JP2006062967A - Plant growth-adjusting agent, cinnamic acid derivative compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a plant growth-adjusting agent easily decomposable under a natural environment, and having a high safety to human body. <P>SOLUTION: The plant growth-adjusting agent contains a cis-cinnamic acid and/or cis-cinnamic acid derivative compound as an active ingredient, and the cis-cinnamic acid derivative is expressed by formula (1) [wherein, R<SP>1</SP>is a substituent capable of maintaining the cis-structure of the cinnamic acid by adding to the cis-cinnamic acid and also easily hydrolyzable]. The compound expressed by formula (2) [wherein, R<SP>2</SP>is a furanosyl group or pyranosyl group which may have a substituent] is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a plant growth regulator, a novel cinnamic acid derivative compound, and a method for producing the same.

  Many agricultural herbicides are used in farmland to avoid weed damage. In addition, many synthetic compounds have been introduced as plant growth regulators in order to perform appropriate vegetation management in green spaces such as parks. There are many types of these plant growth regulators such as phenols, diphenyl ethers, acid amides, triazines, carbamates, phenoxys, etc., all of which are organic compounds synthesized artificially. Is the mainstream. These preparations are generally highly hydrophobic and are often difficult to decompose in the natural environment (see, for example, Non-Patent Document 1).

  In addition, since synthetic herbicides are likely to accumulate in specific organs and cause damage in the human body, in recent years, more safe plant growth regulators are required for the environment and human body. (See Non-Patent Document 2, for example).

  On the other hand, it has been reported that fatty acids and cinnamic acid, which are natural products that are easy to decompose in nature and are considered safe, are also used as herbicides, but their effects as biological growth regulators are not always sufficient. (See, for example, Patent Document 1 and Patent Document 2).

Japanese Patent Laid-Open No. 08-217605 JP 2003-321309 A Hiroshi Ishizaki “Agricultural Chemical Science” Yokendo 1987 Shusaku Uemura, et al. “Encyclopedia of Pesticide Toxicity” Sanseido 1988

  An object of the present invention is to provide a plant growth regulator that is easily decomposed in a natural environment and that is highly safe for the human body.

  The present inventor has found that cis-cinnamic acid has a strong plant growth inhibitory effect in the study of allelopathy (irritant action) of plants, and has led to the present invention. That is, the present invention

<1> A plant growth regulator comprising cis-cinnamic acid and / or cis-cinnamic acid derivative compound as an active ingredient.

<2> The cis-cinnamic acid derivative compound relates to a plant growth regulator represented by the following general formula (1).

一般式(１)

General formula (1)

R ¹ represents a substituent that maintains the cis structure of cinnamic acid and is easily hydrolyzed by addition with cis-cinnamic acid.

<3> R ¹ is an alkaline earth metal, an amino group, a C _1-5 alkylammonium salt, an optionally substituted C _1-5 linear alkyl group, and an _optionally substituted C _{1. A -5} branched alkyl group, an optionally substituted C _1-5 alkenyl group, an optionally substituted C _5-8 cycloalkyl group, an _optionally substituted phenyl group, Or it concerns on the plant growth regulator as described in said <1> which is a heterocyclic group which may have a substituent.

<4> The plant growth regulator according to <1>, wherein R ¹ is a furanosyl group or a pyranosyl group which may have a substituent.

<5> The plant growth regulator according to <1>, wherein R ¹ is a glucosyl group which may have a substituent.

<6> It relates to a compound represented by the following general formula (2).

一般式(２)

General formula (2)

R ² represents a furanosyl group or a pyranosyl group which may have a substituent.

<7> The compound according to <6>, wherein R ² is a glucosyl group which may have a substituent.

<8> The method for producing a compound according to <6>, which comprises esterification of cis-cinnamic acid and furanose or pyranose.

  According to the present invention, it is possible to provide a plant growth regulator that is easily decomposed in a natural environment and that is highly safe for the human body. In addition, a novel cis-cinnamic acid derivative compound useful as a plant growth regulator can be provided.

