JP6061321B2 - Plant activator - Google Patents

Description

  The present invention relates to a plant activator that activates an endogenous defense system of a plant to control disease.

  Crops disease is a major cause of yield loss, and as a countermeasure against this, crop protection using a combination of agricultural chemicals such as fungicides and disease resistant varieties is widely carried out. A major problem is that pathogens become resistant. In order to solve this problem, a method using a combination of several fungicides with different mechanisms of action is widely adopted, but the current strategy centered on fungicides is concerned about the impact on the environment. Therefore, the development of new disease control methods with consideration for the environment is required.

  Under such circumstances, a plant activator (also called a plant vital agent or a disease resistance inducer) that activates an endogenous defense system of a plant to control a disease has attracted attention. The plant activator has no problem of forming resistance against phytopathogenic fungi and has little direct impact on the ecosystem itself. Therefore, the plant activator is expected to serve as a crop protection means that greatly reduces the burden on the environment.

  When a plant detects the invasion of a pathogen, it activates a defense mechanism called hypersensitive cell death that spontaneously kills cells around the site of infection, and prevents the spread of infection by forming a characteristic necrotic lesion. Elucidation of the formation process of hypersensitive cell death is expected to lead to an understanding of plant disease resistance reaction activation mechanism, but the details are not yet clear.

  Recently, acyltransferase (OsAT1) has been identified as a gene involved in the biosynthesis of rice (Plant Mol. Biol., 63, pp.847-860, 2007). Induction of marker gene PBZ1, PR1 expression, accumulation of rice phytoalexin, and improved resistance to blast have been reported (The 33rd Annual Meeting of the Japanese Pesticide Society, Matsuda et al., Title: C312, 2008) April 1 of the year). Since it is speculated that the product of the reaction catalyzed by OsAT1 triggers the induction of a series of disease resistance reactions, Matsuda et al. Found six components whose content always increases when OsAT1 is overexpressed, and MS / MS From the analysis, one of them (UK1) is reported to be an amide compound of amino-containing compound and hydroxylauric acid. However, the chemical structure of this material has not been fully specified.

  On the other hand, spermidine is one of representative polyamines, and is known to be involved in cell death induction such as HR (Hypersensitive Response) through the production of hydrogen peroxide (Plant Mol. Biol., 70 (1-2), pp. 896-876, 2003; Plant Physiol. 132 (4), pp. 1973-1981, 2009) Also, reactive oxygen species such as hydrogen peroxide and monoxide, which are important signals for HR Since nitrogen is an important signal in other disease resistance reactions, it may be involved in disease resistance other than HR.

  Conventionally, it has been known that 4N-hexanoylspermidine accumulates in plants as peas age (Plant Physiol. 10 (4): 1177-86, 1996). There is no report that spermidine derivatives induce resistance to plant diseases. In addition, several cinnamic acid derivatives of spermidine are known. Disease-inducing hydroxycinnamic acid derivatives existing in Arabidopsis (The Plant Cell, 21, pp.318-333, 2009), and insecticidal hydroxy derivatives. Cinnamic acid derivatives (Phytochemistry, 63, pp.315-334, 2003) and polyamine derivatives (Nat. Prod. Rep., 22, pp.647-658, 2005) have been reported. There has been no report on the resistance-inducing action of plant derivatives against plant diseases.

Plant Mol. Biol., 63, pp.847-860, 2007 (The 33rd Annual Meeting of the Japanese Pesticide Science Society, presentation number: C312, April 1, 2008) Plant Mol. Biol., 70 (1-2), pp.896-876, 2003 Plant Physiol. 132 (4), pp.1973-1981, 2009 Plant Physiol. 10 (4): 1177-86, 1996 The Plant Cell, 21, pp.318-333, 2009 Phytochemistry, 63, pp.315-334, 2003 Nat. Prod. Rep., 22, pp.647-658, 2005

  The subject of this invention is providing the compound useful as a plant activator which activates the endogenous defense system which a plant has, and controls disease.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that acylated spermidine derivatives can induce disease-resistant reaction against rice and can be used as plant activators. In addition, it has been found that spermidine substituted with a linear alkanoyl group as an acyl group has a strong action as a plant activator, and that a compound having a hydroxyl group introduced into a linear alkanoyl group has a stronger action. It was. The present invention has been completed based on the above findings.

That is, according to the present invention, the following general formula (I):
(R ³ ) NH- (CH ₂ ) ₄ -N (R ¹ )-(CH ₂ ) ₃ -NH (R ² )
(In the formula, any ^one of R ¹ and R ² is a straight chain alkanoyl group or straight chain alkenoyl group having 6 to 18 carbon atoms (the straight chain alkanoyl group or straight chain alkenoyl group is 1 to 3 carbon atoms) A hydroxyl group and / or an alkyl group having 1 to 4 carbon atoms (which may have 1 to 3 carbon atoms), the other represents a protecting group for a hydrogen atom or an amino group; R ³ represents a hydrogen atom or an amino group Or a salt thereof is provided.

According to a preferred embodiment of the above invention, either ^one of R ¹ and R ² is a straight chain alkanoyl group or straight chain alkenoyl group having 8 to 13 carbon atoms (the straight chain alkanoyl group or straight chain alkenoyl group is 1 to 3 hydroxyl groups), the other is a hydrogen atom or an amino group protecting group, and R ³ is a hydrogen atom or an amino group protecting group, or a salt thereof; One of R ¹ and R ² is a straight chain alkanoyl group having 8 to 13 carbon atoms (the straight chain alkanoyl group may have 1 to 3 hydroxyl groups), and the other is hydrogen The above compound or a salt thereof, which is an atom or amino protecting group and R ³ is a hydrogen atom or amino protecting group; the linear alkanoyl group is a linear alkanoyl group having 9 to 12 carbon atoms (The linear alkanoyl group may have 1 to 2 hydroxyl groups) Or a salt thereof; wherein the linear alkanoyl group is a linear alkanoyl group having 9 to 12 carbon atoms (the linear alkanoyl group has one hydroxyl group); And the above-mentioned compound or a salt thereof, wherein the straight-chain alkanoyl group is a straight-chain alkanoyl group having 9 to 12 carbon atoms (the straight-chain alkanoyl group has one hydroxyl group at the end); . As the amino-protecting group, for example, a linear or branched alkanoyl group having 2 to 6 carbon atoms or a linear or branched alkoxycarbonyl group having 2 to 6 carbon atoms is preferable.

