JPH03215483A - Indole derivative, its production and plant growth regulator containing the derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I ((n) is 1-3). EXAMPLE:1-[(3-Indole)methanoyl]-2-piperidone. USE:A plant growth regulator. PREPARATION:The objective compound can be produced by converting a compound of formula II (e.g. 3-indoleacetic acid) into acid chloride and coupling with an alkyl metal compound of 2-piperidone (e.g. trimethylsilylated 2- piperidone) preferably at or below room temperature.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an indole derivative represented by the general formula (I) (where n is 1, 2 or 3), a method for producing the same, and a process for producing the same. This invention relates to a plant growth regulator containing as an active ingredient. (Prior art) Auxins, gibberellins, cytokinins, abscisic acid, and ethylene have been known as plant hormones useful for plant growth, and recently research has been conducted to develop brassinoid growth regulators. It is being said. However, all of these plant hormones have narrow optimal concentration ranges, and their effects vary greatly depending on the applied concentration, causing problems regarding their inhibitory effects at high concentrations. Therefore, in actual fields, only gibberellins and some natural auxins are currently used. (Problems to be Solved by the Invention) Under the current circumstances, the present inventors have solved the above-mentioned problems by chemically modifying natural auxin so that it can be applied in a wide concentration range and As a result of repeated studies on substances that can act efficiently, we have discovered a plant growth regulator containing an indole derivative as an active ingredient, which will be described in detail below, and completed the present invention. (Means for Solving the Problems) That is, the present invention provides an indole derivative represented by the general formula (1) n H (where n is 1, 2, or 3), a method for producing the same, and an effective method for producing the same. This article relates to a plant growth regulator as an ingredient. Therefore, the indole derivative of the present invention is a novel compound and has an excellent growth regulating effect as an unprecedented plant growth regulator. (Function) The present invention will be explained in detail below. The indole derivative of the present invention is a novel compound whose general formula (I) is represented by 0.sup.1 (in the formula, n is 11 2 or 3). Regarding the method for producing this compound, after acid chloridizing the carpoxyl group of the compound represented by the general formula (n) n (in the formula, n is l1 2 or 3), an alkyl metal compound of 2-biveridone is prepared. It can be obtained by coupling reaction with For acid chloridation, thionyl chloride, phosphorus pentachloride, phosphorus trichloride, oxalyl chloride, etc. can be used, but it is preferable to use oxalyl chloride. Further, in the coupling reaction, an alkyl metal compound of 2-biperidone is used, and an example of such a compound is a trimethylsilylated compound of 2-biperidone. The acid chloridation reaction must be carried out at room temperature or lower to avoid the formation of side reactants. After the acid chloridation reaction, the compound of the present invention represented by general formula (I) can be obtained by dissolving the coupling reaction product in an organic solvent and stirring the solution in contact with an aqueous alkaline solution for a short time. The compounds of the present invention produced in this manner exhibit excellent growth regulating effects on plants. As for the method of using the plant growth regulator of the present invention, it is preferable to dissolve it in a suitable solvent such as ethyl acetate and use it in the form of a solution.The concentration varies depending on the type of plant, but when the purpose is to promote growth, , approximately LX 10-'~LX 1
It is desirable to apply at 0-'+ag/L. In addition, methods such as foliar spraying, application to soil, and addition to fertilizer solution in hydroponic methods can be adopted. Alternatively, it may be added to the transplant soil or hydroponic cultivation tank before planting the plants. Generally, the application period is preferably the seedling stage, but is not limited to this.

(Examples) The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Moreover, all percentages indicate weight % unless otherwise specified.