  The present invention is a plant growth regulator comprising cis-cinnamic acid or a cis-cinnamic acid derivative compound as an active ingredient, and further a cis-cinnamic acid derivative compound represented by the following general formula (2). The present invention will be described in detail below.

一般式（２）

General formula (2)

<Plant growth regulator>
As we study the allelopathic phenomenon in which plants secrete some growth regulators to other plants, several species of Rosaceae such as snow willow and white-spotted plants grow significantly stronger than other plants. It was found to show an inhibitory action. As a result of research on the causative substance of plant growth inhibitory activity existing in the plant body, using the rose willow plant, it was elucidated that the causative substance was glycopyranosyl-cis-cinnamic acid. Furthermore, the plant growth inhibitory activity main body of glycopyranosyl-cis-cinnamic acid was found to be cis-cinnamic acid.

  Conventionally, it has been known that cinnamic acid, which is a natural product, has an effect of suppressing plant growth. Cinnamic acid has a cis form and a trans form because of its structure, but cis form is unstable and cinnamic acid present in nature is in the trans form. Regarding cinnamic acid, it was not known that cis-cinnamic acid has an inhibitory effect on plant growth.

  Glycopyranosyl-cis-cinnamic acid extracted from the willow will easily be hydrolyzed with acid or alkali to form cis-cinnamic acid. The glycopyranosyl-cis-cinnamic acid is presumed to have a pyranosyl group added to cis-cinnamic acid in order to maintain a non-toxic state and an unstable cis-type structure in plants such as the snow willow. When it is secreted from the willow willow, it is easily hydrolyzed in the natural environment, and when acting on other plants, it is considered to exhibit an effect as cis-cinnamic acid.

  The plant growth regulator of the present invention comprises cis-cinnamic acid and / or a derivative compound thereof as an active ingredient. The structure of cis-cinnamic acid is shown in the following structural formula (1).

構造式(１)

Structural formula (1)

  The cis-cinnamic acid may form a salt with an alkali metal. Examples of the alkali metal include sodium and potassium.

  The cis-cinnamic acid derivative compound of the present invention is represented by the following general formula (1).

一般式 (１)

General formula (1)

R ¹ is a substituent that maintains the cis structure of cinnamic acid by addition with cis-cinnamic acid and is easily hydrolyzed in an acid or alkaline environment.

In the general formula (1), R ¹ specifically includes an alkaline earth metal, an amino group, a C _1-5 alkylammonium salt, an optionally substituted C _1-5 linear alkyl group, a substituted group. C _1-5 branched chain alkyl group which may have a group, C _1-5 alkenyl group which may have a substituent, C _5-8 cycloalkyl group which may have a substituent, substituent And a phenyl group which may have a heterocyclic group or a heterocyclic group which may have a substituent.

  Examples of the alkaline earth metal include calcium and magnesium.

Examples of the C _1-5 alkylammonium salt include a tetramethylammonium salt and a tetrabutylammonium salt.

The C _1-5 linear alkyl group is more preferably an ethyl group, a propyl group, or a butyl group.

The C _1-5 branched chain alkyl group is more preferably an isopropyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

The C _1-5 alkenyl group is more preferably an allyl group, a propenyl group, an isopropenyl group, or a butenyl group.

The C _5-8 cycloalkyl group includes, in addition to a monocyclic saturated monovalent group, a monovalent unsaturated hydrocarbon monovalent group, among which a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclopentenyl group. A cyclohexeneyl group is more preferable.

  Examples of the heterocyclic group include furyl, tetrahydrofuryl, pyranyl, tetrahydropyral, chromenyl, chromanyl, isobenzofuranyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl, isoxazolinyl, thiazolyl, isothiazolyl, thiazolidinyl, thiazolidinyl , Isothiazolinyl, pyrazolyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, oxadiazolyl, oxadiazolinyl, thiadiazolinyl, triazolyl, triazolinyl, triazolidinyl, tetrazolyl, tetrazolinyl, pyridyl, dihydropyridyl, dihydropyridyl, diperopridyl , Thiazinyl, dihydrothi Jiniru, thiamorpholino, pyridazinyl, dihydro pyridazinyl, tetrahydropyran pyridazinyl, hexahydrophthalate pyridazinyl,