  From another aspect, the present invention provides a plant activator comprising the compound represented by the above general formula (I) or a salt thereof as an active ingredient. According to a preferred embodiment, the above-mentioned plant activator used for controlling diseases in plants is provided. Further, an activator of a plant endogenous defense system comprising the compound represented by the above general formula (I) or a salt thereof as an active ingredient; the compound represented by the above general formula (I) or a salt thereof as an active ingredient A plant disease resistance inducer comprising: a compound represented by the above general formula (I) or a salt thereof as an active ingredient an activator of plant hypersensitive cell death; represented by the above general formula (I) A phytoalexin production enhancer in a plant containing the compound or salt thereof as an active ingredient; and a disease resistance gene in the plant containing the compound represented by the above general formula (I) or a salt thereof as an active ingredient Is provided. By using a compound represented by the above general formula (I) or a salt thereof in combination with a polyamine oxygenase (PAO) inhibitor, the promotion of the expression of a disease resistance gene can be further enhanced.

  From another aspect, according to the present invention, there is provided a method for controlling a disease in a plant, which comprises a step of applying to the plant an effective amount of the compound represented by the general formula (I) or a salt thereof; A method for activating an endogenous defense system of a plant, comprising a step of applying to the plant an effective amount of the compound represented by the above general formula (I) or a salt thereof; A method comprising the step of applying an effective amount of the compound represented by the above general formula (I) or a salt thereof to a plant; activating hypersensitive cell death after invasion of pathogenic bacteria in the plant A method comprising the step of applying to a plant an effective amount of the compound represented by the above general formula (I) or a salt thereof; production of phytoalexin produced in a disease resistance reaction in the plant A method for increasing the amount, wherein the above general formula ( A method comprising a step of applying an effective amount of a compound represented by I) or a salt thereof to a plant; a method for promoting the expression of a disease resistance gene in a plant, which is represented by the above general formula (I) A method comprising applying an effective amount of a compound or a salt thereof to a plant; and a method for promoting the expression of a disease resistance gene in a plant, comprising the compound represented by the above general formula (I) or a compound thereof A method is provided comprising the step of applying a polyamine oxygenase (PAO) inhibitor with a salt to a plant.

The compound represented by the above general formula (I) or a salt thereof has an action of activating the endogenous defense system of the plant, and as a plant activator, for example, induces disease resistance of the plant, It can be used to control diseases. Among the compounds represented by the above general formula (I), for example, a compound having a lauroyl group having one hydroxyl group at the terminal as R ¹ has been confirmed to exist in a plant body. The plant activator containing the compound represented by (I) or a salt thereof as an active ingredient can minimize the influence on the ecosystem and is useful as a crop protection means that reduces the burden on the environment.

It is the figure which showed the mode of the cell death spot observed after applying a spermidine derivative. It is the figure which showed the intensity | strength of the cell death caused after applying a spermidine derivative. It is the figure which showed the mode of the leaf disk after processing for 72 hours with the aqueous solution of spermidine or a spermidine derivative (Lau). It is the figure which showed the phytoalexin production amount after treating for 72 hours with the aqueous solution of spermidine or a spermidine derivative (Lau). The right figure is a partially enlarged view of the left figure. It is the figure which showed the resistance gene expression level in the rice leaf blade processed with the spermidine derivative. It is the figure which showed the resistance gene expression level in the rice leaf blade processed by YIS12OH1N (1NHydLau) or YIS12OH4N (HydLau). mock indicates the result of treatment with a solution containing no test compound. It is the figure which showed the result of having measured the number of lesion spots on the 6th day after inoculation after inoculating and infecting blast fungus after spraying YIS12OH1N (1NHydLau) or YIS12OH4N (HydLau) to rice at the 5th leaf stage. mock shows the result of spraying a solution containing no test compound. In the figure, ** and *** indicate significant differences at the 1% and 0.1% levels, respectively. It is the figure which showed the result of having inoculated and infected the blast fungus after spraying YIS12OH1N or YIS12OH4N to the rice of the 5th leaf stage, and observing the state 6 days after inoculation. It is the figure which showed the result of having measured the number of lesion spots on the 6th day after inoculation after inoculating and infecting blast fungus after spraying YIS12OH1N (1NHydLau) or YIS12OH4N (HydLau) to rice at the 5th leaf stage. mock shows the result of spraying a solution containing no test compound. It is the figure which showed the result of having determined the antibacterial effect of YIS12OH1N or YIS12OH4N with respect to the blast fungus by the presence or absence of formation of a prevention circle. It is the figure which showed the result of having identified the natural type YIS12OH4N which exists in the rice which overexpresses OsAT1 using the synthetic sample. It is the figure which showed the intensity | strength of the cell death caused after applying the compound which introduce | transduced the hydroxyl group into the lauroyl group. In the figure, HydLau: YIS12OH4N, 1NHydLau: YIS12OH1N are shown. It is the figure which showed the mode of the cell death spot observed after applying the compound which introduce | transduced the hydroxyl group into the uroyl group. (A) shows the results for HydLau: YIS12OH4N, and (B) shows the results for 1NHydLau: YIS12OH1N. It is the figure which showed the result of having investigated the resistance gene induction effect by YIS12OH4N (HydLau) (3 mM) in presence of the polyamine oxygenase inhibitor guazatine. In the figure, mock indicates the result of treatment with a solution containing no test compound, and ABA indicates abscisic acid. Although ABA has been reported to show an inhibitory effect on disease resistance due to resistance to systemic acquisition, it has also shown an inhibitory effect on disease resistance caused by the compounds of the present invention. It is the figure which showed the intensity | strength of the cell death caused after applying a spermidine derivative with respect to Arabidopsis thaliana. 3d shows the result after 3 days and 7d shows the result after 7 days. It is the figure which showed the result of having examined the PR1 gene expression effect by YIS12OH1N (1NHydLau) or YIS12OH4N (HydLau) with respect to Arabidopsis thaliana. The left figure shows the result after 24 hours and the right figure shows the result after 72 hours.

In general formula (I), ^one of R ¹ and R ² is a straight chain alkanoyl group having 6 to 18 carbon atoms or a straight chain alkenoyl group having 6 to 18 carbon atoms (the number of carbon atoms is carbonyl). The other is a hydrogen atom or an amino-protecting group. R ³ represents a hydrogen atom or an amino-protecting group. The straight-chain alkanoyl group or the straight-chain alkenoyl group represented by any ^one of R ¹ and R ² has 1 to 3 hydroxyl groups and / or 1 to 3 alkyl groups having 1 to 4 carbon atoms It may be. The number of double bonds contained in the alkenoyl group is, for example, about 1 to 3, preferably 2, and more preferably 1. Examples of the linear alkanoyl group or the alkyl group having 1 to 4 carbon atoms that can exist on the linear alkenoyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec -A butyl group, an isobutyl group, a cyclopropyl group, a cyclobutyl group, etc. are mentioned.

