant can be suppressed, and the amount of pollen scattered in the air can be reduced. Being reduced, it is considered to be effective in controlling hay fever (reduction of patients and reduction of Z or symptoms). In addition, some ornamental plants (eg, lilies) emit large amounts of pollen from large anthers, polluting petals and clothing. In such plants, it is thought that the value and commercial value as ornamental plants are improved by suppressing pollen formation. Such prevention of pollen scattering is achieved not only by suppressing pollen formation but also by suppressing anther cleavage.

 Furthermore, by administering the pesticidal composition of the present invention during the flowering period of a plant, it is possible to prolong the flowering period, that is, to maintain the plant in a flowered state for a long time. There are advantages such as improving the commercial value. The effect of extending the flowering period is also effective for cut flowers, and by using the pesticidal composition of the present invention, it is possible to maintain the cut flowers in good condition for a long period of time (keep freshness). Become.

In addition, it has been known that jasmonic acid is involved in the dormancy of plant seeds. By administering the pesticidal composition of the present invention, jasmonic acid can break the dormancy of seeds with reduced germination ability due to long-term storage and the like. It can promote germination. Further, as described above, since the disease resistance and / or stress response function of a plant is reduced by administration of the pesticidal composition of the present invention, the pesticidal composition of the present invention may have herbicidal activity. In addition, herbicides that act specifically on plant species (such as harmful plants) that you want to control

By administering (including a specific pathogen) together with the pesticidal composition of the present invention, the herbicide's resistance to stress and / or disease is reduced, and as a result, the effect of the herbicide is enhanced. With smaller amounts of herbicides, only the plant species that you want to control can be selectively removed.

 The pesticidal compositions of the present invention can be used in the form of directly sprayable aqueous solutions, powders, suspensions, and highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, It can be administered to plants in any form, such as by spraying, atomizing, dusting, dusting or mixing in growing soil or water, in the form of a spray material or granules. In addition, it can be used as a mixture with an auxiliary agent and other components described below. The form of the composition, the administration method and the like can be appropriately selected according to the target control target, target plant species and growth stage. For example, when the purpose is to suppress pollen formation in plants, an aqueous solution containing the compound at an appropriate concentration (for example, 10 / M) is sprayed on the flowers during or immediately before the flower formation and / or pollen formation, Alternatively, absorb with water. If the purpose is to extend the flowering period, it may be administered just before or during the flowering period. When the purpose is to promote germination, it may be applied by spraying or applying to the seeds or immersing the seeds in an aqueous solution of the compound. Furthermore, if the purpose is weed control, it may be administered by any method before or after germination of the plant to be removed. When used with another herbicide, the herbicide may be administered simultaneously or continuously. As used herein, the term "herbicide" refers to any herbicidally active agent or pathogen to a plant known in the art, which depends on the plant species of interest and its growth stage, but If appropriate, appropriate ones can be selected (for example, commonly used light demanding herbicides, photosynthesis inhibitors, etc.).

 Suitable auxiliaries include, but are not limited to, the following:

Medium to high boiling mineral oil fractions, such as kerosene and diesel oils, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example para Fin, tetrahydronaphthalene, alkylated naphthalene and their derivatives, alkylated benzene and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strong polar Solvents include, for example, amines such as N-methylpyrrolidone and water.

 Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the compounds according to the invention are themselves or dissolved in oils or solvents and are dissolved in water with wetting agents, tackifiers, dispersants or emulsifiers. It can be made uniform. Alternatively, concentrates can be prepared which comprise the active compound, wetting agents, tackifiers, dispersants or emulsifiers and / or solvents or oils, which concentrates are suitable for dilution with water . A suitable surfactant (adjuvant) may also be included in the composition.

 Suitable auxiliaries can be appropriately selected by a person skilled in the art according to the application.

 The compositions in powder, dusting and dust form can be prepared by mixing or grinding the compound of the active ingredient with a solid carrier.

 Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by combining the active ingredients with a solid carrier. The solid carriers are mineral earths, such as silica, silica gel, silicate, talc, kaolin, limestone, lime, chalk, porcelain clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, Ground synthetic materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and products of plant origin, such as cereal flour, bark flour, wood flour and nut shell flour, cellulose flour, or other It may be a solid carrier, but is not limited to these.

 The concentration of the compound of the present invention or a salt thereof may vary. In general, these preparations contain at least one active ingredient in the range of about 0.05-0.1% by weight, preferably 0.25-0.5%.

Furthermore, the pesticidal composition of the present invention can be applied in the form of a mixture of the active ingredient compound alone or in combination with other herbicides. A method of inhibiting jasmonate biosynthesis in a plant by administering the compound of the present invention to the plant as described above is also within the scope of the present invention. By suppressing the biosynthesis of jasmonic acid, it suppresses pollen formation, suppresses pollen tube elongation, induces male sterility, maintains cut flower freshness, prolongs flowering period, promotes germination, reduces disease resistance, reduces disease resistance, etc. A method for inducing a plant to have one or more effects selected from the group consisting of reduced stress response function is also included in the present invention.

 The present invention provides a jasmon comprising a step of bringing a test substance into contact with a plant-derived AOS and a step of selecting a test substance that inhibits the activity of a plant-derived AOS, in addition to the compound and the pesticide composition. Methods for screening for substances that specifically inhibit acid biosynthesis are also included. The reason why AOS is suitable as a target enzyme in such a screening method is as follows.

 Regulation of physiological phenomena such as stress response and pollen function expression of plants is expected to have a great impact on various fields such as agricultural production, horticulture and environmental measures. Jasmonic acid is known as a signal transmitter that plays a central role in these physiological phenomena, that is, regulation of the jasmonic acid signal achieves regulation of plant stress response and expression of pollen function. To indicate that As a means for regulating the jasmonate signal, an inhibitor that specifically inhibits biosynthesis can be an effective tool.

