JPS6277366A - Indoleacetic acid derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is H, alkali metal atom or lower alkyl). EXAMPLE:4-Chloro-6-methoxy-indole-3-acetic acid. USE:Plant growth regulator. PREPARATION:The compound of formula II is subjected to cyclization reaction with a compound of formula III (Y is CN or COOR1; R1 is lower alkyl; R is CH3 or C2H5) in the presence of a condensation catalyst (preferably zinc chloride) at 100-160 deg.C to obtain a mixture of the compounds of formula IV and formula V. Optionally after separating the mixture into each compound, the mixture is hydrolyzed preferably in a water-alcohol system of potassium carbonate at room temperature -80 deg.C to obtain a compound of formula I wherein X is H or alkali metal atom.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a novel indoleacetic acid derivative, which is useful as a plant growth regulator.

[Conventional technology]

has long been known to have an elongating effect on young plants. IAA-induced plant cell elongation is brought about by first loosening the cell wall and then increasing water absorption growth, and IAA also has the effect of promoting the formation of new adventitious roots from excised stems and leaves. It is said.

[Problem that the invention seeks to solve]

Conventional indole-3-acetic acid derivative (IAA).

Indole-3-acetic acid methyl ester, indole-3
-Acetamide, etc.) are easily oxidized and decomposed in plants due to the high reactivity of the carbon atom at the 3-position of the indole ring. v-”, has drawbacks.

[Means for solving problems]

By introducing a chlorine atom at the 4-position and a methoxy group at the 6-position of the indole ring, as shown in the formula (wherein X represents hydrogen, an alkali metal atom, or a lower alkyl group), We have now discovered a derivative that is highly stable in plants and has excellent plant elongation effects.

A compound having a chlorine atom at the 4-position and a methoxy group at the 6-position of the indole ring is a novel compound that has not been found in previous literature, probably because it is difficult to synthesize.

Indole acetic acid of formula (1) can be produced as follows.

First, a compound represented by the formula and a lower alkyl group are shown, and R represents a methyl group or an ethyl group. ) is condensed and ring-closed in the presence of a condensation catalyst to obtain a mixture of compounds represented by the formula (wherein R has the same meaning as above).

Here, as a condensation catalyst, zinc chloride, hydrochloric acid gas-acetic acid, B
Examples include F3-acetic acid, sulfuric acid-acetic acid, hydrochloric acid-acetic acid, and zinc chloride is preferred. The temperature of the condensation ring closure reaction is generally 80 to 200°C, preferably 100 to 160°C.

In the above reaction, the compound of formula (3) can be used as a reaction solvent, but an inert solvent such as octane that does not react directly with the compound of formula (3) can also be used. In addition, in carrying out the above reaction, the formula (2
) The compound of formula (3) is 1.5 to 2 moles of the compound of formula (3)
It is preferable to use the condensation catalyst in a range of 0.5 to 2 moles. Formulas (4) and (51
The compounds of the formula (formula (R2 represents hydrogen or an alkali metal atom) can be obtained.

The hydrolysis reaction is preferably carried out in a water-alcohol system of potassium carbonate. The temperature of the hydrolysis reaction is room temperature to 80℃.
It is preferable to do so.

When the compound of formula (]) of the present invention is used as a plant growth regulator, depending on the purpose of use, it may be used as it is or mixed with a pesticide adjuvant to enhance or stabilize the effect, which is generally used in the field of pesticide manufacturing. Depending on the method used, powder,
It can be used in the form of granules, granules, wettable powders, floor blocks, emulsions, and the like.

For clinical use, these various formulations can be used directly or diluted with water to the desired concentration.

The agrochemical auxiliary agents mentioned herein include carriers (diluents) and other auxiliary agents such as spreading agents, emulsifiers, wetting agents, dispersants, fixing agents, and disintegrants.

Liquid carriers include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexane, animals and plants. Examples include oil, fatty acids, fatty acid esters, etc.

Solid carriers include clay, kaolin, talc, diatomaceous earth,
Examples include silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, and sawdust.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, and cationic surfactants. , nonionic surfactant, and amphoteric surfactant.

All formulations can not only be used alone, but also mixed with fungicides, insecticides, plant growth regulators, acaricides, agricultural and horticultural fungicides, soil fungicides, soil conditioners, or nematicides. (It can also be used in combination with fertilizers and other herbicides.)

The active ingredient compound content in the plant growth regulator of the present invention is:
It varies depending on the formulation form, method of application, and other conditions, and in some cases, only the active ingredient compound may be used.
Usually 0.5 to 95% (by weight) preferably 2 to 50% (by weight)
weight).

In addition, when applying the plant growth regulator of the present invention, the amount used varies depending on the compound used and the place of application, but it is usually in the range of 10 g to 0.1 g of the active ingredient compound, and 0.0 g in the case of an aqueous solution. .001~] Oppm concentration per are]-e~20 ffl is used in the spray water amount.

〔Effect of the invention〕

The novel indole acetic acid of the present invention is chemically stable and has a good plant growth regulating effect.

〔Example〕

The present invention will be explained below by way of examples.