One of R ¹ and R ² is preferably a straight chain alkanoyl group or straight chain alkenoyl group having 8 to 13 carbon atoms, and the other is a hydrogen atom or a protective group for an amino group. In this case, it is preferable that R ³ is either a hydrogen atom or an amino-protecting group. The linear alkanoyl group or linear alkenoyl group is preferably a linear alkanoyl group or linear alkenoyl group having 9 to 12 carbon atoms. When the straight-chain alkanoyl group or straight-chain alkenoyl group has a hydroxyl group, the number of hydroxyl groups is 1 to 3, preferably 1 or 2, and more preferably 1 hydroxyl group. As the straight-chain alkanoyl group or straight-chain alkenoyl group, preferably a straight-chain alkanoyl group or straight-chain alkenoyl group having 9 to 12 carbon atoms having one hydroxyl group at the terminal can be used. More preferably, one of R ¹ and R ² is a linear alkanoyl group having 9 to 12 elementary atoms, and one hydroxyl group may be substituted on the linear alkanoyl group . Particularly preferred is a case where the straight-chain alkanoyl group represented by R ¹ or R ² has one hydroxyl group at the end, and most preferred is a straight-chain alkanoyl group having 11 or 12 carbon atoms at the end. This is the case of having a hydroxyl group.

  The kind of the protecting group for the amino group is not particularly limited, and an appropriate protecting group can be selected and used. For example, a straight or branched alkanoyl group having 2 to 6 carbon atoms such as an acetyl group, a straight chain having 2 to 6 carbon atoms such as a tert-butoxycarbonyl group or a 2,2,2-trichloroethoxycarbonyl group. Chain or branched alkoxycarbonyl groups, aralkyloxycarbonyl groups such as benzyloxycarbonyl groups, aralkyl groups such as benzyl groups and p-methoxybenzyl groups, 9-fluorenylmethyloxycarbonyl groups, or allyloxycarbonyl groups, etc. As amino-protecting groups, those well known in the art can be preferably used, but are not limited thereto. For the amino-protecting group, reference can be made to, for example, Green et al., Protective Groups in Organic Synthesis, 3rd Edition, 1999, John Wiley & Sons, Inc. A particularly preferred protecting group is the tert-butoxycarbonyl (Boc) group. When a plurality of amino protecting groups are present in the compound represented by the general formula (I), they may be the same or different, but the plurality of amino protecting groups are the same protecting group. It is preferable.

In the compound represented by the general formula (I), when R ¹ or R ² is a linear alkanoyl group or a linear alkenoyl group having a hydroxyl group other than the terminal, the compound represented by the general formula (I) Has one or more asymmetric carbons, but is in a pure form of an optically active or diastereoisomer based on one or more asymmetric carbons, as well as any mixture of isomers (eg, two or more Any mixture of diastereoisomers) or racemates is included within the scope of the present invention. In addition, when R ¹ or R ² is a straight-chain alkenoyl group, E or Z geometric isomers are present, but pure forms of geometric isomers and mixtures thereof are also included in the scope of the present invention. .

  The compound represented by the general formula (I) can form an acid addition salt. There are no particular restrictions on the type of salt, such as salts with mineral acids such as hydrochloric acid and sulfuric acid, salts with organic acids such as p-toluenesulfonic acid, methanesulfonic acid, and tartaric acid, and salts with amino acids such as glycine. Can be mentioned. Furthermore, the compound represented by the above formula (I) or a salt thereof may exist as a hydrate or a solvate, and these substances are also included in the scope of the present invention.

  In the compound represented by the general formula (I), an amino group other than the amino group to be acylated in spermidine is appropriately protected with an amino-protecting group such as a tert-butoxycarbonyl group (Boc group), and then introduced into the acyl group. It can be produced by acylating an unprotected amino group using an acid halide of a carboxylic acid corresponding to the group, and protected by deprotecting the protecting group of the amino group under appropriate conditions as necessary. A compound having no group can be obtained with high yield. In the case of introducing an alkanoyl group or alkenoyl group having a hydroxyl group, the hydroxyl group may be appropriately protected. For the types of protecting groups for hydroxyl groups, the conditions for introducing protecting groups, and the conditions for removing protecting groups, see, for example, Green et al., Protective Groups in Organic Synthesis, 3rd Edition, 1999, John Wiley & Sons, Inc. This can be selected as appropriate.

  The compound represented by the above general formula (I) or a salt thereof has an action of activating an endogenous defense system of a plant, and can increase resistance to plant diseases. For example, the compound represented by the above general formula (I) or a salt thereof activates a hypersensitive cell death that spontaneously causes death of cells around the infected site after invasion of pathogenic bacteria in a plant, and activates an infection protection system. It can be made. It is also possible to increase the production of phytoalexins (for example, phytocasans A to E and momilactone A and B) produced in disease resistance reactions that occur in plants, and genes involved in disease resistance in plants Can also be activated. Examples of the disease resistance gene include OsPR1b (Biochem. Biophys. Res. Commun., 278, pp. 290-298, 2000), PBZ1 (Plant Cell Physiol., 37, pp. 9-18, 1996), WRKY45 ( Plant Cell, 19, pp. 2064-2076, 2007), OsNPR1 (Mol. Plant-Microbe Interact., 18, pp. 511-520, 2005). Reference can also be made to Mol. Geneti. Genomics 279 (4), pp. 415-427, 2008; Biosci. Biotechnol. Biochem., 65 (1), pp. 205-208, 2001.

  Based on the above action, the compound represented by the above general formula (I) or a salt thereof can be used as a plant activator. The type of plant disease is not particularly limited. For example, it is possible to control diseases caused by fungi, viruses, bacteria, etc., preferably diseases caused by fungi. It is not limited to the disease.