Jasmonic acid is biosynthesized starting from lenolic acid, an unsaturated fatty acid, as shown in Fig. 1. Analysis of the function of jasmonic acid biosynthesis revealed that biosynthetic intermediates 12-oxophytodienoic acid (0PDA) and 15, 16-dihydro12-oxophytodienoic acid (OPC 8: 0) were secondary metabolic in the same manner as jasmonic acid. It shows product-inducing activity (Phytochemistry, 47, 527-537). Also, in stress responses, 0PDA plays a complementary role with jasmonic acid (Proc Natl Acad Sci USA 98, 12837-12842). The above studies suggest that biosynthetic intermediates such as OPDA and OPC8: 0, which have synthesized five-membered ring skeletons, function in the jasmonate signaling system. Therefore, in order to design inhibitors that block the jasmonate signal, it is necessary to focus on the biosynthesis step before OPDA is synthesized. That is, attention is paid to A0C, AOS, and L0X. Of these three candidates, L0X has several products Since it is a substrate of the biosynthetic pathway, it is judged that it is not a desirable target from the viewpoint of creating an inhibitor specific to jasmonic acid biosynthesis. The biosynthetic substrate of A0C is extremely unstable and difficult to handle in the laboratory. These findings suggest that AOS is the optimal target for biosynthesis inhibitors to block the jasmonate signal. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a diagram showing the biosynthetic pathway of jasmonic acid.

 FIG. 2 is a photograph showing Arabidopsis cultured in a medium containing Compound 11;

 FIG. 3 is a photograph showing Arabidopsis thaliana flowers sprayed with compound 11;

 FIG. 4 is a photograph showing tobacco pollen in a solution containing compound 11; FIG. 5 is a photograph showing cut flower chrysanthemums inserted into a solution containing compound 11; BEST MODE FOR CARRYING OUT THE INVENTION

 (Example 1)

 Heptyl 8- [1- (2,4-dicyclohexyl) -2-imidazolylethoxy] -octanoate (Compound 11)

1- (1 imidazole-1-yl) -2- (2,4-dichloromethane) Ethanol (l. Og, 3.9 mmol) (ACROS ORGANICS) in DMF ( ³ mL) While stirring, sodium hydride (0.156 g, 3.9 mmol) was gradually added at room temperature. The reaction solution was stirred at 40 ° C for 30 minutes with stirring. After cooling to 115 ° C, the reaction mixture was added to a solution of 8-bromooctanoic acid heptyl ester (1.25 g, 3.9 mmol) in DMF, followed by stirring at room temperature. After evaporating the solvent under reduced pressure, the residue was diluted with chloroform. The mouth layer was washed with water and dried over anhydrous sodium sulfate. silica gel Purification by column chromatography (form: methanol = 10: 1; v: v) according to the above gave 0.48 _§ (yield 29.8%) of the above compound (light yellow oil).

Light yellow oil.Ή NMR (CDC1 ₃ ) δ 0.88 (t, J = 3.3 Hz, 3H), 1.27-1.40 (m, 10H), 1.51-1.71 (m, 10H), 2.29 (t, J = 7.2 Hz, 2H), 3.20-3.24 (m, IH), 3.29-3.35 (m, IH), 3.98 (dd, J = 7.4, 14.6 Hz, IH), 4.03-4.19 (m, 3H), 4.81 (dd, J = 2.6, 7.3 Hz, IH), 6.92 (s, 1H), 7.02 (s, 1H), 7.26 (s, 2H), 7.41 (s, IH), 7.45 (s, IH). ESI-MS m / e 498 . (M + H) Anal, calcd for C 26 H 38 C1 2 N 2 0 3:. C, 62.77; H, 7.70; N, 5.63; CI, 14.25 Found: C, 62.85; H, 7.85; N, 5.83 CI, 14.34.

 (Example 2)

l- [2-aryloxy-2- (2,4-dichlorophenyl) -ethyl] '1H-imidazole (compound 1)

 The above compound was synthesized according to the method described in Example 1.

Light yellow oil. NMR (CDC1 ₃ ) δ 3.74 (dd, J = 5.9, 12.8 Hz, IH), 3.93 (dd, J = 5.1, 12.8 Hz, IH), 4.02 (dd, J = 7.3, 14.2 Hz, 1H ), 4.19 (dd, J = 2.6, 14.3 Hz, IH), 4.93 (dd, J = 2.6, 7.3 Hz, IH), 5.15-5.20 (m, 2H), 5.70-5.80 (m, IH), 6.92 ( s, IH), 7.02 (s, 1H), 7.27 (s, 2H), 7.42 (s, 1H), 7.45 (s, IH). ESI-MS m / e 297 (M + H). Anal, calcd for _{C 14 H 14 C1 2 N 2} 0:. C, 56.58; H, 4.75; N, 9.43; CI, 23.86 Found: C, 56.48; H, 4.80; N, 9.49; CI, 23.96.

 (Example 3)

 l- [2- (2,4-dichlorophenyl) -2- (3-methyl-2-butenyloxy) -ethyl] -IH-imidazole (compound 2)

上記化合物を実施例 1記載の方法に準じて合成した Light yellow oil. ¾ NME, (CDC1₃) δ 1.50 (s, 3H), 1.71 (s， 3H), 3.75 (dd, J= 7.9, 10.9 Hz, IH), 3.87 (dd, J= 6.4, 10.9Hz, IH), 3.98 (dd, J= 7.3, 14.3 Hz, IH), 4.15 (dd, J= 2.6, 14.3 Hz, 1H)， 4.91 (dd, J二 2.5, 7.3 Hz, IH), 5.19 (br, IH), 6.92 (s， IH), 7.02 (s, IH), 7.27 (s, 2H), 7.41 (s, IH), 7.45 (s, IH). ESI-MS m/e 326 (M+H). Anal, calcd for C₁₆H₁₈C1₂N₂0: C， 59.09； H, 5.58； N, 8.61； CI, 21.80. Found: C, 58.96； H, 5.45； N， 8.72； CI, 21.88.

The above compound was synthesized according to the method described in Example 1. Light yellow oil. ¾ NME, ( CDC1 3) δ 1.50 (s, 3H), 1.71 (s, 3H), 3.75 (dd, J = 7.9, 10.9 Hz, IH), 3.87 (dd, J = 6.4, 10.9Hz , IH), 3.98 (dd, J = 7.3, 14.3 Hz, IH), 4.15 (dd, J = 2.6, 14.3 Hz, 1H), 4.91 (dd, J-2.5, 7.3 Hz, IH), 5.19 (br, IH), 6.92 (s, IH), 7.02 (s, IH), 7.27 (s, 2H), 7.41 (s, IH), 7.45 (s, IH). ESI-MS m / e 326 (M + H) _{. Anal, calcd for C 16 H} 18 C1 2 N 2 0:. C, 59.09; H, 5.58; N, 8.61; CI, 21.80 Found: C, 58.96; H, 5.45; N, 8.72; CI, 21.88.

