JPH04108761A - Plant growth regulator - Google Patents

Abstract

NEW MATERIAL:A 3-beta-hydroxy-epidihydrojasmonate derivative of formula I ((n) is 1-4; R is lower alkyl). USE:A plant growth regulator. The acceleration of the plant by the compound of formula I permits to increase the yield of the plant and the improvement in the quality of the crop, and the control of the plant allows to prevent the succulent of the crop and save the labor of the cultivation control thereof. PREPARATION:For example, a compound of formula II is subjected to a Wittig reaction using a suitable alkyl triphenyl phosphine to prepare a compound of formula III. The compound of formula III is subjected to an alkali hydrolysis reaction and subsequently to an esterification reaction with diazomethane and the resultant compound of formula IV is hydrogenated in the presence of a metal catalyst to prepare the compound of formula I wherein R is methyl.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a novel compound useful as a plant growth regulator, a composition containing the regulator, and a plant that is characterized by promoting or inhibiting the growth of crops. The present invention relates to a growth regulator composition.

(Prior Art) Methyl jasmonic acid (MJA) has been discovered as a naturally occurring plant physiologically active substance, and research is underway to elucidate its growth regulating effects on plants and to utilize it, including its related compounds. [Chemical Regulation of Plants, Volume 22, Nα1.1
~9 pages (1987) and 24 volumes, Nα2.147~
150 pages (1989)]. However, based on these findings, no compound has yet been found that exhibits greater efficacy than the natural MJA. Furthermore, there has been no report yet on the physiological activity of evijasmonate derivatives having a β-hydroxyl group at the 3-position. In particular, stereoselective synthesis of jasmonate compounds is extremely difficult, and it has been difficult to create a substance that is superior to MJA in terms of physiological activity and has high effects that can be put to practical use.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a plant growth regulator that is superior to dimasmonate methyl ester in physiological activity, and to provide a plant growth regulator composition containing the substance. .

(Means for Solving the Problems) The present inventors have established a stereoselective synthesis method for jasmonate compounds, and selected from among the various jasmonate compounds produced by this method a plant growth regulating effect superior to that of natural MJA. The inventors have discovered an evidihydrojasmonate derivative having the following characteristics, and have completed the present invention.

That is, the present invention provides a novel compound represented by the following general formula (I) which is an shrimp dihydrojasmonate derivative having a β-hydroxy group at the 3-position, a plant regulator represented by the formula (1), and a plant regulator represented by the formula (1); The present invention provides a plant growth regulator composition containing the agent as an active ingredient.

Formula (I) shows the relative configuration of the compound, and in the compound represented by the abdominal formula, n is an integer of 1 to 4, preferably 2 to 4.
3, and R is a lower alkyl group, preferably having 1 to 1 carbon atoms.
4, which may be a straight-chain or branched alkyl group, particularly preferably an alkyl group having 1 to 3 carbon atoms. The compound of the present invention includes not only two types of optically active substances having the relative configurations shown by formula (I), but also any mixture of the optically active substances, and a racemate which is a mixture of equal amounts.

Specific examples of these compounds are shown below as structural formulas, but the plant growth regulator of the present invention is not limited to these compounds (the following formulas show the relative configuration of the compounds, where M
e represents a methyl group).

One example of the method for producing the compound represented by formula (1) will be explained using the scheme shown below for the above-mentioned specific compound (in the scheme, the formula indicates the relative configuration of the compound).

Compounds (4a-d) were prepared by a known method (Pharmaceutical Society of Japan No. 107
Collected abstracts of conference lectures, 1987, p235, JP-A-63
-218638)).
1), each can be easily synthesized in a good yield through a Wittig reaction using an appropriate alkylidene triphenylphosphorane, an alkaline hydrolysis reaction, and an esterification reaction using diazomethane. Compound (4a
When -cH is subjected to catalytic reduction at normal pressure and room temperature using a metal catalyst, compound (la-d) is obtained almost quantitatively.

When applying the compound represented by general formula (I) to crops, it may be used as such, but it is usually blended with carriers, surfactants, dispersants, or auxiliary agents, such as emulsions, powders, etc. , wettable powders, granules, aqueous or oily suspensions, aerosols, and other compositions. Suitable carriers include benzene, xylene, toluene, kerosene, alcohols (methanol, ethanol, ethanol, m-butanone, ethylene glycol, propylene glycol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), Examples include solvents such as N-methylpyrrolidone, liquid carriers such as water, and solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea.

In addition, surfactants and dispersants for stabilizing and improving the adhesion and absorption of water solutions to plants include, for example, alcohol sulfate esters, alkyl sulfonates, lignin sulfonates, and polyoxyethylene glycols. Examples include ethers.