  The plant activator of the present invention can be prepared as an agrochemical composition using, for example, pharmaceutical additives well known in the art. The form of the composition for agricultural chemicals is not particularly limited, and any form may be adopted as long as it is a form that can be used in the art. For example, a composition in the form of an emulsion, solution, oil, water solvent, wettable powder, flowable, powder, fine granule, granule, aerosol, fumigant, or paste can be used. A method for producing the composition for agricultural chemicals is not particularly limited, and any method available to those skilled in the art can be appropriately employed. In order to prevent oxidation of the amine moiety in the compound represented by the general formula (I), it may be preferable to use an active ingredient in the form of a salt such as hydrochloride. In addition, a means that can be used as an antioxidant means for an active ingredient in an agrochemical composition can be appropriately employed.

  As an active ingredient of the plant activator of the present invention, two or more compounds represented by the above general formula (I) or a salt thereof may be used in combination. Moreover, you may mix | blend the active ingredient of other agricultural chemicals, such as an insecticide, a fungicide, an insecticide fungicide, and a herbicide, according to the application purpose. By applying a polyamine oxygenase (PAO) inhibitor such as guazatine (GAZ) to a plant together with the compound represented by the above general formula (I) or a salt thereof, it is possible to further enhance the expression of a disease resistance gene. There is a case. The application method and application amount of the plant activator of the present invention can be appropriately selected by those skilled in the art according to conditions such as application purpose, dosage form, application location, and the like. For example, about 1 to 5 mM can be selected for rice and the like, but the application amount is not limited to the above specific range.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the following examples.
Example 1
Spermidine (Spd, 4.48 g, 22.7 mmol) was dissolved in dehydrated tetrahydrofuran (THF, 50 ml), triethylamine (9.75 ml, 68.1 mmol) was added, and Boc-ON (13.9 g, 56.5 mmol) was kept at 0 ° C. ) In dehydrated THF (50 ml) was added dropwise with vigorous stirring and stirred at 0 ° C. overnight. After THF was distilled off under reduced pressure, 1M NaOH (50 ml) was added to the residue and extracted with dichloromethane (50 ml × 3) .The organic layers were combined, brine (50 ml), H ₂ O (50 ml × 2). ). Sodium sulfate was added for dehydration, followed by filtration and recrystallization in dichloromethane / n-hexane. The resulting crystals were washed with n-hexane to obtain N ¹ , N ⁸ -bis-Boc-Spd (6.68 g, 85.4%) as white amorphous crystals.

83 mg (0.234 mmol) of the obtained N ¹ , N ⁸ -bis-Boc-Spd was dissolved in 10 ml of dichloromethane containing 2% (v / v) of triethylamine, and lauryl chloride (200 μl, excess) was dissolved. And stirred at room temperature for 2 hours. Dichloromethane was distilled off under reduced pressure, 10 ml of H ₂ O was added to the residue, and the mixture was extracted with ethyl acetate (10 ml × 3), washed with brine (10 ml) and H ₂ O (10 ml × 2). did. After dehydration with sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (ethyl acetate: n-hexane = 1: 1, v / v). Add 2 ml of trifluoroacetic acid (TFA) to the total amount of the purified compound, stir at room temperature for 30 minutes, and then distill off the solvent under reduced pressure. did. Wash the residue several times with n-hexane, add 5 ml of 1M NaOH, transfer to a separatory funnel, extract with dichloromethane (5 ml × 4), extract with brine (5 ml) and H ₂ O (10 ml × 2). After washing and dehydrating by adding sodium sulfate, the mixture was filtered to obtain N ⁴ -lauroyl-Spd (62 mg, 81.0%) as a yellow oil.
Other ⁴ N-alkanoyl spermidines were also synthesized by the same method as described above.

Example 2
Diaminobutane (1.2 g, 13 mmol) was dissolved in 10 ml of methanol containing 10% (v / v) of triethylamine, and Boc ₂ O (1.0 g, 4.6 mmol) was dissolved in 2 ml of methanol at 0 ° C. The solution was added dropwise with vigorous stirring and stirred at 0 ° C. for 30 minutes and then at room temperature overnight. The solvent was distilled off under reduced pressure, almost removed, and then dissolved again in dichloromethane (20 ml), and washed with 1M NaOH (20 ml) and H ₂ O (20 ml × 2). Sodium sulfate was added for dehydration, followed by filtration to obtain yellow oily N-Boc-diaminobutane (589 mg, 69.6%).

The obtained N-Boc-diaminobutane was dissolved in acetonitrile (20 ml), potassium carbonate (800 mg) was added thereto, and bromopropylphthalimide (838 mg, 3.13 mmol) was added with stirring. Thereafter, the mixture was stirred at room temperature for 15 minutes and then stirred at 45 ° C. overnight. Acetonitrile was distilled off under reduced pressure, H ₂ O (20 ml) was added to the residue, and the mixture was extracted with dichloromethane (20 ml × 2), washed with brine (10 ml) and H ₂ O (20 ml × 2). The product was dehydrated with sodium sulfate, filtered, and concentrated to give a crude product as a colorless oil. Purification by silica gel column chromatography (dichloromethane: methanol = 9: 1, v / v) gave colorless oily N ⁸ -Boc-N ¹ -phtal-Spd (695 mg, 59.2%).

The obtained N ⁸ -Boc-N ¹ -phtal-Spd was dissolved in 5 ml of methanol containing 10% (v / v) of triethylamine, and Boc ₂ O (0.56 g, 2.52 mmol) was added to the stirring place, Stir overnight at room temperature. The solvent was almost removed by distillation under reduced pressure, H ₂ O (10 ml) was added, and the mixture was extracted with ethyl acetate (10 ml × 2) .The organic layers were combined, brine (10 ml), H ₂ O (10 ml × 2) Washed. After dehydrating by adding sodium sulfate, filtration and purification by silica gel column chromatography (ethyl acetate: n-hexane = 1: 3, v / v), colorless oily N ⁴ , N ⁸ -bis-Boc- N ¹ -phtal-Spd (332 mg, 81.2%) was obtained.

The obtained N ⁴ , N ⁸ -bis-Boc-N ¹ -phtal-Spd was dissolved in ethanol (1 ml), hydrazine monohydrate (0.2 ml) was added, and the mixture was stirred overnight at room temperature. H ₂ O (10 ml) was added and the mixture was extracted with dichloromethane (10 ml) and washed with H ₂ O (5 ml × 2). Sodium sulfate was added for dehydration, followed by filtration, and the solvent was distilled off under reduced pressure to obtain colorless oily N ⁴ , N ⁸ -bis-Boc-Spd (225 mg, 93.4%).