Oxadiazinyl, dihydrooxadiazinyl, tetrahydrooxadiazinyl, thiadiazolyl, thiadiazinyl, dihydrothiadiazinyl, tetrahydrothiadiazinyl, pyrimidinyl, dihydropyrimidinyl, tetrahydropyrimidinyl, hexahydropyrimidinyl, pyrazinyl, dihydropyrazinyl, tetrahydropyrazinyl , Piperazinyl, triazinyl, dihydrotriazinyl, tetrahydrotriazinyl, hexahydrotriazinyl, tetrazinyl, dihydrotetrazinyl, indolyl, indolinyl, isoindolyl, indazolyl, quinazolinyl, dihydroquinazolyl, tetrahydroquinazolyl, carbazolyl , Benzoxazolyl, benzoxazolinyl, benzisoxazolyl, benzisoxazolinyl, benzothi Zoriru, benzisothiazolyl, benzoisothiazolyl sulfonyl, benzimidazolyl,

Indazolinyl, quinolinyl, dihydroquinolinyl, tetrahydroquinolinyl, isoquinolinyl, dihydroisoquinolinyl, tetrahydroisoquinolinyl, pyridoindolyl, dihydrobenzoxazinyl, cinnolinyl, dihydrocinnolinyl, tetrahydrocinnolyl, phthalazinyl , Dihydrophthalazinyl, tetrahydrophthalazinyl, quinoxalinyl, dihydroquinoxalinyl, tetrahydroquinoxalinyl, purinyl, dihydrobenzotriazinyl, dihydrobenzotetrazinyl, phenothiazinylfuranyl, thienyl, benzofuranyl, benzothienyl Etc. These heterocyclic groups can also include those having an oxo form or thioketone form at any substitutable position.

Among these, R ¹ is preferably a furanosyl group or a pyranosyl group, particularly preferably a glucosyl group, because it is easily decomposed in a natural environment and has high safety to the human body.

C _1-5 linear alkyl group which may have a substituent, C _1-5 branched chain alkyl group which may have a substituent, C _1-5 alkenyl group which may have a substituent Examples of the substituent include a halogen atom, a hydroxyl group, and a methyl group.

Examples of the substituent in the phenyl group which may have a substituent and the heterocyclic group which may have a substituent include a halogen atom, a hydroxyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, and C _1. Mention may be made of a _-6 haloalkyl group, an amino group, a mono- or di-C _1-6 alkyl ammonium salt.

Cis cinnamic acid, which is a plant growth regulator of the present invention,
3-Phenyl-2-propynoic acid can be obtained by dissolving in dry methanol and causing a reduction reaction with hydrogen gas.

  Alternatively, cis-cinnamic acid can also be obtained by irradiating commercially available trans-cinnamic acid with ultraviolet rays. The cis-cinnamic acid compound obtained as a mixture can be purified by high performance liquid chromatography equipped with a column packed with chemically modified silica gel.

  The cis-cinnamic acid derivative, which is a plant growth regulator of the present invention, is a halide of a compound having a hydroxyl group in which cis-cinnamic acid is dissolved in a solvent such as acetonitrile and in the presence of a catalyst, ethyldiisopropylamine (Hunig'sbase). Can be obtained.

  The cis-cinnamic acid derivative can also be obtained by adding cis-cinnamic acid and heating with a compound having a hydroxyl group in the presence of an acid catalyst such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like.

  Furthermore, the cis-cinnamic acid derivative can be obtained by dissolving cis-cinnamic acid, cis-cinnamic acid salt, or cis-cinnamic acid halide in a basic organic solvent such as pyridine, and adding a compound having a hydroxyl group.

  The plant growth regulator of the present invention does not limit the target plant. For example, in paddy fields, it can be used as a herbicide for paddy fields for the purpose of controlling annual perennial weeds such as Tainubie, Tamagayatsuri, Azena, and perennial weeds such as firefly, Mizugatatsu, Urikawa and the like.