When the plant growth regulator of the present invention is used as a composition, the concentration of the active ingredient is 1 to 50% by weight based on the total weight of the composition.
These preparations may be diluted in water and applied to crops at an appropriate concentration.

It can also be used in combination with other agricultural chemicals, such as insecticides, fungicides, plant growth regulators, etc.

When the plant growth regulator used in the present invention is dissolved in an organic solvent or dispersed in water, it is usually 1/1100.
It is preferable to use it in the range of ppm to 5.000 ppm. The most preferable concentration is not necessarily constant depending on the type of crop, the time of use, or the method of use, but when the purpose is to promote growth or increase yield, it is 0.1 to 10.
A range of 0 ppm is appropriate, and when suppressing growth, a range of 100 to 3.000 ppm is preferred. The crops to which the present invention can be applied are not particularly limited, but for example, when the purpose is to increase yield, crops whose roots are harvested include radish, onions, beets, and potatoes; crops whose fruits are harvested include rice, wheat, etc. Examples include grains, legumes, and fruits such as apples and tangerines.

In addition, when the purpose is to suppress the growth, petals of chrysanthemums, roses, lilies, etc. and green flowering trees can be mentioned.

In addition, the timing, amount, and application method of the plant growth regulator of the present invention are not necessarily fixed depending on the type of plant to be applied and the purpose of use, but for example, when the plant growth regulator is actively growing, An example of such a method is to spray the entire surface of the crop at 100 to 500 liters per 10 are.

(Effects of the Invention) The plant growth regulator of the present invention can promote the growth of crops, increase yields, and improve the quality of harvested products. Furthermore, by suppressing the growth of plants, it is possible to prevent crops from becoming elongated, save labor in cultivation management, and improve the value of ornamental crops.

(Examples) The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Manufacture of the compound represented by formula (1) The plant growth regulator of the present invention is prepared from the compound (
1) (Compound numbers correspond to the schemes in this specification. The same applies hereinafter).

Synthetic compound (1) of Example 1-a (1)-(2a)
(400 mg; 2.00 mmol) in tetrahydrofuran (2 ml), sodium amide (2.0 mmol) was added to a solution of sodium amide (2.
4mg; 6. Ommol) and methyltriphenylphosphonium bromide (2,15g; 6.01++
A solution of salt-free methylene triphenylphosphorane (produced by Onol) in tetrahydrofuran (20 ml?) was added dropwise at -78°C at room temperature in a nitrogen stream. After the dropwise addition was completed, the temperature was gradually raised, and after stirring at room temperature for about 10 hours, the reaction solution was poured into water and extracted with diethyl ether. The ether layer was washed with saturated brine, dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: dichloromethane = 1:1) to obtain compound (2a) (310 mg; 93%). ) was obtained as a colorless oil.

'H-NMR (CDCf3) ppm: 4.62 (
LH, m), 4.93-5.26 (2H).

5, 86 (IH, ddt, J=16.9.10.9
゜6.7)1z).

Example 1-b Synthesis of (1)-(2b) Example 1-a
Compound (1) (4
00mg; 2.00m+nol), and sodium amide (234mg; 6.0mmol) and ethyltriphenylphosphonium bromide (2.23cm;
Compound (2b) (3
45■; 96%) was obtained as a colorless oil.

'H-NMR (CDCIt 3) ppm: l, 64
(3H, dd, J=6.3.0.7 Flz).

4.60 (IH, m), 5.22-5.72 (2H)
.

Example 1-c Synthesis of (1)-(2c) Example 1-a
Compound (1) (4
00mg; 2.0 Ommol), and sodium 7
(234 mg; 6. Ommol) and n-propyltriphenylphosphoniumpromy)' (2,32
■; 6. Compound (2C) (357 ml; 92%) was obtained as a colorless oil from salt-free n-propylene triphenylphosphorane prepared from Q 2 mmcil.

'H-NMR (CDCji!s) 99m: 0.97
(3H, t, J=7.7 Hz).

4,60 (IH,m), 5.16-5.68 (
2H).

Example 1-d Synthesis of (1)-(2d) Example 1-a
Compound (1) (4
00 mg; 2.0 Ommol), and sodium amide (234 mg; 6.0 Ommol> and n-
butyltriphenylphosphoniumpuromy)'(2,4
0■; 6. The compound (
2d) (374 cm; 90%) was obtained as a colorless oil.

'H-NMR (CD[: j!s) ppm '0.9
H3H,t, J=7.7 Hz).

4.60 (LH, +n), 5.20-5.60 (2H
).