Dissolve 83 mg (0,234 mmol) N ⁴ , N ⁸ -bis-Boc-Spd in 10 ml dichloromethane containing 2% (v / v) triethylamine, add lauryl chloride (200 μl, excess) and add 2 Stir for hours. Dichloromethane was distilled off under reduced pressure, 10 ml of H ₂ O was added to the residue and extracted with ethyl acetate (10 ml × 3), brine (10 ml), H ₂ O (10 ml × 2) Washed with After dehydration with sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (ethyl acetate: n-hexane = 1: 1, v / v). 2 ml of TFA was added to the total amount of the purified compound, and the mixture was stirred at room temperature for 30 minutes, and then the solvent was distilled off under reduced pressure. Wash the residue several times with n-hexane, add 5 ml of 1M NaOH, transfer to a separatory funnel, extract with dichloromethane (5 ml × 4), wash with brine (5 ml) and H ₂ O (10 ml × 2). Sodium sulfate was added for dehydration, followed by filtration to obtain ¹ N-lauroyl-Spd (62 mg, 81.0%) as a yellow oil.
Other ¹ N-alkanoyl spermidines were also synthesized by the same method as above.

⁴ N-hexanoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 0.90 (3H, t, J _{H, H} = 7.0 Hz, H ₂ -6 '), 1.26-1.49 (6H, m, H ₂ -3' to 5 '), 1.54 -1.73 (6H, m, H ₂ -2,6,7), 2.29 (2H, m, H ₂ -2 '), 2.64-2.77 (4H, m, H ₂ -1,8), 3.21-3.46 ( (4H, m, H ₂ -3, 5)
⁴ N-nonanoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 0.88 (3H, t, J _{H, H} = 6.5 Hz, H ₂ -9 '), 1.22-1.36 (10 H, m, H ₂ -4' to 8 '), 1.45 (2H, m, H ₂ -3 '), 1.53-1.73 (6H, m, H ₂ -2,6,7), 2.29 (2H, m, H ₂ -2'), 2.64-2.76 (4H, m, H ₂ -1,8), 3.21-3.44 (4H, m, H ₂ -3,5)
⁴ N-lauroylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 0.88 (3H, t, J _{H, H} = 6.8 Hz, H ₂ -12 '), 1.26-1.30 (16H, m, H ₂ -4' to 11 '), 1.45 (2H, m, H ₂ -3 '), 1.50-1.73 (6H, m, H ₂ -2,6,7), 2.29 (2H, m, H ₂ -2'), 2.64-2.76 (4H, m , H ₂ -1,8), 3.24-2.42 (4H, m, H ₂ -3,5)

⁴ N-stearoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 0.88 (3H, t, J _{H, H} = 7.0 Hz, H ₂ -18 '), 1.20-1.35 (28H, m, H ₂ -4' to 17 '), 1.46 (2H, m, H ₂ -3 '), 1.54-1.74 (6H, m, H ₂ -2,6,7), 2.29 (2H, m, H ₂ -2'), 2.66-2.76 (4H, m , H ₂ -1,8), 3.23-3.45 (4H, m, H ₂ -3,5)
⁴ N-benzoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 1.45-1.86 (6H, m, H ₂ -2,6,7), 2.48-2.73 (4H, m, H ₂ -1,8), 3.18-3.63 (4H, m, H ₂ -3,5), 7.32-7.44 (5H, m, Ph)
⁴ N-cinnamoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 1.47-1.79 (6H, m, H ₂ -2,6,7), 2.71-2.80 (4H, m, H ₂ -1,8), 3.41-3.57 (4H, m, H ₂ -3,5), 6.84-7.00 (1H, dd, J _{H, H} = 68.1 Hz, 15.6 Hz, CHPh), 7.21-7.52 (5H, m, Ph), 7.68-7.72 (1H, dd , J _{H, H} = 15.3 Hz, 5.5 Hz, CHCO)

¹ N-hexanoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 0.89 (3H, t, J _{H, H} = 6.8 Hz, H ₂ -6 '), 1.31 (4H, m, H ₂ -4', 5 '), 1.48-1.70 (8H, m, H ₂ -2,6,7,3 '), 2.15 (2H, t, J _{H, H} = 7.6 Hz, H ₂ -2'), 2.62 (2H, t, J _{H, H} = 6.8 Hz, H ₂ -8), 2.72 (4H, m, H ₂ -3.5), 3.34 (2H, dt, J _{H, H} = 6.1 Hz, 6.1 Hz, H ₂ -1), 6.88 (1H, s, -NHCO-)
¹ N-nonanoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 0.88 (3H, t, J _{H, H} = 6.9 Hz, H ₂ -9 '), 1.21-1.34 (10H, m, H ₂ -4'-8'), 1.44 -1.69 (8H, m, H ₂ -2,6,7,3 '), 2.14 (2H, t, J _{H, H} = 7.6 Hz, H ₂ -2'), 2.61 (2H, t, J _{H, H} = 6.9 Hz, H ₂ -8), 2.71 (4H, m, H ₂ -3.5), 3.34 (2H, dt, J _{H, H} = 6.1 Hz, 6.1 Hz, H ₂ -1), 6.69 (1H, s, -NHCO)
¹ N-lauroylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 0.88 (3H, t, J _{H, H} = 6.9 Hz, H ₂ -12 '), 1.22-1.33 (16H, m, H ₂ -4'-11'), 1.46 -1.70 (8H, m, H ₂ -2,6,7,3 '), 2.15 (2H, t, J _{H, H} = 7.6 Hz, H ₂ -2'), 2.62 (2H, t, J _{H, H} = 6.9 Hz, H ₂ -8), 2.72 (4H, m, H ₂ -3,5), 3.35 (2H, dt, J _{H, H} = 6.1 Hz, 6.1 Hz, H ₂ -1), 6.70 ( 1H, s, -NHCO)