  In fields and orchards, herbicides or plant growth regulators for annual and orchard use, such as annual and perennial weeds such as damselfish, yamgra, barnyard grass, and giant puffer, as well as perennial weeds such as giant persimmon, periwinkle, and cyper Can be used as

  Furthermore, the plant growth regulator of the present invention includes, in addition to paddy fields and upland fields, for example, fallow fields, ridges, farm roads, waterways, pastures, cemeteries, parks, roads, playgrounds, open spaces around buildings, clearing land, tracks, It can also be used to control general weeds in forests.

  The plant growth regulator of the present invention exhibits a particularly excellent growth inhibitory effect on plants before emergence and 1-3 days after emergence. Therefore, the present invention is to pre-treat the planting site of the useful plant or treat it within one month after the planting of the useful plant (including the case where the useful plant has already been planted like an orchard) within one month of occurrence of weeds. This is desirable from the viewpoint of effectively expressing the physiological activity of the plant growth regulator.

  However, the plant growth regulator of the present invention is not limited to the initial growth stage of weeds, but is effective for controlling weeds in the vegetative growth period or the reproductive vegetative period after one month after the occurrence.

  The plant growth regulator of the present invention can be used by dissolving a single compound in water, but is dissolved or dispersed in a liquid carrier such as a surfactant or a solvent, or mixed or adsorbed with a powder carrier such as bentonite. Are more preferable. Further, for the purpose of enhancing the effect, these plant growth regulators of the present invention dissolved or dispersed, mixed or adsorbed, and emulsifiers, dispersants, suspending agents, spreading agents, penetrating agents, wetting agents, stabilizers, etc. Can be used as preparations such as emulsions, oils, wettable powders, powders, and aqueous solvents.

  The plant growth regulator of the present invention is applied at a concentration of 0.001 to 100% directly to the foliage of a plant for the purpose of growth inhibition or killing. In addition, in order to prevent the generation of plants, it is used by directly treating the soil at the target location.

  The amount of the plant growth regulator of the present invention is used in various factors, for example, the target plant, the development / growth status of the plant, the growth tendency of the plant, the weather, the environmental conditions, the dosage form, the application method, the application location, the application. It varies depending on the time. The dosage form and application rate are appropriately selected according to the purpose.

  The plant growth regulator of the present invention can also be used in combination with other herbicides, plant growth regulators, etc. for the purpose of controlling the species of plants to be controlled, for the expansion of the control period, or for the purpose of reducing the dosage. It is.

<Ciscinnamic acid derivative compound>
Furthermore, the present invention is a cis-cinnamic acid derivative compound represented by the following general formula (2).

一般式 (２)

General formula (2)

In the general formula (2), R ² represents a furanosyl group or a pyranosyl group which may have a substituent.

Among them, the compound represented by the following structural formula (2),
[1-O-cis-cinnamoyl-bd-glucopyranose],
And a compound represented by the structural formula (3),
[6-O- (4′-hydroxy-2′-methylene-butyroyl) -1-O-cis-cinnamoyl-bd-glucopyranose] can be noted as a natural compound extracted from snow willow.

構造式(２)

Structural formula (2)

構造式(３)

Structural formula (3)

  The compounds represented by the structural formula (2) and the structural formula (3) of the present invention can be obtained from, for example, the leaves of a snowy plant or a white lizard that is a plant of the Rosaceae family. The leaves of snow willow or white sage are extracted with methanol or a mixture of methanol and water, etc., the solvent is distilled off, added to water, suspended and distributed with ethyl acetate. By performing fractionation using activated carbon, silica gel, chemically modified silica gel, alumina, column chromatography using cellulose as a carrier, etc., the compound represented by the structural formula (2) is obtained from the water fraction from the ethyl acetate fraction. A compound represented by the structural formula (3) can be obtained.

  Further, a cis-cinnamic acid compound represented by the structural formula (1) can be obtained by acid or alkali hydrolysis of the compound represented by the structural formula (2) or the structural formula (3).

  The contents of the present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the description of the examples.