 (Example 4)

 l- [2- (2,4-Dicyclohexyl) -2-nonyloxy-ethyl] _1H-imidazole (Compound 3)

上記化合物を実施例 1記載の方法に準じて合成した。

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. ¾ NMR (CDC1 3) δ 0.88 (t, J = 7.0 Hz 3H), 1.25 (br, 16H), 1.49-1.56 (m, 2H), 3.19-3.25 (m, 1H), 3.32-3.35 (m, 1H), 3.98 (dd, J = 7.4, 14.6 Hz, IH), 4.17 (dd, J = 2.7, 14.5 Hz, IH), 4.83 (dd, J = 2.7, 7.4 Hz, IH), 6.92 ( s, IH), 7.01 (s, IH), 7.25 (s, 2H), 7.41 (s, 1H), 7.45 (s, IH). ESI-MS m / e 412 (M + H) +. Anal, calcd for C _{2. H 28 C1 2 N 2 0:} . C, 62.66; H, 7.36; N, 7.30; CI, 18.50 Found: C, 62.58; H, 7.29; N, 7.25; CI, 18.55.

 (Example 5)

上記化合物を実施例 1記載の方法に準じて合成した。 l- [2-Butoxy-2- (2,4-dichlorophenyl) -ethyl] -IH-imidazole (compound 4)

The above compound was synthesized according to the method described in Example 1.

Light yellow oil.¾ NMR (CDC1 ₃ ) δ 0.88 (t, J = 7.5 Hz 3H), 1.25-1.37 (m, 2H), 1.48-1.55 (m, 2H), 3.20-3.26 (m, IH), 3.31 -3.36 (m, IH), 3.97 (dd, J = 7.5, 14.6 Hz, 1H), 4.17 (dd, J = 2.6, 14.3 Hz, IH), 4.83 (dd, J = 2.7, 7.3 Hz, 1H), 6.92 (t, J = 1.3 Ηζ, ΐΗ), 7.01 (d, J = 1.1 Ηζ, ΐΗ), 7.25 (s, 2H), 7.41 (s, 1H), 7.45 (s, IH) .ESI-MS m / e 314 (M + . H) Anal, calcd for C 15 H 18 C1 2 N 2 0:. C, 57.52; H, 5.79; N, 8.94; CI, 22.64 Found: C, 57.53; H, 5.70; N, 8.96; CI, 22.69 .

 (Example 6)

上記化合物を実施例 1記載の方法に準じて合成した。 Etinole 5- [l- (2,4-dichlorophenyl) -2-imidazolylethoxy] pentanoate (Compound 5)

The above compound was synthesized according to the method described in Example 1.

Light yellow oil.Ή ΝΜΕ, (CDC1 ₃ ) δ 1.26 (t, J = 7.1 Hz, 3H), 1.55-1.66 (m, 2H), 2.28 (t, J = 7.1 Hz, 2H), 3.21-3.26 (m , 1H), 3.32 3.37 (m, IH), 3.98 (dd, J = 7.3, 14.6 Hz, 1H), 4.11-4.20 (m, 3H), 4.84 (dd, J = 2.6, 7.3 Hz, 1H), 6.92 (s, IH), 7.02 (s, IH), 7.25 (s, 2H), 7.41 (s, IH), 7.45 (s, IH). ESI-MS m / e 385 (M + H). Anal, calcd _{for C 18 H 22 C1 2 N} 2 0 3:. C, 56.11; H, 5.76; N, 7.27; CI, 18.40 Found: C, 56.11; H, 5.70; N, 7.30; CI, 18.56.

 (Example 7)

 6- [l- (2,4-Dimethyl phenyl) -2-imidazolylethoxy] hexyl hexate (Compound 6)

上記化合物を実施例 1記載の方法に準じて合成した。

The above compound was synthesized according to the method described in Example 1.

^{Light yellow oil. X H NME (} CDC1 3) δ 1.25 (t, J = 7.2 Hz, 3H), 1.55-1.66 (m, 4H), 2.27 (t, J = 7.2 Hz, 2H), 3.19-3.24 (m , IH), 3.31-3.37 (m, IH), 3.97 (dd, J-7.3, 14.6 Hz, IH), 4.10-4.29 (m, 3H), 4.83 (dd, J = 2.6, 7.3 Hz, IH), 6.92 (s, IH), 7.02 (s, IH), 7.25 (s, 2H), 7.41 (s, IH), 7.44 (s, lH). ESI-MS m / e 400 (M + H). Anal. _{calcd for C 19 H 24 C1 2} N 2 0 3:. C, 57.15; H, 6.06; N, 7.02; CI, 17.76 Found: C, 57.11; H, 6.15; N, 7.10; CI, 17.80.

 (Example 8)

 Methyl 8- [l- (2,4-dichloropheninole) -2-imidazolylethoxy] octanoate (Compound 7)

上記化合物を実施例 1記載の方法に準じて合成した。

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. Ή NMR (CDC1 3) δ 1.28 (br, 6H), 1.50-1.69 (m, 4H), 2.30 (t, J = 7.5 Hz, 2H), 3.18-3.22 (m, 1H), 3.29- 3.34 (m, IH), 3.67 (s, 3H), 3.98 (dd, J = 7.3, 14.3 Hz, 1H), 4.16 (dd, J = 2.8, 14.5 Hz, IH), 4.83 (dd, J = 2.6, 7.3 Hz, IH), 6.92 (s, IH), 7.02 (s, IH), 7.25 (s, 2H), 7.41 (s, IH), 7.45 (s, IH) .ESI-MS m / e 413 (M + H) +. Anal, calcd for C ₂₀ H ₂₆ C1 ₂ N ₂ O ₃ : C, 58.12; H, 6.34; N, 6.78; CI, 17.15. Found: C, 58.19; H, 6.39; N, 6.90; CI, 17.25.

 (Example 9)

8- [l- (2,4-Dichlorophenyl) -2-imidazolylethoxy] octanoic acid propynole (Compound 8)

 The above compound was synthesized according to the method described in Example 1.