Example 1 3-indoleacetic acid was added to a reaction flask fitted with a calcium chloride tube. 0g of anhydrous tetrahydrofuran (hereinafter abbreviated as THF) and 5ml of anhydrous benzene were added under stirring conditions. Next, 0.9 g of oxalyl chloride was added to this, and the mixture was stirred at 10°C for 6 hours. After stirring, by suctioning the inside of the flask, T}I
F, benzene, unreacted oxalyl chloride and generated gas were removed, the reaction flask was placed in a water bath, and anhydrous THF was added.
N-}limethylsilyl-2-hi0 to 0 dissolved in S■l
182 g of litone was added dropwise. Next, the reaction flask was taken out of the water bath and stirred at room temperature for 1 hour. After stirring, add water and ethyl acetate to the reaction flask.
After separating the ethyl acetate phase, the ethyl acetate solution was washed in the following order: 1N hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, saturated sodium chloride aqueous solution, and water. After dehydration over anhydrous sodium sulfate, ethyl acetate was distilled off. Brown oil 1. 3g
I got it. Next, this was subjected to alumina gel column chromatography using chloroform as an eluent to obtain 0.9 g of a yellow oily compound.
I got it. Furthermore, this was subjected to alumina gel column chromatography using a mixed solvent of ethyl acetate and hexane (7:3) as an eluent.
0.5 g of a pale yellow oily compound was obtained. IR this compound
, NMR measurement, and the following measurement results show that this compound is a compound of the present invention, l-[(3-intole)
It was confirmed that it was a methanoyl-2-1-triton. I R (C}{Cl.) 3480cm-'()N-
H), 1690cm-'(>C=0)' H-N
M R (90MHz, CDCIa): δp
pm+1.77 (4}1, m, 冫N-CL-CL
-CL-)2.48 (28,m,>N-GO-C time 10Ht-)3.67 (2B,m,>N-C}12
-CH2-)4.40 (2H,s,arom.-C
Ht-)8.3 ~6.7 (61{,m,aro
m. -8) Example 2 1.0 g of 3-indolebrobionic acid was placed in a reaction flask equipped with a calcium chloride tube, and under stirring conditions THF5
ml and 5 ml of anhydrous benzene were added. Next, 0.8 g of oxalyl chloride was added to this, and the mixture was stirred at 10°C for 6 hours. After stirring, the inside of the flask is suctioned to remove THF.
, benzene, unreacted oxalyl chloride and generated gas were removed, the reaction flask was placed in a water bath, and anhydrous T}IF was added.
1.1 g of 0 lithium was added dropwise to 5 ml of N-}lymethylsilyl 2-1 dissolved in the solution. Next, the reaction flask was taken out of the water bath and stirred at room temperature for 1 hour. After stirring, add water and ethyl acetate to the reaction flask.
After separating the ethyl acetate phase, the ethyl acetate solution was washed in the following order: 1N hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, saturated sodium chloride aqueous solution, and water. After dehydration over anhydrous sodium sulfate, ethyl acetate was distilled off. 1.4 g of brown oil was obtained. Next, this was subjected to alumina gel column chromatography using chloroform as an eluent, and a yellow oily compound 1. 0
I got g. Furthermore, this was subjected to alumina gel column chromatography using a mixed solvent of ethyl acetate and hexane (7:3) as an eluent.
0.6 g of a pale yellow crystalline compound was obtained. This compound is I
This compound was subjected to NMR measurement, and the following measurement results confirmed that this compound was 1-[2-(3-intoyl)ethanoyl]-2-pyhelytone, which is a compound of the present invention.

I R (CHCL) 3480cm-'(冫N
-H), 1690cm-' ()C=0)H-
NMR (90MHz, CDCls)
: δppm1.76 (4H, m, 冫N-CH2-
CH2-CH2-)2.49 (2H,m,〉N-C
o-CL-CL-)3.18 (2H,t,arom
．． cHt-CHz-)3.25 (2H,t,aro
m. -CH. -CL-)3.69 (2H,m,冫N.-CH.-CH2-)8.3 ~6.7 (6}
1,m,arom. -H) Example 3 3-indolebutyric acid 1. 5 ml of TllF and 5 ml of anhydrous benzene were added under stirring conditions.