(Test 1)
<Purification of cis-cinnamic acid derivative compound>
110 g of fresh leaves of snow willow were extracted with 2.6 L of methanol, and then the methanol was distilled off from the obtained extract using a rotary evaporator, followed by concentration and drying. This was suspended in water and partitioned with ethyl acetate to obtain a water fraction and an ethyl acetate fraction.

  The water fraction was subjected to column chromatography using activated carbon (activated carbon for chromatography, manufactured by Wako Pure Chemical Industries, Ltd., packed with water) as an adsorbent. After washing the column with water, 90% methanol Eluted with. The fraction eluted with methanol was concentrated to dryness under reduced pressure using a rotary evaporator, and dissolved in a small amount of methanol.

  Next, the fraction dissolved in methanol was subjected to column chromatography using silica gel (Wakogel C-200, manufactured by Wako Pure Chemical Industries, Ltd.) as an adsorbent. After washing the column with chloroform, 20% methanol / Eluted with chloroform. This fraction was dried under reduced pressure using a rotary evaporator, concentrated, and dissolved in a small amount of water.

  Next, the fraction dissolved in water was subjected to column chromatography using an adsorbent (Bondesil C18, manufactured by GL Sciences) modified with silica gel with octadecyl group, and 20% methanol / water was extracted from the column. And eluted. The obtained fraction was dried under reduced pressure using a rotary evaporator, concentrated, and dissolved again in a small amount of water.

Next, the fraction dissolved in water was obtained by using a column (Inertsil ^(R) ODS-3, 4.6 mmf × 250 mm, manufactured by GL Sciences Inc.) packed with an adsorbent in which silica gel was modified with octadecyl groups. The sample was injected into a preparative high performance liquid chromatography and eluted with 30% methanol / water (flow rate: 4 mL min ⁻¹ ) while monitoring at UV 280 nm. The peaks detected 37 to 40 minutes after injection of the sample were collected, and dried and concentrated under reduced pressure using a rotary evaporator to obtain Compound A as a paste.

  The ethyl acetate fraction was evaporated to dryness under reduced pressure using a rotary evaporator, and dissolved in a small amount of water. The fraction dissolved in water was subjected to column chromatography using an adsorbent in which silica gel was modified with octadecyl group (Bondesil C18, manufactured by GL Sciences), and the column was washed with 20% methanol / water. Eluted with 60% MeOH. The obtained fraction was dried under reduced pressure using a rotary evaporator, concentrated, and dissolved again in a small amount of water.

Next, the fraction dissolved in water was collected using a column (Inertsil ^(R) ODS-3, 4.6 mmf × 250 mm, manufactured by GL Sciences Inc.) packed with an adsorbent modified with silica gel with octadecyl group. And was eluted with 50% methanol / water while monitoring at UV 280 nm (flow rate: 4 mL min ⁻¹ ). The peaks detected 54 to 58 minutes after the injection of the sample were collected, and dried and concentrated under reduced pressure using a rotary evaporator to obtain Compound B as a paste.

(Test 2)
<Structure Determination of Compound A>
Compound A was separated by high performance liquid chromatography equipped with a photodiode array detector, and when the UV absorption spectrum of the peak was measured on the chromatogram, it showed a peak at 279 nm. Compound A was dissolved in deuterated methanol, and ¹ H-NMR, ¹³ C- ¹ H COZY, ¹³ C-NMR and DEPT spectra were measured. One pyranose (95.7 ppm; one anomeric carbon per molecule) , 71.1-78.9 ppm; -CH (OH)-4 carbons, 62.4 ppm; terminal -CH ₂ OH 1 carbon present) and 1 cinnamic acid (166.1 ppm; 1 carboxyl carbon, 119.5 and 146.4 ppm) The presence of one alkene carbon pair (—CH═CH—), 129.0-136.0 ppm, 6 carbons corresponding to the 1-substituted benzene). HMBC analysis revealed that the carboxyl carbon at the C1 position of cinnamic acid and the C1 position of the sugar had a glycosidic bond.