Synthesis Example 1: 4-chloro-6-medoxiindole 3
-Preparation of a mixture of acetate and 4-chloro-6-medoxiindole-3-acetonitrile 3-57 g (0,02 mo+) of 3-chloro-5-
Methoxyphenylhydrazine and 2.94 g (0,028
mol) with β-cyanopropionaldehyde dimethyl acetal was stirred well to form a clear solution, to which 3.53 g (0.026 mol) of anhydrous zinc chloride was added. This mixture was heated at 40° C. for 2 hours.

The reaction solution was cooled to room temperature, and then acetic acid-water (3:1) was added.
The mixture was added to a solution of and dissolved, and extracted three times with ethyl acetate. The ethyl acetate phase was washed with a saturated aqueous sodium bicarbonate solution, water, and saturated saline, and dried over anhydrous sodium sulfate.

The constant black oily substance obtained by distilling off ethyl acetate was purified twice by column chromatography (silica gel) to obtain a concentration of 0.6
g of methyl 4-chloro-6-medoxiindole-3-
Acetate and 0.4 g of 4-chloro-6-medoxyindole-3-acetonitrile were obtained.

The analysis results of these compounds are shown below.

I'HNNJR, (CD3CN, TlnS)pI)m
MS (75ev) 7, 31 (] H9br-m)
m/z 255 (M+y 12%).

7, 18 (] H, br, s) 253
(M”, 55%), 196 (26%).

6.91 (IH, d, J=2, IHz) 19
4 (100%), 181 (5%).

6.68 (] H, d, J=2.] IH) 17
9 (1.5%).

3.92 (2H, s) 3.80 (3H, s) 3.64 (3H, s) 1HNMR (CD3CN, TMS) ppm7
．． 1) (IH,s) 7.01 (IH,'d, J= 1.5Hz)6
．． 46 (] H, d, J = 1.5Hz)3
．． 87 (3H,s) 3.84 (2H,s) Synthesis example 2. : A method for producing 4-chloro-6-medoxyindole-3-acetic acid.

0.92 g (0,0036 mol) of methyl 4-chloro-
Methoxyindole-3-acetate methanol 50
A solution consisting of 10 ml of an aqueous solution of 5 g (0.36 mol) of caustic potash was added to a solution consisting of ml of caustic potash, and the solution was heated at 50° C. for 4 hours, and the reaction solution was a-condensed until it became an aqueous solution. Acidify with acetic acid and extract with ethyl acetate.
child. The ethyl acetate phase was washed with distilled water and saturated brine, and dried over anhydrous sodium sulfate. Next, ethyl acetate was distilled off under reduced pressure to obtain a crude product, which was purified by column chromatography (silica gel) to obtain 0.67 g of 4-chloro-6-methodindole-3-acetic acid as a colorless powder.

The NMR analysis results of this compound are shown below.

'1 (NMR (CDJCN, TMS) ppm9
．． 20 (IH, br, s) 7.06 (]h+ S) 6.88 (IH, d, J=2.1Hz) 6.71
(I H, d, J = 2.1 Hz) 3.87
(2H,s) 3.79 (3H,s) Synthesis Example 3. : Production of intermediate 3-chloro-5-methoxyphenylhydrazine.

0.61 g (0,0039 mol) of 3-chloro-5-methoxy-aniline was cooled to OoC, and while stirring, 3 ml of concentrated hydrochloric acid was added and the mixture was further stirred for 20 minutes. Add 3 ml of an aqueous solution of 0.4 g of sodium nitrite to ice-sa! t
It was added dropwise to the above solution while cooling in a bath. After 30 minutes, 2.64 g (0,01
2 mol) of stannous chloride in 5 ml of hydrochloric acid, and the mixture was stirred for 1 hour. The reaction solution was made alkaline with a 4N aqueous caustic soda solution and extracted with ethyl acetate. ethyl acetate phase water,
It was washed with saturated brine and dried over anhydrous sodium sulfate. Next, ethyl acetate was distilled off under reduced pressure, and the resulting crude product was purified by thin layer chromatography (silica gel) to obtain 0.53 g of the desired 3-chloro-5-methoxyphenyl hydracinca.

The NMR and MS analysis results of this product are shown below.

lHNMR (200MHz) (CDCl3.TM
S ) ppm6.74 (I H,t, J = 1
．． 9Hz)6.70 (2H, cl, J = 1.
9Hz) 5.28 (IH, br, m) 3.37 (2H, br, m) MS (75ev) (relative 1nte
nsity, %) m/z 180 (M, 1)
), 178 (M, 66), 176 (M, 100
), 162(14), 161(23).

160(18), 141(30), 133(20).

124(21), 1)1(20).

Claims (2)

[Claims] (1) Formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, X is hydrogen, an alkali metal atom, or a Indole acetic acid derivatives represented by (indicating an alkyl group) (2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) Compounds represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, Y is a cyano group or ▲ Numerical formulas, chemical formulas, tables, etc. etc. ▼ represents a group, R_1 represents a lower alkyl group, R represents a methyl group or an ethyl group) and is condensed and ring-closed in the presence of a condensation catalyst to form the formula There are ▼(4) and ▲Mathematical formulas, chemical formulas, tables, etc.▼(5) (In the formula, R indicates the same thing as above) A mixture of compounds represented by the above is manufactured, and if desired, the above formula (4) is prepared.
Or a formula characterized by hydrolyzing the compound of (5) or a mixture thereof ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (6) (In the formula, R_2 represents a hydrogen atom or an alkali metal atom)
A method for producing an indole acetic acid derivative shown in