Example 2-a Synthetic compounds of (2a)-(3a) (
2a) To a solution of (300 μ; 1.8 Ommol) in methanol (3.6 mf) were added water (0.4 ml) and potassium hydroxide (200 g; 3.56 mmol), and the mixture was stirred at room temperature in a nitrogen stream for 24 hours. After evaporating the solvent, water and n-hexane were added to the residue, and the aqueous layer was separated using a separatory funnel.The aqueous layer was neutralized with 2N sulfuric acid under water cooling, and extracted with dichloromethane.The organic layer was saturated. After washing with brine and drying with sodium sulfate, the solvent was distilled off, and crude compound (3a) (3
30■; 99%) was obtained as a pale yellow oil.

')l-NMR (CDC1'3)J)pm' 4.2H
IH, m), 4.88-5.22 (2H).

5, 90 (LH, ddt, J=16.5.9.Skin 6
, 6 Hz), 6.66 (21(, br s).

Example 2-b Synthesis of (2b)→(3b) Example 2-
Compound (2b) was prepared using the same reaction conditions and procedures as in a.
(300 mg; 1.66 mmol), crude compound (3b) (317 cm; 96%) was obtained as a pale yellow oil.

'H-NMR (CD (1!3) ppm: 1.64 (3
H, br d, J = 5.7 Hz).

4, 23 (1)1. m), 5.20-5.70
(2H).

6, 41 (2H, br　s).

Example 2-c, Synthesis of (2c)→(3C) Example 2-a
Compound (2c) was prepared using the same reaction conditions and procedures as
(300 mg; 1.54 mmol), the crude compound (
3c) (325■; 99%) was obtained as a pale yellow oil.

'H-NMR (CDC123) ppOl: Q, 97 (
3H, t, J=7.6 Hz).

4, 22 (1H, m), 5.18-5.62 (
2t().

6, 36 (2) 1. br　s).

Example 2-d Synthesis Example 2 of (2,d)-(3d)
Compound (2d) was prepared using the same reaction conditions and procedures as in -a.
(300 mg; 1.44 mmol), the crude compound (3
d) (319; 98%) was obtained as a pale yellow oil.

'H-NMR (COCl a) pHffl' 0.9
H3)1. t, J=7.7 Hz〉.

4, 23 (IH, 1Tl), 5.20-5.60
(2H).

6,40 (2H,brs).

Example 3-a Synthesis of (3a) = (-4a) Crude compound (3a) (330mg; 1.79+++mo
A diethyl ether solution of diazomethane was added dropwise to the diethyl ether (4-) solution of 1) under ice-cooling and stirring until the yellow color of the solution remained. After evaporating the solvent, the residue was subjected to silica gel column chromatography (hexane: ethyl acetate = 1:1).
) to obtain compound (4a) (330 mm; 93%) as a colorless oil.

'H-NMR (CDCj! 3) ppffl '3.6
6 (3tl, s), 4.20 (IH, m).

4, 88-5.22 (2Ff), 5.89 (I
t(, ddt.

J=16.5.9.9.6.6)+2).

Example 3-b Synthesis of (3b)-(4b) Example 3-
Following the same reaction conditions and procedures as a, crude compound (3b)
(317■; L 60 mmol), the compound (
4b) D10■; 91%) was obtained as a colorless oil.

'H-NMR (CDCl 3) ppm '1.65<3
H,br d, J=5.1)1z).

3, 66 (3H, s>, 4.201) 1. m).

5, 20-5.70 (2H).

Example 3-c Synthesis of (3c) = (4C) Example 3
-a, crude compound (3c
) (325 mg; 1.53 mmol), compound (4c) (339 cm; 98%) was obtained as a colorless oil.

'H-NMR (CDC13) ppm: Q, 97
(3H, t, J=7.5 Hz).

3,66 (3H,s), 4.20 (LH,m)
.

5, 18-5.64 (2H).

Example 3-d Synthesis of (3d)-(4d) Example 3-
Following reaction conditions and procedures similar to a, crude compound (36)
(319 mg; 1.41 m+++ol), compound (4d) (320 ml; 95%) was obtained as a colorless oil.

'H'NMR (CDC13) ppm: 0.91 (
3H, t, J=7.7 Hz).

3.66 (3H, s), 4.22 (LH, m).

5, 20-5.60 (2) 1).

4a-Ia (compound N (L 1 ) 10% in 1-solution of compound (4a) in ethyl acetate
10 μm of palladium-carbon was added, and the mixture was stirred at room temperature under a hydrogen atmosphere for 4 hours. After the catalyst was filtered through Celite, the solvent was distilled off to obtain 97 cm (96%) of compound (5a) as a colorless oil.