In order to clarify the sugar composition of the compound A, the compound A was reacted with 5% dry hydrochloric acid / methanol at 80 ° C. for 18 hours to obtain a methylated monosaccharide, which was solidified, dissolved in pyridine, A mixed solution (2: 1) of hexamethyldisilazane and trimethylchlorosilane was added and heated at 80 ° C. for 20 minutes to be trimethylsilylated, and the retention time was compared with that of the standard trimethylsilylated sugar by gas chromatographic analysis. The retention time was compared with the standard trimethylsilylated sugar, and it was confirmed that the peaks were completely matched by co-injection for those that matched. As a result, it was confirmed that the sugar contained in the compound A was glucose. The conformation of the C1 position (anomeric position) of glucose was determined to be b because the ¹ H-NMR binding constant was 8 Hz. The conformation of the alkene carbon pair in cinnamic acid was determined to be cis because the ¹ H-NMR binding constant was 13 Hz.

Further, [M + H] ⁺ = 311.1147 was obtained by high-resolution FAB-MS analysis. Therefore, the molecular weight of Compound A was 310, and the elemental composition was determined to be C ₁₅ H ₁₉ O ₇ . From the above information, it was revealed that the compound A was 1-O-cis-cinnamoyl-bd-glucopyranose represented by the following structural formula (2).

構造式(２)

Structural formula (2)

(Test 3)
<Structure Determination of Compound B>
Compound B was separated by high performance liquid chromatography equipped with a photodiode array detector, and when the UV absorption spectrum of the peak was measured on the chromatogram, it showed a peak at 280 nm. Compound B was dissolved in deuterated methanol, and ¹ H-NMR, ¹³ C- ¹ H COZY, ¹³ C-NMR and DEPT spectra were measured. One pyranose (95.7 ppm; one anomeric carbon per molecule) 71.4-78.0 ppm; -CH (OH)-4 carbons, 64.2 ppm; 1 terminal -CH ₂ OH carbon), 1 cinnamic acid (166.2 ppm; 1 carboxyl carbon, 119.4 and 146.0 ppm; alkene carbon 1 pair (-CH = CH-), 129.1-136.0 ppm, 6 carbons corresponding to 1-substituted benzene), and 1 2-methylene butyrate (168.3 ppm; 1 carboxyl carbon, 138.7 and 128.0 ppm The presence of one alkene carbon (—CH═CH—) pair, 36.4 ppm; one methylene carbon, 61.6 ppm; one terminal —CH ₂ OH carbon). HMBC analysis revealed that the carboxyl carbon at the C1 position of cinnamic acid and the C1 position of the sugar had a glycosidic bond, and the carboxyl carbon of 2-methylenebutyrate was bonded to the C6 position of the sugar.

In order to clarify the saccharide composition of the compound B, the compound B was reacted with 5% dry hydrochloric acid / methanol at 80 ° C. for 18 hours to obtain a methylated monosaccharide, which was dried and dissolved in pyridine. A mixed solution (2: 1) of hexamethyldisilazane and trimethylchlorosilane was added and heated at 80 ° C. for 20 minutes to be trimethylsilylated, and the retention time was compared with that of the standard trimethylsilylated sugar by gas chromatographic analysis. The retention time was compared with the standard trimethylsilylated sugar, and it was confirmed that the peaks were completely matched by co-injection for those that matched. As a result, it was confirmed that the sugar contained in the structural formula (3) of the present invention was glucose. The conformation at the C1 position (anomeric position) of glucose was determined to be b because the ¹ H-NMR binding constant was 8 Hz. The conformation of the alkene carbon pair in cinnamic acid was determined to be cis because the ¹ H-NMR binding constant was 13 Hz.

Further, since [M + H] ⁺ = 409.1529 was obtained by high resolution FAB-MS analysis, the molecular weight of the compound B was 408, and the elemental composition was determined to be C ₂₀ H ₂₅ O ₉ . From the above information, the compound B is represented by the following structural formula (3).
6-O- (4'-hydroxy-2'-methylene-butyroyl) -1-O-cis-cinnamoyl-bd-glucopyranose was found.