Light yellow oil.Ή NMR (CDC1 ₃ ), δ 0.94 (t, J = 7.3 Hz, 3H), 1.24-1.29 (m, 2H), 1.50- 1.69 (m, 10H), 2.30 (t, J = 7.3 Hz , 2H), 3.19-3.24 (m, 1H), 3.29-3.35 (m, 1H), 3.98 (dd, J = 7.5, 14.7 Hz, 1H), 4.03-4.19 (m, 3H), 4.82 (dd, J = 2.6, 7.3 Hz, IH), 6.92 (s, 1H), 7.02 (s, 1H), 7.26 (s, 2H), 7.41 (s, IH), 7.45 (s, IH). ESI-MS m / e 442 (M + H). Anal, calcd for C ₂₂ H ₃ . _{Cl 2 N 2 O 3:.} C, 59.86; H, 6.85; N, 6.35; CI, 16.04 Found: C, 59.99; H, 6.82; N, 6.39; CI, 16.06. (Example 10)

8- [l- (2,4-Dichlorophenyl) -2-imidazolylethoxy] -butyl octanesate (Compound 9)

 The above compound was synthesized according to the method described in Example 1.

Light yellow oil.Ή NMR (CDC1 ₃ ) δ 0.93 (t, J = 7.3 Hz, 3H), 1.24-1.30 (m, 4H), 1.51-1.71 (m, 10H), 2.29 (t, J = 7.2 Hz, 2H), 3.20-3.24 (m, IH), 3.29-3.35 (m, IH), 3.98 (dd, J = 7.4, 14.6 Hz, IH), 4.03-4.19 (m, 3H), 4.81 (dd, J = 2.6, 7.3 Hz, IH), 6.92 (s, 1H), 7.02 (s, IH), 7.26 (s, 2H), 7.41 (s, 1H), 7.45 (s, IH). ESI-MS m / e 456 (M + H) +. Anal, calcd for C ₂₃ H ₃₂ Cl ₂ N ₂ O ₃ : C, 60.66; H, 7.08; N, 6.15; CI, 15.57. Found: C, 60.59; H, 6.90; N, 6.22; CI, 15.69.

 (Example 11)

上記化合物を実施例 1記載の方法に準じて合成した。 3-methylbutyl 8- [l- (2,4-dicyclohexyl) -2-imidazolylethoxy] octansanoate (Compound 10)

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. Ή NMR (CDC1 3) δ 0.87 (s, 3H), 0.89 (s, 3H), 1.24-1.27 (m, 8H), 1.48- 1.73 (m, 6H), 2.30 (t, J = 7.2 Hz, 2H), 3.20-3.24 (m, IH), 3.29-3.35 (m, IH), 3.98 (dd, J = 7.5, 14.6 Hz, 1H), 4.08-4.19 (m, 3H), 4.82 (dd, J = 2.7, 7.2 Hz, IH), 6.92 (s, 1H), 7.02 (s, IH), 7.27 (s, 2H), 7.41 (s, IH), 7.45 (s, IH) .ESI-MS m / e 470 (M + H). Anal, calcd for C ₂₄ H ₃₄ Cl ₂ N ₂ O ₃ : C, 61.41; H, 7.30; N, 5.97; CI, 15.10. Found: C, 61.52; H, 7.35; N , 6.02; CI, 15.14.

 [Example 12]

 ll- [l- (2,4-dichlorophenyl) -2-imidazolylethoxy] ethyl decanoate

上記化合物を実施例 1記載の方法に準じて合成した。 (Compound 1 2)

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. Ή NMR (CDC1 3) δ 1.25-1.28 (m, 17H), 1.52 (t, J = 6.9 Hz 2H), 1.62 (t, J = 7.3 Hz 2H), 2.28 (t, J = 7.7 Hz , 2H), 3.19-3.24 (m, IH), 3.31-3.35 (m, 1H), 3.98 (dd, J _x = 7.3, = 14.6 Hz, 1H), 4.10-4.29 (m, 3H), 4.83 (dd , J = 2.6, 7.3 Hz, IH), 6.92 (s, 1H), 7.02 (s, IH), 7.25 (s, 2H), 7.41 (s, IH), 7.44 (s, IH) .ESI-MS m / e 470 (M + H). Anal, calcd for C ₂₄ H ₃₄ Cl ₂ N ₂ O ₃ : C, 61.41; H, 7.30; N, 5.97; CI, 15.10. Found: C, 61.51; H, 7.35; N, 5.92; CI, 15.15.

 (Example 13)

 l- (2,4-dichlorophenyl) -2-imidazolyl-1- (phenylmethoxy) ethane (Compound 13)

 The above compound was synthesized according to the method described in Example 1.

Light yellow oil.Ή NMR (CDC1 ₃ ) δ 4.02 (dd, J, = 7.5, J ₂ = 14.7 Hz, IH), 4.18- 4.23 (m, 2H), 4.40 (d, J = 12.1 Hz, IH), 4.95 (dd, J, = 4.7, J ₂ = 6.9 Hz, IH), 6.90 (s, IH), 6.94 (d, J = 7.3 Hz, IH), 7.04 (s, 1H), 7.23-7.45 (m, .. 6H), 8.01 (s , IH) ESI-MS m / e 348 (M + H) Anal, calcd for C 18 H 16 C1 2 N 2 0: C, 62.26; H, 4.64; N, 8.07; CI Found: C, 62.29; H, 4.61; N, 8.12; CI, 20.38.

 (Example 14)

上記化合物を実施例 1記載の方法に準じて合成した。 l- (2,4-Dicyclohexyl) -2-y midazolyl-1- (3-phenylpropoxy) ethane (Compound 14)

The above compound was synthesized according to the method described in Example 1.

. Light yellow oil ¾ NMR (CDC1 3) δ 1.85 (t, t, J t = 7.3; J = 6.7 Hz 2H), 2.61 (t, J = 6.9 Hz 2H), 3.19-3.24 (m, 1H), 3.33 -3.35 (m, 1H), 3.98 (dd, J, = 7.3, J ₂ = 14.6 Hz, IH), 4.10-4.29 (m, IH), 4.83 (dd, J, = 2.6; J ₂ = 7.3 Hz, IH), 6.92 (s, 1H), 7.09-7.27 (m, 6H), 7.38 (s, IH), 7.45 (s, IH). ESI-MS m / e 376 (M + H). Anal, calcd for _{C 20 H 20 Cl 2 N 2} O:. C, 64.01; H, 5.37; N, 7.46; CI, 18.89 Found: C, 64.05; H, 5.32; N, 7.52; CI, 18.92.