'H-NMR (CDCl,)99m' 0.94 (
3N, m>, 3.66 (3) 1. S).

4, 20 (LH, m).

4b-Ib (Compound No. 2) Following the same reaction conditions and operations as in Example 1, compound (4)
From bMOO■, 99■ (98%) of compound (5b) was obtained as a colorless oil.

'H-NMR<CDC123) 99m'0.9H3H
, m), 3.55 (3) 1. s).

4, 20 (IH, m).

4cm+Ic (compound Nα3) Following the same reaction conditions and operations as in Example 1, compound (4cm+Ic)
c) From 100 µm, 95 µm (94%) of compound (5c) was obtained as a colorless oil.

'H-NMR (COCl3) pprn: 0.8
9 <3)1. m), 3.66 (31(,S)
.

4.20(1)1. m).

4ci-Id (Compound Nα4) Following the same reaction conditions and operations as in Example 1, 5), compound (
4a) 99mg (98%) of compound (5d) from 100mg
) was obtained as a colorless oil.

'l(-NMR(CDcl,)99rn: 0.
89(3)1. m), 3.66(3)1. s).

4, 20 (LH, m).

Formulation Example 1 To 20 parts by weight of the plant growth regulator of the present invention, 50 parts by weight of a mixture of xylene and methylnaphthalene (1:1) was added and dissolved, and to this was added polyoxine ethylene alkylphenyl ether and calcium alkylbenzenesulfonate. of?
An emulsion was obtained by mixing 30 parts by weight of 1 m (822).

Formulation Example 2 70 parts by weight of xylene was added to 20 parts by weight of the plant growth regulator of the present invention.
Parts by weight and 10 parts by weight of toxanone were added and uniformly mixed and dissolved to obtain an emulsion.

Test Example 1 (Growth regulating effect of Hatsuka radish) Hatsuka radish (variety: Akamaru Komebuto) was conventionally cultivated in the field, and when the root diameter was 5 mm on average, it was treated with the plant growth regulator of the present invention. The formulation prepared in Formulation Example 1 was diluted with water, and a chemical solution having a compound concentration of 1000.10,0,1 ppm was sprayed at 10β per area. Each plot was 5 m long, and each treatment plot was treated in duplicate. After three late blooms of spraying, 15 plants were randomly harvested from each plot. The total root weight of the 15 plants was measured, and the average value for the two plots was determined. The percentage of the root weight of the treated area was calculated and the results shown in Table 1 were obtained.For comparison of effects, natural M
JA was tested at the same time. As a result, the compound of the present invention has 1
．． Growth was strongly suppressed in the OOOppm plot, but
0.1 f) Ilm promoted growth and showed an effect of increasing yield. All compounds showed a growth promoting effect superior to that of natural MJA.

Table 1 Test Example 2 (Wheat Yield Increase Test) Beer wheat was conventionally cultivated in a field and treated with the plant growth regulator of the present invention at the beginning of the milk ripening period, two weeks after flowering.

The formulation prepared in Formulation Example 2 was diluted with water to give a compound concentration of 5.
0 and i o ppm of the chemical solution at 15β per are.
Spread. During the conventional harvest season, 500 ears were randomly harvested from each plot. After drying in the sun for 10 days, the total tank weight was measured and the value (%) compared to the untreated area was calculated. Table 2 shows the results. It can be seen that treatment with the plant growth regulator of the present invention clearly increased tank weight and yield.

Table 2 Test Example 3 (Elongation Growth Suppression Test) Soybeans and corn were grown individually in pots with a diameter of 5 am and grown in a greenhouse. Soybeans were treated at the leaf-to-leaf stage, and corn was treated at the 3-leaf stage by diluting a preparation containing the plant growth regulator of the present invention and natural MJA using the method of Formulation Example 1 with water. 10rnI per 4 pots of chemical solution with a compound concentration of 500 ppm! Spread. Two weeks after spraying, the average plant height was measured, and the values compared to the untreated plot were calculated and shown in Table 3.

All of the compounds of the present invention showed an elongation inhibitory effect superior to that of natural MJA.

Table 3

Claims (4)

[Claims] (1) A compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Formula (I) indicates the relative configuration of the compound, where n is 1
represents an integer of 4 to 4, and R represents a lower alkyl group. ) (2) A plant growth regulator represented by general formula (I) according to claim (1). (3) A plant growth regulator composition containing the plant growth regulator according to claim (1) as an active ingredient. (4) The composition according to claim (3), which promotes or inhibits the growth of crops.