¹ N-stearoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 0.88 (3H, t, J _{H, H} = 7.0 Hz, H ₂ -18 '), 1.20-1.32 (28H, m, H ₂ -4'-17'), 1.46 -1.69 (8H, m, H ₂ -2,6,7,3 '), 2.14 (2H, t, J _{H, H} = 7.6 Hz, H ₂ -2'), 2.61 (2H, t, J _{H, H} = 6.9 Hz, H ₂ -8), 2.72 (4H, m, H ₂ -3,5), 3.34 (2H, dt, J _{H, H} = 6.0 Hz, 6.0 Hz, H ₂ -1), 6.68 ( 1H, s, -NHCO)
¹ N-benzoylspermidine
¹ H NMR (500MHz CDCl ₃ ), 1.43-1.58 (4H, m, H ₂ -6,7), 1.78 (2H, qi, H ₂ -2), 2.65 (2H, t, J _{H, H} = 7.0 Hz _{, H 2 -8), 2.69 (} 2H, t, J H, H = 6.9 Hz, H 2 -5), 2.83 (2H, t, J H, H = 5.8 Hz, H 2 - 3), 3.58 (2H , dt, J _{H, H} = 5.7 Hz, 5.7 Hz, H ₂ -1), 7.41 (2H, m, H _ph -3,5), 7.48 (1H, m, H _ph -4), 7.80 (2H, m, H _ph -2,6), 8.20 (1H, s, -NHCO)
¹ N-cinnamoylspermidine
¹ H NMR (500MHz CDCl ₃ ), δ 1.48-1.59 (4H, m, H ₂ -6,7), 1.74 (2H, qi, J _{H, H} = 6.3 Hz, H ₂ -6), 2.64 (2H, _{t, J H, H = 7.0} Hz, H 2 -5), 2.72 (2H, t, J H, H = 6.5 Hz, H 2 - 3), 2.77 (2H, dt, J H, H = 6.0 Hz, _{6.0 Hz, H 2 - 3)} , 3.48 (2H, m, H 2 -1), 6.38 (1H, dd, J H, H = 15.5 Hz, CHPh), 7.22-7.51 (5H, m, Ph), 7.59 (1H, dd, J _{H, H} = 15.5 Hz, CHCO)

Example 3
A compound in which a lauroyl group having one hydroxyl group introduced at the end was bonded to the 1-position or 4-position was synthesized as follows.

10 ml of dichloromethane was added to 12-hydoroxylauric acid (225 mg, 1.04 mmol), and EDCI (200 mg, 1.04 mmol) and DMAP (127 mg, 1.04 mmol) were added under a nitrogen gas atmosphere and stirred until the whole was dissolved. ¹ N, ⁸ N-diBoc-spermidine (300 mg, 0.870 mmol) was dissolved in 5 ml of dichloromethane and added thereto, and the mixture was stirred at room temperature for 3d in a nitrogen gas atmosphere.

After completion of the stirring, 10 ml of citric acid aqueous solution (10%, w / w) was added to the reaction solution and stirred for 5 minutes to stop the reaction, followed by extraction with dichloromethane (10 ml × 3) and dehydration with sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.62 g of a colorless oily crude product. Purification by silica gel column chromatography (ethyl acetate: n-hexane = 4: 1) gave ¹ N, ⁸ N-diBoc- ⁴ N- (12-hydoroxylauroyl) -spermidine (155 mg, 32.8%) as a colorless oil. Obtained.
¹ H NMR (500MHz, CDCl ₃ ), δ 1.28 (16H, s, H ₂ -4'-11 '), 1.44 (20H, m, 2 x Boc, H ₂ -3'), 1.56-1.69 (6H, m, H ₂ -2, 6, 7), 2.34 (2H, t, J _{H, H} = 7.5 Hz, H ₂ -2 '), 3.07-3.40 (9H, m, H ₂ -1, 3, 5, 8, -OH), 3.62 (2H, t, J _{H, H} = 6.5 Hz, H ₂ -12 ')

This was stirred in 10 ml of trifluoroacetic acid / dichloromethane (20% v / v) for 1 hour, trifluoroacetic acid was azeotroped with methanol and evaporated under reduced pressure, 5 ml of 1M NaOH was added, and the mixture was transferred to a separatory funnel. Extracted with dichloromethane (5 ml × 4), washed with distilled water (5 ml), dehydrated with sodium sulfate and evaporated under reduced pressure to give ⁴ N- (12-hydoroxylauroyl) -spermidine as white amorphous crystals (73 mg, 24.5%) was obtained.

To 12-hydoroxylauric acid (300 mg, 1.39 mmol) was added 15 ml of dichloromethane, and EDCI (275 mg, 1.39 mmol) and DMAP (170 mg, 1.39 mmol) were added under a nitrogen gas atmosphere and stirred until the whole was dissolved. ⁴ N, ⁸ N-diBoc-spermidine (400 mg, 1.16 mmol) was dissolved and added to 5 ml of dichloromethane, and the mixture was stirred at room temperature for 3 days in a nitrogen gas atmosphere.

After completion of stirring, 10 ml of citric acid aqueous solution (10%, w / w) was added to the reaction solution and stirred for 5 minutes to stop the reaction, followed by extraction with dichloromethane (10 ml × 3), and dehydration with sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.68 g of a colorless oily crude product. Purification by silica gel column chromatography (ethyl acetate: n-hexane = 4: 1) and colorless oily ⁴ N, ⁸ N-diBoc- ¹ N- (12-hydoroxylauroyl) -spermidine (311 mg, 49.3%) Obtained.
1H NMR (500MHz, CDCl ₃ ), δ1.27 (16H, s, H ₂ -4'-11 '), 1.44 (20H, m, 2 x Boc, H ₂ -3'), 1.51-1.64 (6H, m, H ₂ -2, 6, 7), 2.18 (2H, t, J _{H, H} = 7.8 Hz, H ₂ -2 '), 3.13-3.28 (9H, m, H ₂ -1, 3, 5, 8, -OH), 3.63 (2H, m, H ₂ -12 ')

This was stirred in 10 ml of trifluoroacetic acid / CH ₂ Cl ₂ (20% v / v) for 1 hour, trifluoroacetic acid was azeotroped with methanol and evaporated under reduced pressure, and 5 ml of 1M NaOH was added to separate the layers. Transfer to a funnel, extract with dichloromethane (5 ml × 4), wash with distilled water (5 ml), dehydrate with sodium sulfate and evaporate the solvent under reduced pressure to give ¹ N- (12- hydoroxylauroyl) -spermidine (160 mg, 40.2%) was obtained.