構造式(３)

Structural formula (3)

(Test 4)
<Elucidation of plant growth inhibitory activity of compounds represented by structural formulas (2) and (3)>
Test examples that confirm that the compounds represented by the structural formulas (2) and (3) of the present invention have a high plant growth inhibitory action are described below.
One filter paper of the same diameter (Toyo filter paper, No. 1) is laid on a glass Petri dish having a diameter of 27 mm, and the compound represented by structural formula (2) or structural formula (3) of the present invention is added to 0.1 μM, It was added as 7 sections of 0.3 μM, 1.0 μM, 3.0 μM, 10.0 μM, 30.0 μM and 100.0 μM. After decompression and drying at 40 ° C., 0.7 mL of water was added, and 6 seeds of lettuce sprouting were placed. Thereafter, incubation was carried out at 20 ° C. in the dark for 48 hours, and the growth inhibition activity against the radicle elongation was detected by measuring the length of the root of the plant that grew during this period. Plant growth inhibitory activity was expressed as a percentage of the root length of the plant in the control group to which only water was added. For comparison, cis-abscisic acid having a strong plant growth inhibitory activity as a natural organic compound was also tested. The results are shown in Table 1.

The compounds represented by structural formulas (2) and (3) of the present invention inhibited lettuce radicle elongation by 50% at around 10 ⁻⁶ M. This activity was approximately 10 times stronger than cis-abscisic acid. Cis abscisic acid is known to have a very strong activity as a natural plant growth inhibitor, but the compounds represented by structural formulas (2) and (3) of the present invention are cis-abscisic acid. It was shown that the plant growth inhibitory activity was clearly stronger than that.

(Test 5)
<Elucidation of the main body of plant growth inhibitory activity of compounds represented by structural formulas (2) and (3)>
In order to elucidate from which part of the chemical structure the strong plant growth inhibitory activity of the compounds represented by the structural formulas (2) and (3) of the present invention is derived, the compound of the structural formula (2) and the structure Cis cinnamic acid, which is a partial structure of the compound of formula (3), was prepared by the following method, and its plant growth inhibitory activity was examined.

  Commercially available trans-cinnamic acid (Wako Pure Chemical Industries) was dissolved in a solvent such as acetone or methanol and poured into a container such as a petri dish, followed by UV irradiation (254 nm) for 24 hours. By this operation, the trans-cinnamic acid solution became a mixed solution of cis-cinnamic acid and trans-cinnamic acid. This mixed solution is injected into a preparative high performance liquid chromatography equipped with a column (Shim-packPREP-ODS (H), 4.6 mmf × 250 mm, manufactured by Shimadzu Corporation) packed with an adsorbent modified with silica gel with octadecyl group, Elution with 50% methanol / water or acetonitrile / water while monitoring at UV 280nm, collect the detected peaks, and dry and concentrate under reduced pressure using a rotary evaporator to obtain high purity cis-cinnamic acid. did it.

  The plant growth inhibitory activity of cis-cinnamic acid was carried out in the same manner as in Test 4. For comparison, a compound of structural formula (2), a compound of structural formula (3), and transcinnamic acid were also tested. The results are shown in Table 2.

  As a result, it was found that the plant growth inhibitory activity of cis-cinnamic acid was exactly the same as the compounds represented by the structural formulas (2) and (3) of the present invention. That is, the plant growth inhibitory activity of the compounds represented by the structural formulas (2) and (3) of the present invention is cis-cinnamic acid, which is a partial structure of the compounds represented by the structural formulas (2) and (3). It became clear that it originated from. In addition, trans-cinnamic acid, which only changes the C2 position of cis-cinnamic acid, has a plant growth inhibitory activity of about 1/1000. That is, the active main body of the compounds represented by the structural formulas (2) and (3) of the present invention is cis-cinnamic acid, and transcinnamic acid in which the steric structure of the double bond portion is changed to trans is extremely inferior in activity. I found.

(Test 6)
<Plant Growth Inhibitory Activity of Various Plants of the Plant Growth Regulator of the Present Invention>
The plant growth inhibitory activity of the plant growth regulator of the present invention on various plants is represented by the compound of the structural formula (2), the compound of the structural formula (3), cis-cinnamic acid which is the active body (structural formula (1) Compound) and transcinnamic acid. Plant growth inhibitory activity was performed in the same manner as in Test 4 except that the plant body was changed. Table 3 shows the results of the timothy root.