 (Example 15)

 [l- (2,4-dichloropheninole) -2-imidazolyl] (2-phenoxyethoxy) methane (compound 15)

上記化合物を実施例 1記載の方法に準じて合成した。

The above compound was synthesized according to the method described in Example 1.

_{Light yellow oil. NMR (CDC1 3} ) δ 3.61-3.74 (m, 2H), 3.98-4.28 (m, 3H), 4.99-5.02 (m, IH), 6.62-6.88 (m, 5H), 6.95-7.47 ( ESI-MS m / e 408 (M + H). Anal, calcd for C ₂ . H _{2. C1 2 N 2 0 3:.} C, 58.98; H, 4.95; N, 6.88; CI, 17.41 Found: C, 58.92; H, 4.91; N, 6.80; CI, 17.50.

 (Example 16)

上記化合物を実施例 1記載の方法に準じて合成した。 l- (2,4-Diphenyl phenyl) -l-[(2-diphenyl) methoxy] -2-imidazolylethane (Compound 16)

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. NMR (CDC1 ₃ ) δ 4.08 (dd, J _x = 7.3, 4 = 14.6 Hz, 1H), 4.23 (dd, J _x = 2.5, ₂ = 14.6 Hz, IH), 4.40 (d, J = 12.7 Hz, IH), 4.54 (d, J = 12.5 Hz, IH), 5.04 (dd, = 2.6, J ₂ = 7.3 Hz, IH), 6.90 (s, 1H), 7.00 (s, IH), 7.23- .. 7.45 (m, 8H) ESI-MS m / e 382 (M + H) Anal, calcd for C 18 H 15 Cl 3 N 2 O: C, 56.64; H, 3.96; N, 7.34; CI, 27.87. Found: C, 56.68; H, 3.90; N, 7.38; CI, 27.80.

 (Example 17)

 l- (2,4-Diphenyl phenyl) -l-[(4-chloropheninole) methoxy] -2-imidazolylethane (Compound 17)

上記化合物を実施例 1記載の方法に準じて合成した。

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. Ή NMR (CDC1 3) δ 4.05 (dd, J x = 7.5, 4 = 14.6 Hz, 1H), 4.12- 4.18 (m, 2H), 4.43 (d, J = 11.7 Hz, IH), 4.97 (dd, ^ = 2.6, J ₂ = 7.7 Hz, 1H), 6.90 (s, IH), 7.00-7.03 (m, 3H), 7.15 (s, IH), 7.21-7.33 (m, 4H), 7.44 ( .. t, J two 5.1Hz, 2H) ESI-MS m / e 382 (M + H) Anal, calcd for C 18 H 15 C1 3 N 2 0: C, 56.64; H, 3.96; N, 7.34; CI , 27.87. Found: C, 56.60; H, 3.88; N, 7.34; CI, 27.82.

 (Example 18)

上記化合物を実施例 1記載の方法に準じて合成した。 l- (2,4-Dimethyl phenyl) -l-[(6-Di (3-pyridyl) methoxy] -2-imidazolylethane (Compound 18)

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. Ή NMR (CDC1 3) δ 4.11-4.26 (m, 3H), 4.47 (d, J = 12.5 Hz, IH), 5.00 (dd, = 2.6, J 2 = 7.3 Hz, IH), 6.82 ( s, 1H), 6.82 (s, IH), 7.01 (s, 1H), 7.24-7.58 (m, 4H), 7.77 (s, 1H), 8.06 (s, lH) ESI-MS m / e 383 (M + H). Anal, calcd for C ₁₇ H ₁₄ Cl ₃ N ₃ O: C, 53.34; H, 3.69; N, 10.98; CI, 27.79. Found: C, 53.42; H, 3.68; N, 10.68; CI, 27.82.

 (Example 19)

 l- (2,4-Dimethyl phenyl) -l-[(2,3-Diphenyl) methoxy] -2-imidazolylethane (Compound 19)

上記化合物を実施例 1記載の方法に準じて合成した。

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. Ή NMR (CDC1 3) δ 4.09 (dd,, = 7.2, J 2 = 14.6 Hz, 1H), 4.24 (dd, J x = 2.9, = 14.6 Hz, IH), 4.40 (d, J = 12.7 Hz, 1H), 4.53 ( d, J = 12.8 Hz, 1H), 5.05 (dd, ^! = 2.5, J 2 = 9.3 Hz, IH), 6.90 (s, 1H), 7.01 (s, IH), 7.18-7.45 (m, 7H). ESI-MS m / e 417 (M + H). Anal, calcd for C ₁₈ H ₁₄ Cl ₄ N ₂ O: C, 51.95; H, 3.39; N, 6.73; CI, 34.08. Found: C, 51.92; H, 3.35; N, 6.70; CI, 34.12.

 (Example 20)

上記化合物を実施例 1記載の方法に準じて合成した。 l- (2,4-Dichlorophenol) -l-[(2,4-Diphenylphenyl) methoxy] -2-imidazolylethane (Compound 20)

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. ¾ NMR (CDC1 3) δ 4.06 (dd, J x = 7.3, 2 = 14.5 Hz, IH), 4.23 (dd, J x = 2.9, J 2 = 14.6 Hz, IH), 4.34 (d, J = 12.5 Hz, IH), 4.48 (d, J = 12.5 Hz, IH), 5.02 (dd, ^! = 2.6, J ₂ = 7.6 Hz, IH), 6.89 (s, IH), 7.01 (s, IH) ), 7.19-7.38 (m, 5H), 7.43 (t, J = 1.9Hz, 2H). ESI-MS m / e 417 (M + H). Anal, calcd for C ₁₈ H ₁₄ Cl ₄ N ₂ O: C, 51.95; H, 3.39; N, 6.73; CI, 34.08. Found: C, 51.98; H, 3.30; N, 6.68; CI, 34.02.

 (Example 21)

 l- (2,4-dichlorophenyl) -l-[(2,6-dichlorophenyl) methoxy] -2-imidazolylethane (Compound 21)

上記化合物を実施例 1記載の方法に準じて合成した。

The above compound was synthesized according to the method described in Example 1.