YIS12OH1N (compound in which -CO- (CH ₂ ) ₁₀ CH ₂ -OH is bound to the 1-position amino group of spermidine)
¹ H NMR (500MHz, CDCl ₃ ), δ 1.28 (16H, m, H ₂ -4'-11 '), 1.44-1.67 (9H, m, H ₂ -2,6,7,3',-OH) , 2.30 (2H, m, H ₂ -2 '), 2.64-2.76 (4H, m, H ₂ -1,8), 3.00-3.47 (4H, m, H ₂ -3,5), 3.62 (2H, t, J _{H, H} = 6.5 Hz, H ₂ -1 ')
YIS12OH4N (compound in which -CO- (CH ₂ ) ₁₀ CH ₂ -OH is bound to the 4-position amino group of spermidine)
¹ H NMR (500MHz CDCl ₃ ) δ 1.28 (16H, m, H ₂ -4'-11 '), 1.50-1.67 (9H, m, H ₂ -2,6,7,3',-OH), 2.14 (2H, t, J _{H, H} = 7.5 Hz, H ₂ -2 '), 2.61 (2H, t, J _{H, H} = 6.8 Hz, H ₂ -8), 2.71 (4H, m, H ₂ -3 , 5), 3.35 (2H, dt, J _{H, H} = 6.0 Hz, 6.0 Hz, H ₂ -1), 3.63 (2H, t, J _{H, H} = 6.5 Hz, H ₂ -12), 6.73 (1H , s, -NHCO)

Example 4
It is known that spermidine forms HR (Hypersensitive Response) -like cell dead spots in the treatment of leaf blades in various plant species (Plant Physiol. 132 (4), pp.1973-1981, 2009). Add 5 μl each of the spermidine derivative obtained in Example 1 as a 1 mM aqueous solution (with Tween 20 added to a final concentration of 0.1%) on the leaves of rice (Nipponbare) about 1 month after seeding, and let it air dry. Thereafter, the intensity of cell death (Severity) was evaluated visually using the severity of cell death and the ratio to the dropping site as an index (FIGS. 1 and 2). As a result, formation of fine cell death spots different from spermidine (Spd) itself was observed in Non, Lau, ¹ N Non, ¹ N Lau and the like. In addition, while cell death due to Spd was observed only in some treated leaves, these spermidine derivatives gave cell death spots in many treated leaves earlier than spermidine.

Example 5
Phytoalexin is an antibacterial substance produced in the disease resistance reaction of plants, and phytocasan A to E (PA to PE), momilactone A, B (MA, MB) and the like are known. Cut out leaf discs from rice leaves, prepare 0.5 mM aqueous solution of spermidine or Lau that showed strong cell death inducing effect in Example 2, and soak leaf discs in this aqueous solution to determine the amount of phytoalexin produced 72 hours later. It was measured. As a result, although it was weaker than copper chloride, which is known as a substance that induces phytoalexin production, browning of leaf disk and clear accumulation of phytoalexin, which are specific to copper chloride, were recognized by Lau treatment. (Figures 3 and 4).

Example 6
Each spermidine derivative was made into a 1 mM aqueous solution, and Tween 20 having a final concentration of 0.01% was added. This aqueous solution was sprayed on the leaf blades of rice grown for 1 week in hydroponics, and RNA was extracted 24 hours later. The expression of rice disease resistance marker genes OsPR1b, PBZ1, and WRKY45 in each sample was measured using real-time PCR. As a result, these spermidine derivatives tended to induce the expression of resistance marker genes (FIG. 5).

  YIS12OH1N (1NHydLau) or YIS12OH4N (HydLau) was made into a 1 mM aqueous solution, and Tween 20 having a final concentration of 0.01% was added. This aqueous solution was sprayed on the leaf blades of rice grown for 1 week in hydroponics, and RNA was extracted 24 hours later. The expression of rice disease resistance marker genes OsPR1b, PBZ1, and WRKY45 in each sample was measured using real-time PCR. As a result, these spermidine derivatives tended to induce the expression of resistance marker genes (FIG. 6).

Example 7
Five-leaf rice is sprayed with YIS12OH1N (1NHydLau) or YIS12OH4N (HydLau) at a concentration of 1 mM or 5 mM, and the next day the blast fungus (Kyu89-246, MAFF101506, race 003.0, 3.4x10 ⁵ spores / ml) Was inoculated. The results of measuring the number of lesions on the 6th day after inoculation are shown in FIG. 7 and FIG. In the spray treatment (mock) without the test compound, blast was infected and many lesions appeared, but when YIS12OH1N or YIS12OH4N was treated at a concentration of 5 mM, blast resistance was shown. YIS12OH1N was resistant to 1 mM treatment. Cell necrosis was not observed only by spraying the test compound (5 mM). Similarly, YIS12OH1N (1NHydLau) or YIS12OH4N (HydLau) was sprayed at a concentration of 1 mM to rice at the 5th leaf stage, and the rice blast fungus (Kyu89-246, MAFF101506, race 003.0, 3.4x10 ⁵ spores / ml) the next day Was inoculated. The results of measuring the number of lesions on the 6th day after inoculation are shown in FIG.

Example 8
Infiltrate 20 μl of an aqueous solution (1 mM, 5 mM, or 10 mM) of YIS12OH1N (1NHydLau) or YIS12OH4N (HydLau) into a 6 mm diameter filter paper, air-dry, and use this filter paper to blast fungus (Kyu89-246, MAFF101506 , race 003.0) was evaluated. No inhibition circles were observed after 5-6 days of incubation at 28 ° C in the dark (Figure 10), confirming that these compounds themselves have no antibacterial activity against blast at 10 mM concentration It was done.

Example 9
The leaf blades freeze-pulverized with LN ₂ from rice with OsAT1 overexpression were extracted with methanol, fractionated with 1M NaOH-CH ₂ Cl ₂ , and then recovered from the organic layer with 1M HCl and purified by Oasis® column. Samples were prepared, and the natural YIS12OH4N present in rice was identified by LC / MSMS using the synthetic YIS12OH4N. The results are shown in FIG. It was confirmed that YIS12OH4N is present in rice overexpressing OsAT1. The measurement conditions for LC / MS are as follows.
Waters Acquity UPLC
Column: AQUITIY C18BEH 1.7 μm 2.1 × 50 mm column
Flow rate: 0.2 mL / min
Mobile phase A: 0.1% formic acid aqueous solution / B: 0.1% formic acid methanol gradient conditions
min flow AB
0 0.2 70 30
1 0.2 70 30
10 0.2 0 100

Waters Xevo (R) TQ MS
Capillary voltage: 3.0 kV
Cone voltage: 34 V
Source temperature: 150 ° C
Desolvation temperature: 400 ℃
Cone gas flow rate: 50 L / Hr
Desolvation gas flow rate: 800 L / Hr
Detection mode: MRM mode (positive)
Collision voltage: 22/16 V (Ch1 / Ch2)
Channel condition: 344.46> 256.30 / 344.46> 273.34 (CH1 / Ch2)
Data analysis: MassLynx (registered trademark)

Example 8
In the same manner as in Example 4, YIS12OH1N or YIS12OH4N was used to examine the formation of cell dead spots and the intensity of cell death. The results of cell death intensity are shown in FIG. 12, and the formation of cell dead spots is shown in FIG. Compounds with one hydroxyl group introduced into the terminal carbon atom of the lauroyl group (HydLau: YIS12OH4N, 1NHydLau: YIS12OH1N) have enhanced cell death strength compared to compounds without a hydroxyl group (Lau or ¹ N Lau). It was.