Next, 0.8 g of oxalyl chloride was added to this, and the mixture was stirred at 10°C for 6 hours. After stirring, by suctioning the inside of the flask, T}I
F, benzene, unreacted oxalyl chloride and generated gas were removed, the reaction flask was placed in a water bath, and anhydrous THF was added.
Totrimethylsilyl-2-1 heliton dissolved in 5 ml 1.2? was dropped. Next, the reaction flask was taken out of the water bath and stirred at room temperature for 1 hour. After stirring, add water and ethyl acetate to the reaction flask.
After separating the ethyl acetate phase, the ethyl acetate solution was washed in the following order: 1N hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, saturated sodium chloride aqueous solution, and water. After dehydration over anhydrous sodium sulfate, ethyl acetate was distilled off. 1.3 g of brown oil was obtained. Next, this was subjected to alumina gel column chromatography using chloroform as an eluent to obtain 1.1 g of a yellow oily compound.
I got it. Furthermore, this was subjected to alumina gel column chromatography using a mixed solvent of ethyl acetate and hexane (6:4) as an eluent.
0.6 g of a pale yellow oily compound was obtained. IR this compound
, NMR measurement, and the following measurement results show that this compound is the compound of the present invention, 1-[3-(3-into-
It was confirmed that it was a 12-hire resin. I R (CHCIg) 3480cm-'(〉N-H
), 1690cm-' ■C:0)H-N M R
(90MHz, CDCI.): δppm1.79
(4H, m, 冫N-CHt-CHi-CHt-)2.
07 (2H, quint, aroma.-CH, -C
Ht-CHa-)2.51 (2H,m,冫NG-G
o-CHi-CH, 1)2. 82 (2H, t,
aroI6. -CH, -CI{2-Ct{i-)3
．． 00 (2}1,t,arom.-CH,-C}I
2-CH2-)3.69 (2H,m,)N-CH.
-CH,-)8.2 ~6.7 (6H,m,aro
a+. -1-1) Above, the compounds of the present invention produced in Examples 1 to 3 are shown in No. 1*.

Table 1 Example 4 The compounds of the present invention shown in Table 1 were mixed with ethyl acetate.
10-"10-210-', lag/I, put filter paper (70++++++φ) in a Petri dish, added 2 ml of this sample solution, and as a comparative test, prepared a sample in the same manner using indole acetic acid. 2+++1 was added to the Petri dish in the same way. Furthermore, 2 ml of ethyl acetate was added to the Petri dish as a control. After distilling off the solvent under reduced pressure, 2 ml of sterile water was added, and 25 Komatsuna seeds were added. Sowing at 25°C in the dark.
I kept it. After 48 hours, the stem length and machine length were measured and the rate of change was determined. These results are shown in Table 2. Example 5 Rice seeds (Tankinmoto) were selected in a saline solution with a specific gravity of 1.13, thoroughly washed with water, immersed in 70% ethanol for 2 minutes, and washed with sterile water. Next, this was immersed in a 1% sodium hypochlorite aqueous solution, and after 30 minutes, it was thoroughly washed with sterile water. The seeds were placed in a vetri dish and germinated by keeping them in the dark at 25°C in a shrub state. Next, sample solutions of the compounds of the present invention shown in Table 1 at concentrations of 10-'l, 10, and 100 g/l were prepared with ethyl acetate. 2 ml of the sample solution was added to a vetri dish containing filter paper (70 m x φ), and after ethyl acetate was distilled off under reduced pressure, sterilized water 21 was added. Next, 10 of the germinated rice seeds were transferred to this and kept at 25°C in a dark place. After 100 hours, the stem length and tap root length of the rice plants were measured and the rate of change was calculated. For comparison, the same test was conducted using indole acetic acid and only ethyl acetate solution as a control. These results are shown in Table 3.

Claims (3)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) Indole derivatives represented by (in the formula, n is 1, 2 or 3). (2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) After acid chloridation of the compound represented by (in the formula, n is 1, 2 or 3), 2-piperidone The general formula (I) is characterized by a coupling reaction with an alkyl metal compound of Method for producing indole derivatives. (3) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, n is 1, 2 or 3) A plant growth regulator containing an indole derivative as an active ingredient .