Light yellow oil.¾ NMR (CDC1 ₃ ) δ 4.07 (dd, J, = 7.3, J ₂ = U.6 Hz, IH), 4.23 (dd, J _x = 2.5, ₂ = 14.6 Hz, IH), 4.33 ( d, J = 12.7 Hz, 1H ), 4.48 (d, J = 12.8 Hz, 1H), 5.02 (dd, = 2.6, J 2 = 7.3 Hz, IH), 6.90 (s, IH), 7.01 (s, 1H ..), 7.17-7.45 (m, 7H) ESI-MS m / e 417 (M + H) Anal, calcd for C 18 H 14 Cl 4 N 2 O: C, 51.95; H, 3.39; N, 6.73; CI, 34.08. Found: C, 51.96; H, 3.35; N, 6.65; CI, 34.15.

 [Example 22]

上記化合物を実施例 1記載の方法に準じて合成した。 l- (2,4-Dicyclohexyl) -l-[(3,5-difluorophenyl) methoxy] -2-imidazolylethane (Compound 22)

The above compound was synthesized according to the method described in Example 1.

Light yellow oil. Ή NMR (CDC1 3) δ 4.35-4.62 (m, 4H), 5.17-5.20 (m, 1H), 6.67 (m, 3H), 7.05-7.41 (m, 6H). ESI-MS m / e 384 (M + H) Anal , calcd for C 18 H 14 Cl 2 F 2 N 2 O:.. C, 56.42; H, 3.68; N, 7.31; CI, 18.50; F, 9.92 Found: C, 56.36; H, 3.72; N, 7.36; CI, 18.550; F, 9.96.

 (Example 23)

 8- (l-biphenyl-4-isle-2- [l, 2,4] triazole-1-yl-ethoxy) -octanoic acid heptyl (compound 23)

1 - biphenyl - 4-I le - ² - bromo - dissolved ethanone in THF, and with K ₂ C0 ₃ the presence, 1.5 eq of 1 - [1, 2, 4] Toriazo Ichiru was added, 12 hours The reaction was carried out at reflux. The reaction mixture was filtered, the filtrate was concentrated, and the concentrate was purified by silica chromatography to give 1-biphenyl-1-isyl-2- [1,2,4] triazole-1-ylethanetanone. Obtained. This compound was dissolved in dichloromethane and methanol (1: 1), NaBH ₄ (1 equivalent) was added, and the mixture was allowed to react at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and then mixed with saturated saline. Extracted three times in the mouth platform. After concentration under reduced pressure, 1-biphenyl-2-yl-2- [1,2,4] triazole-1-yl-ethanol was obtained by silica chromatography purification.

1-Bifeninole-4 -inole-2-[1,2,4] triazoinole-1 -inole -ethanore and 8-bromobutanoic acid heptyl ester were reacted according to the method described in Example 1. , The above compound was obtained.

Light yellow οϋ.Ή NMR (CDC1 ₃ ) δ 0.88 (t, J = 7.0 Hz, 3H), 1.22-1.32 (m, 14H), 1.46 (t, J = 6.6 Hz, 2H), 1.55-1.62 (m, 4H), 2.28 (t, J = 7.3 Hz, 2H), 3.14-3.19 (m, IH), 3.37-3.43 (m, 1H), 4.05 (t, J = 7.0 Hz, 2H), 4.34 (t, J = 5.2 Hz, 2H), 4.67 (t, J = 5.5 Hz, IH), 7.33-7.46 (m, 5H), 7.59 (t, J = 7.0 Hz, 4H), 7.96 (s, IH), 7.11 (s , IH). ESI-MS m / e 506 (M + H).

 (Example 24)

 8- (l-biphenyl-4-yl-2- [l, 2,4] 1, lyazol-1-yl-ethoxy) -methyl octanoate (compound 24)

 The above compound was synthesized according to the method described in Example 23.

_{Light yellow οΠ.Ή NMR (CDC1 3)} δ 1.22-1.23 (m, 8H), 1.47 (t, J = 6.6 Hz, 2H), 1.55- 1.63 (m, 4H), 2.29 (t, J = 1.1 Hz, 2H), 3.14-3.19 (m, IH), 3.37-3.42 (m, 1H), 3.66 (s, 3H), 4.34 (t, J = 5.5 Hz, 2H), 4.67 (t, J = 5.5 Hz, IH ), 7.34-7.46 (m, 5H), 7.60 (t, J 7.9 Hz, 4H), 7.96 (s, IH), 8.11 (s, IH). ESI-MS m / e 422 (M + H). (Example 25)

 8- (l-biphenyl-4-yl-2-imidazole-1-ylethoxy) -octanoic acid heptinole (compound 25)

上記化合物を実施例 2 3記載の方法に準じて合成した。

The above compound was synthesized according to the method described in Example 23.

_{Light yellow oil H NMR (CDC1 3} ) δ 0.88 (t, J = 6.5 Hz, 3H), 1.27-1.31 (m, 14H), 1.50- 1.62 (m, 6H), 2.28 (t, J = 7.3 Hz, 2H ), 3.19-3.24 (m, IH), 3.35-3.41 (m, 1H), 4.03-4.17 (m, 4H), 4.47 (dd, J = 7.3, 6.1 Hz, IH), 6.93 (s, IH), 7.02 (s, IH), 7.26-7.59 (m, 9H), ESI-MS m / e 505 (M + H).

 (Example 26)

 8- (2-imidazole-1-yl-1-phenyl-ethoxy) -heptyl octanoate (compound 26)

 The above compound was synthesized according to the method described in Example 23.

^{Light yellow oil. 1 !! NME (} CDC1 3) δ 0.88 (t, J = 6.8 Hz, 3H), 1.27-1.35 (m, 14H), 1.48- 1.65 (m, 6H), 2.28 (t, J = 7.7 Hz, 2H), 3.17-3.21 (m, IH), 3.30-3.40 (m, 1H), 4.03-4.14 (m, 4H), 4.41 (dd, J = 7.7, 9.0 Hz, IH), 6.90 (s, IH), 7.01 (s, IH), 7.21-7.41 (m, 5H), ESI-MS m / e 429 (M + H).