Example 9
In the same manner as in Example 6, YIS12OH4N (HydLau) 3 mM rice disease resistance marker genes OsPR1b, PBZ1, WRKY45, and OsNPR1 were expressed in the presence of 5 mM polyamine oxygenase (PA) inhibitor guazatine (GAZ). investigated. The results are shown in FIG. The expression promotion of rice disease resistance marker gene by YIS12OH4N (HydLau) was further enhanced in the presence of guazatine.

Example 10
The dicotyledon Arabidopsis thaliana was treated with YIS12OH1N (1NHydLau), YIS12OH4N (HydLau), 1N Non, Bnz, and spermidine (Spd) in the same manner as in Example 4, and cell death was observed with the naked eye. . The results are shown in FIG. Also in Arabidopsis thaliana, 1NHydLau, HydLau, and 1N Non caused strong cell death. The results of examining the PR1 gene expression promoting action using YIS12OH1N (1NHydLau) and YIS12OH4N (HydLau) are shown in FIG. After 24 hours and 82 hours, HydLau exerted a PR1 gene promoting action about 3 times that of 1NHydLau.

  In addition, all the content described in the cited reference described in this specification shall be taken in as reference in this specification.

Claims (9)

The following general formula (I):
(R ³ ) NH- (CH ₂ ) ₄ -N (R ¹ )-(CH ₂ ) ₃ -NH (R ² )
(In the formula, any ^one of R ¹ and R ² is a straight chain alkanoyl group or straight chain alkenoyl group having 8 to 13 carbon atoms ( the straight chain alkanoyl group or straight chain alkenoyl group is 1 to 3 carbon atoms) A hydroxyl group and / or an alkyl group having 1 to 4 carbon atoms (which may have 1 to 3 carbon atoms), the other represents a protecting group for a hydrogen atom or an amino group; R ³ represents a hydrogen atom or an amino group Or a salt thereof , wherein the amino-protecting group is a linear or branched alkanoyl group having 2 to 6 carbon atoms, or 2 to 6 carbon atoms. From a linear or branched alkoxycarbonyl group, benzyloxycarbonyl group, benzyl group, p-methoxybenzyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, and tert-butoxycarbonyl (Boc) group. Any one selected from the group Or a salt thereof (provided that R ¹ is a hydrogen atom, R ² is a linear alkanoyl group having 12 carbon atoms, and R ³ is a hydrogen atom; R ¹ is a carbon atom having 12 carbon atoms ; A compound in which R ² and R ³ are Boc groups, and a compound in which R ¹ is a linear alkanoyl group having 12 carbon atoms and R ² and R ³ are hydrogen atoms, Excluding hydrochloride) . One of R ¹ and R ² is a straight chain alkanoyl group having 8 to 13 carbon atoms (the straight chain alkanoyl group may have 1 to 3 hydroxyl groups), and the other is hydrogen The compound or a salt thereof according to claim 1, which is a protecting group for an atom or an amino group, and R ³ is a protecting group for a hydrogen atom or an amino group. Straight-chain alkanoyl groups, according to claim 1 or 2 carbon atoms is 9-12 straight-chain alkanoyl group (straight-chain alkanoyl group may have two hydroxyl groups from 1) Or a salt thereof. The compound or a salt thereof according to claim 1 or 2 , wherein the straight-chain alkanoyl group is a straight-chain alkanoyl group having 9 to 12 carbon atoms (the straight-chain alkanoyl group has one hydroxyl group). The compound or a salt thereof according to claim 1 or 2 , wherein the linear alkanoyl group is a linear alkanoyl group having 9 to 12 carbon atoms (the linear alkanoyl group has one hydroxyl group at the terminal). . Any one of the protective group of the amino groups claims 1 to 6 straight-chain or branched-chain alkoxycarbonyl group number of 2 linear or branched alkanoyl group or a carbon atom from 2 carbon atoms of six 5 2. The compound according to item 1 or a salt thereof. The following general formula (I):
(R ³ ) NH- (CH ₂ ) ₄ -N (R ¹ )-(CH ₂ ) ₃ -NH (R ² )
(In the formula, any ^one of R ¹ and R ² is a straight chain alkanoyl group or straight chain alkenoyl group having 6 to 18 carbon atoms (the straight chain alkanoyl group or straight chain alkenoyl group is 1 to 3 carbon atoms) A hydroxyl group and / or an alkyl group having 1 to 4 carbon atoms (which may have 1 to 3 carbon atoms), the other represents a protecting group for a hydrogen atom or an amino group; R ³ represents a hydrogen atom or an amino group a group or a salt thereof with a protecting a group), the protecting group of amino group is, six straight or branched chain alkanoyl group having 2 carbon atoms of six, from 2 carbon atoms From a linear or branched alkoxycarbonyl group, benzyloxycarbonyl group, benzyl group, p-methoxybenzyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, and tert-butoxycarbonyl (Boc) group. Any one selected from the group A plant activator comprising a compound or a salt thereof as an active ingredient. The plant activator according to claim 7 , which is used for controlling diseases in plants. A method for controlling diseases in plants, the following general formula (I):
(R ³ ) NH- (CH ₂ ) ₄ -N (R ¹ )-(CH ₂ ) ₃ -NH (R ² )
(In the formula, any ^one of R ¹ and R ² is a straight chain alkanoyl group or straight chain alkenoyl group having 6 to 18 carbon atoms (the straight chain alkanoyl group or straight chain alkenoyl group is 1 to 3 carbon atoms) A hydroxyl group and / or an alkyl group having 1 to 4 carbon atoms (which may have 1 to 3 carbon atoms), the other represents a protecting group for a hydrogen atom or an amino group; R ³ represents a hydrogen atom or an amino group a group or a salt thereof with a protecting a group), the protecting group of amino group is, six straight or branched chain alkanoyl group having 2 carbon atoms of six, from 2 carbon atoms From a linear or branched alkoxycarbonyl group, benzyloxycarbonyl group, benzyl group, p-methoxybenzyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, and tert-butoxycarbonyl (Boc) group. Any one selected from the group And a step of applying to the plant an effective amount of the compound or salt thereof .