  Table 4 shows the results of Cinadales Zumaya root.

  Table 5 shows the results of the root of the blue-headed toe.

  The results of Chinese cabbage root are shown in Table 6.

  The results of red clover root are shown in Table 7.

  From the results shown in Tables 1 to 7, it can be seen that the plant growth regulator comprising the cis-cinnamic acid and the cis-cinnamic acid derivative compound of the present invention as an active ingredient is effective for a wide range of plants.

<Method for producing cis-cinnamic acid derivative compound>
(Test 7)
The compound of the present invention can be prepared by the method shown in Test 1 or 5, but cis-cinnamic acid and cis-cinnamic acid derivative compounds can also be artificially synthesized by organic synthesis.

  10 g of 3-Phenyl-2-propynoicacid was dissolved in 100 mL of dry methanol and reacted with hydrogen gas at room temperature in the presence of 0.1 g of inactivated palladium catalyst to obtain 8.5 g of cis-cinnamic acid.

(Test 8)
P-Bromophenacyl ester of cis-cinnamic acid is obtained by dissolving 1 g of cis-cinnamic acid in 50 mL of acetonitrile and adding 2 g of p-bromophenacyl chloride salt in the presence of 0.1 g of the catalyst ethyl diisopropylamine (Hunig's base). 2g was obtained.

(Test 9)
1 g of cis-cinnamic acid was dissolved in 50 mL of dichloromethane, 1 mL of p-toluenesulfonic acid was added as an acid catalyst, 1 mL of allyl alcohol was added, and heated and refluxed for 3 hours to obtain 1.2 g of cis-cinnamic acid allyl ester.

(Test 10)
17.7 g of thionyl chloride and 1 drop of DMF were added to 15 g of cis-cinnamic acid and reacted for 2 hours on a water bath. This was distilled under reduced pressure to obtain 15 g of cis-cinnamic acid chloride. To 1.8 g of this cinnamic acid chloride, 0.35 g of methanol and 2 ml of pyridine were added and reacted at room temperature for 4 hours to obtain 1.5 g of cis-cinnamic acid methyl ester.

In order to protect crops from weed damage in agricultural land or the like, they can be used as herbicides or plant growth regulators that are easily decomposed and highly safe for the human body, either alone or mixed with other compounds.
In addition, in order to properly control the growth of plants in parks, etc., it can be used as a herbicide or plant growth regulator that is easily decomposed and highly safe for the human body, alone or mixed with other compounds. Can do.

Claims (8)

  A plant growth regulator comprising cis-cinnamic acid and / or cis-cinnamic acid derivative compound as an active ingredient. The plant growth regulator according to claim 1, wherein the cis-cinnamic acid derivative compound is represented by the following general formula (1).

General formula (1)
[R ¹ represents a substituent that maintains the cis structure of cinnamic acid and is easily hydrolyzed by addition with cis-cinnamic acid. ] R ¹ is an alkaline earth metal, an amino group, a C _1-5 alkylammonium salt, an optionally substituted C _1-5 linear alkyl group, and an _optionally substituted C _1-5 minute. A branched alkyl group, a C _1-5 alkenyl group which may have a substituent, a C _5-8 cycloalkyl group which may have a substituent, a phenyl group which may have a substituent, or a substituent The plant growth regulator according to claim 1, which is a heterocyclic group which may have The plant growth regulator according to claim 1, wherein R ¹ is a furanosyl group or a pyranosyl group which may have a substituent. The plant growth regulator according to claim 1, wherein R ¹ is a glucosyl group which may have a substituent. A compound represented by the following general formula (2).

General formula (2)
[R ² represents a furanosyl group or a pyranosyl group which may have a substituent. ] The compound according to claim 6, wherein R ² is a glucosyl group which may have a substituent. The method for producing a compound according to claim 6, characterized by esterification of cis-cinnamic acid with furanose or pyranose.