 (Example 27)

 Methyl 8- (2-imidazole-1-yl-1-pheninoleethoxy) -octanoate (Compound 27)

 The above compound was synthesized according to the method described in Example 23.

_{yellow oiVH NMR (CDC1 3) δ} 1.26-1.29 (m, 6H), 1.32-1.63 (m, 4H), 2.29 (t, J = 7.7 Hz, 2H), 3.16-3.18 (m, 1H), 3.30-3.36 (m, 1H), 4.03-4.14 (m, 4H), 4.41 (dd, J = 7.3, 5.0 Hz, 1H), 6.90 (s, IH), 7.01 (s, 1H), 7.21-7.42 (m, 5H ), ESI-MS m / e 335 (M + H).

 (Example 28)

 8-[(2,4-dichloro-phenyl) -pyrimidine-5-yl-methoxy] -heptyl octanoic acid

(Compound 28) 's) SO L' (HI ^<s ) S6'9 '(HT' OL = f 'PP) 66 f' (H £ '∞) trt-SO''(Ηΐ^<ra ) ο ^ ε-οε ε' (HI '∞) T ^ S-LT S' (ικ ' ^Ζ Η ΙΊ = Γ' Ϊ) ιτζ '(Η9' ∞) 29 · RE 8 Ί '(ΗΠ ΐε τ-εδ ΐ' (Η6 's) 60 '(HS' ZHS ^ '%) 6809 ( ^ε ΐθαθ) πΗΝ Η ^. ^ OjpA

. Tsu ^ 导 i i ¾ ^> ¾¾ε z m ^ ^ ^ ^

 (6 Z 呦 导 ¾ 4 /, ^

"(Η + Η) 96 3 / ra SH-ISa '(HT L'2 = Γ' Ρ) TT'6 ΉΖ ΖΗ 9 Ζ = Γ 'Ρ) 698' (HS '^) 2 L-12 L' ( HI 's) tZ / S' (KZ L0 f-20 '(Ηΐ' ∞) 99 S-I9 S '(HZ' ∞) 192-IV2 '(RZ' ∞) OS S-WS '(Η8' ∞) 9 I-SS l mi '∞) τε τ-Δ ^ τ' (Ηε '∞) 88 "o-s8? ( ^Ε τοαο) 丽 NH _x n ° 丛. ip χ ^ _Ί

^Q- ¾¾ ^^ IM 2ϊ¾ ^ ^ ^ 'χ m ^, ¾ d, ^ ^ c¾a-8;? / — / ^ — 'Z

. Y--^ ft Ά-Λ (-^ τΧ τΧ ^^ −, ¾ 濂 ^-^^^. ^ ^^^^ ίΙ ^

 im NT # ¾- $ 3i¾¾L¾ ^ οε ^ W, army ¾¾m ¾

 , 璣 ¾ma ^ η / ^, η. One ^^ 〇. 8-, ¾ ~.

. ^ 导: 2 C ^ Q) 丄 «

L9 Z00 / £ 00ZdT / 13d 9 contract OOZ OAV 1H), 7.51 (s, 1H), ESI-MS m / e 409 (M + H).

[Test Example 1] Measurement of AOS inhibitory activity

In the presence of Compounds 1-29, AOS was reacted with 13- (S) _hydroperoxysilinolenic acid, a substrate of AOS, and the inhibitory activity of Compounds 1-29 on AOS was measured, and IC ₅ was determined. Was calculated.

 As the AOS, an AOS gene derived from Arabidopsis thaliana was expressed in Escherichia coli according to a conventional method, and purified from the Escherichia coli culture was used. In other words, after culturing Escherichia coli incorporating the AOS mass expression vector at 37 ° C for 2 hours, adding IPTG (lmM), culturing at 16 ° C for 8 hours, collecting the Escherichia coli by centrifugation, After crushing with, purification was performed using a Ni-column.

 13- (S) Hydroperoxylinolenic acid was prepared using soybean LOX by the method of Lederer et al. (J. Agric. Food Chem-47, 4611-4620).

The inhibitory activity was determined by the disappearance of the biosynthetic substrate, the reaction was analyzed by HPLC, the absorbance at 235 nm was monitored, and the peak was decreased. IC ₅₀ was calculated according to a standard method. Table 1 shows the results.

 〔table 1〕

Compound number AOS inhibitory activity (IC _fin μΜ)

 1 8.8 ± 2.2

 2 5.9 ± 3.2

 3 0.61 ± 0.2

 4 0.90 ± 0.3

 5 1.0 ± 0.6

 6 0.67 ± 0.2

 7 0.85 ± 0.3

 8 0.21 ± 0.6

 9 0.12 ± 0.02

 10 0.08 ± 0.022

 11 0.0 0.005

 12 6.2

 13 0.6

 14 0.8

 15 3.3

 16 5.3

 17 2.5

18 4.2 19 6.4

 20 3.2

 21 2.1

 22 1.5

 23 86

 24 121

 25 60

 26 42

 27 215

 28 153

 29 46 From these results, among the compounds in Table 1, compounds 3, 4, 6, 7, 8, 9, 10, 11, 13, and 14 have good AOS inhibitory activity, Among them, Compound 11 was found to have the highest AOS inhibitory activity, and thus the following examples were carried out using this compound as an AOS inhibitor.

 [Test Example 2] Effect on plant growth

 It was examined whether or not the compound 11 affects the growth of plants. Under aseptic conditions, Arabidopsis seeds were sown on 0.8% agarose-containing MS medium, a predetermined concentration of compound 11 was added, and the growth state of the plant before the flowering stage was observed. The result is shown in figure 2. Compound 11 was administered to the rightmost plant in the figure with lOM, the second plant from the right was administered, and the third plant from the right was administered 0.1 × M. Compound 11 was not administered to the leftmost plant (control).

 As shown in FIG. 2, administration of compound 11 in the range of 0.1 to: {μ} did not have a significant effect on plant growth. This result suggests that compound 11 does not inhibit the biosynthesis of the plant hormones gibberellin and brassinosteroid.

 [Test Example 3] Inducing male sterility

Compound 11 (10 μΜ) was dissolved in 0.1% methanol, and this was sprayed on Arabidopsis before flowering, and the morphology of the flower was observed. The spraying of Compound 11 was performed every other day at a dose of 0.5 mL / 100 cm ² between 14 and 10 days before flowering. A photograph of Arabidopsis thaliana flowers sprayed with compound 11 is shown in Figure 3b. Fig. 3a shows a photograph of the Arabidopsis thaliana flower (control) in which the i-Daily compound 11 was fogged. As shown in FIG. 3, the cleavage of anthers was clearly suppressed by the compound 11 fog. When the flower was observed for two weeks, no seed was formed. Therefore, it was confirmed that Compound 11 induced male sterility in Arabidopsis thaliana.

 Example 4 Inhibition of pollen tube elongation

 The pollen of tobacco (Nicotiana tabacum) was isolated, and the pollen was put into a solution (10 μ 、) containing compound 11, and the pollen of tobacco was used according to the method of Preuss (Gene Dev., 7, 974-985). Were germinated and observed under a microscope 8 hours later. A photograph of the pollen in the solution containing compound 11 is shown in Figure 4b. Fig. 4a shows a photograph of pollen (control / re) in water without compound 11.

 As shown in FIG. 4b, when placed in a solution containing compound 11, pollen tube elongation was significantly suppressed as compared with the control.

 [Example 5]: Extension of flowering period of flower

 Commercially available cut flower chrysanthemum (Dendranthema grandiflorum: 45cm long)

1) (溶液 μΜ or ΙΟΟμΜ) and leave it at room temperature (25-35 ° C) for 10 days (the solution was changed once during this period). The direction of the flowers was observed, and the freshness retention effect was evaluated based on the observation. Table 2 shows the results. Photos of the flowers 10 days later are shown in Figs. 5a to 5c.

 (Table 2)

表 2及び図 5に示すように、 化合物 1 1を含む溶液に差しておいた花は、 コン トロールに比べて、 有意に開花期間が延長されていた。

As shown in Table 2 and FIG. 5, the flowering period of the flower placed in the solution containing the compound 11 was significantly prolonged compared to the control.

This description includes part or all of the contents as disclosed in the description and / or drawings of Japanese Patent Application No. 2002-258824, which is a priority document of the present application. In addition, all publications, patents, and patent applications cited in the present invention are incorporated herein by reference in their entirety. Industrial applicability

 The compound of the present invention specifically inhibits the biosynthesis of jasmonic acid in plants, male sterility, inhibition of pollen tube elongation, keeping cut flowers fresh, extending flowering period, suppressing pollen formation, promoting germination, weeding, pollen It has the effect of preventing the scattering of water. Among these effects, the effects of suppressing pollen formation and preventing pollen scattering are particularly noteworthy.These actions are used to suppress the scattering of pollen from pollen-causing plants such as cedar, and to prevent the occurrence of pollinosis. Can be reduced.

Claims

Range of request The following equation (I)

[In the formula, is a C ₈ alkyl group, an optionally substituted biphenylyl group (the substituent is a substituent selected from Substituent Group A below.), Which may be substituted A phenyl group (the substituent is a substituent selected from Substituent Group A below); X represents an oxygen atom, a sulfur atom, an imino group, or a methylene group; R ₂ is an optionally substituted ^-( ₁₂ alkyl group (the substituent is a substituent selected from the following Substituent Group B)), an optionally substituted C ₂ _C ₁₂ alkyl group (the substituent is a substituent selected from substituent group _{B.), C 3 -.} C 4 Arukokishikaru Boniruarukiru group, C ₃ -C ₄₀ alkylaminocarbonyl group, optionally substituted A fuunyl group (the substituent is a substituent selected from Substituent Group A below); Y is indicates that ¾ and CH are directly bonded alkylene group C厂C _4, or Y in the absence of, R ₃ is an imidazolyl group, 1, 2, 4-Toriazoriru group, a pyrimidyl group, substituent group A is a halogen atom, a nitro group, Shiano group, a hydroxyl group, - C ₄ Al kill group, C ₄ alkoxy group , - ₍₄ Ha port alkyl group and, (: a厂C ₄ group consisting haloalkoxy group, Substituent group B includes a phenyl group which may be substituted (the substituent is a substituent selected from the above-described substituent group A); a phenoxy group which may be substituted; And a pyridyl group which may be substituted (the substituent is a substituent selected from the above-described substituent group A.). ] And a salt thereof. 2. An agricultural chemical composition comprising the compound according to claim 1 as an active ingredient.  3. A jasmonic acid biosynthesis inhibitor comprising the compound according to claim 1 as an active ingredient. 4. A male sterilizing agent comprising the compound according to claim 1 as an active ingredient.  5. A pollen tube elongation inhibitor comprising the compound according to claim 1 as an active ingredient.  6. A freshness-retaining agent for cut flowers, comprising the compound according to claim 1 as an active ingredient.  7. A flowering period extender comprising the compound according to claim 1 as an active ingredient.  8. A pollen formation inhibitor comprising the compound according to claim 1 as an active ingredient.  9. A germination accelerator comprising the compound according to claim 1 as an active ingredient.  10. A herbicide containing the compound according to claim 1 as an active ingredient.  11. A herbicide comprising the compound according to claim 1 and another compound having herbicidal activity. 12. A pollen scattering inhibitor comprising the compound according to claim 1 as an active ingredient.  13. A method for inhibiting the biosynthesis of jasmonic acid, comprising treating a plant with the compound according to claim 1.  14. A method for male sterilization, comprising treating a plant with the compound according to claim 1. 15. A method for inhibiting pollen tube elongation, comprising treating pollen with the compound according to claim 1.  16. A method for maintaining freshness, comprising treating cut flowers with the compound according to claim 1. 17. A method for extending a flowering period, comprising treating a plant with the compound according to claim 1.  18. A method for suppressing pollen formation, comprising treating a plant with the compound according to claim 1.  19. A method for promoting germination, comprising treating a seed with the compound according to claim 1. 20. A herbicidal method comprising treating a plant with the compound according to claim 1.  21. A herbicidal method comprising treating a plant with the compound according to claim 1 and another compound having herbicidal activity.  22. A method for preventing pollen scattering, comprising treating a plant with the compound according to claim 1. 23. A step of contacting the test substance with a plant-derived allenoxide synthase and a step of selecting a test substance that inhibits the activity of the plant-derived allenoxide synthase. A method for screening a substance that specifically inhibits acid biosynthesis.