JPH11349569A - Fluorine-containing alpha-indolepropionic acid compound, its production and plant growth regulator with the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having plant growth promotive activity. SOLUTION: This new compound is shown by formula I (Y is H or an alkyl; X<1> and X<2> are each H, an alkyl, alkoxy, aryl, or halogen), e.g. methyl 3,3,3- trifluoro-2-(indole-3-)propionate. The compound of formula I is obtained by the following procedure: a compound of formula II (R is H or an alkyl) is dissolved in a polar solvent such as dimethylformamide and then reacted with a chlorinating agent (e.g. thionyl chloride, oxalyl chloride) followed by reducing the reaction product with e.g. sodium borohydride and then, as necessary, carrying out hydrolysis under heating. When the compound of formula I is to be used as a plant growth regulator, it can be used either directly, or in the form of a preparation such as a liquid, powder, granules, wettable powder or flowable through mixing with an auxiliary commonly used in agrochemicals; it is preferable that the compound of formula I is used at a concentration of 1×10<-9> to 1×10<-2> M.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to novel fluorine-containing α-indolepropionic acids having a plant growth regulating action,
The present invention relates to a method for producing the same and a plant growth regulator containing one or more thereof as an active ingredient.

[0002]

2. Description of the Related Art Indole-3-acetic acid (hereinafter "IAA")
) And its derivatives (such as indole-3-acetic acid methyl ester, indole-3-acetamide) promote plant growth and exhibit auxin activity. Also, 4,7-dichloroindole-3-
Acetic acid and 5,7-dichloroindoleacetic acid have anti-auxin activity, as described by Planta, 140 , 89 (1).
978). Also recently, compounds of fluorine-containing β-indolebutyric acids have been developed, and these compounds, namely 4,4,4-trifluoro-3- (indole-3-) butyric acid (hereinafter referred to as “TFIBA”),
4,4,4-trifluoro-2-hydroxy-3- (indole-3-) butyric acid (hereinafter referred to as "TFHIBA"), 4,4,4-trifluoro-3- (indole-
3-) Butyronitrile (hereinafter referred to as "TFIBN") is also known to have a strong root growth promoting activity of plant seeds (Japanese Patent Laid-Open No. 5-279331, October 26, 1993),
Excess that TFIBA has anti-auxin activity
perimentia, 51 , 721 (1995). It is known that substituted TFIBA and its derivatives such as esters also have a stronger growth promoting effect on roots of plant seeds (Japanese Patent No. 2062393, June 24, 1996).

[0003] As the world's population grows, it is important to promote the growth of plants, especially crops used as food. One of the requirements related to the increase in the yield of the crop is the action of elongating the root of the crop. However, conventional plant growth regulators having so-called auxin activity, such as IAA, and other plant growth regulators do not have sufficient root elongation action of plants. On the other hand, a recently developed fluorine-containing β-indolebutyric acid compound, ie, TFI
BA, TFHIBA and TFIBN, as well as substituted TFI
Unlike IAA and its derivatives, BA and its derivatives have a rather strong growth promoting effect on the roots of plant seeds. However, development of a new substance having a plant growth regulating effect in a wider variety of crops is desired in order to utilize the same for practical uses such as increasing the yield of crops.

[0004]

The present inventors have made intensive studies and as a result, have the following formula (I).

[0005]

Embedded image

Wherein Y represents hydrogen or an alkyl group.
One or both of X ¹ and X ² is hydrogen, an alkyl group,
It represents an alkoxy group, an aryl group, or a halogen group. The present inventors have found that fluorine-containing α-indolepropionic acids have an activity of promoting the growth of one or both of the root and hypocotyl of plant seeds, and completed the present invention. That is, an object of the present invention is to provide novel fluorine-containing α-indolepropionic acids having a plant growth promoting action. Another object of the present invention is to provide a method for producing the above compound, and a plant growth regulator containing the compound as an active ingredient.

[0007]

The present invention for solving the above problems comprises the following technical means. (1) represented by the following formula (I)

[0008]

Embedded image

Wherein Y represents hydrogen or an alkyl group.
One or both of X ¹ and X ² is hydrogen, an alkyl group,
It represents an alkoxy group, an aryl group, or a halogen group. ) Fluorine-containing α-indolepropionic acids.

(2) represented by the following formula (II)

[0011]

Embedded image

Wherein R represents hydrogen or an alkyl group.
One or both of X ¹ and X ² is hydrogen, an alkyl group,
It represents an alkoxy group, an aryl group, or a halogen group. A plant comprising reacting 3,3,3-trifluoro-2-hydroxy-2- (indole-3-) propionic acid ester with a chlorinating agent, and then reducing and, if necessary, hydrolyzing the plant. The method for producing a fluorine-containing α-indolepropionic acid according to the above (1), which is a growth regulator.

(3) The above (1) which is a plant growth regulator
A plant growth regulator comprising, as an active ingredient, one or more of the fluorine-containing α-indolepropionic acids described in (1). Hereinafter, the present invention will be described in detail.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing α-indolepropionic acids of the formula (I) (hereinafter referred to as compounds of the formula (I)) can be produced, for example, by the following reaction formula.

[0015]

Embedded image

That is, 3,3 represented by the formula (II)
3-trifluoro-2-hydroxy-2- (indole-3-) propionic acid ester is dissolved in a polar solvent such as dimethylformamide (hereinafter referred to as "DMF") and chlorinated such as thionyl chloride and oxalyl chloride. After the reaction with the agent, for example, sodium borohydride or the like is added and reduced to obtain a compound of the formula (III) (Y =
3,3,3-trifluoro-)
2- (indole-3-) propionic acid ester can be obtained. Then, the compound represented by the formula (III) is heated and hydrolyzed in the presence of a catalyst, preferably an acid, to give a compound represented by the formula (IV) (corresponding to Y = H in the formula (I)). , 3-Trifluoro-2- (indole-3-) propionic acid can be obtained.

The compound of the formula (II), which is a raw material for producing the compound of the formula (I) of the present invention, is, for example, A.I.
E. Zelenin, ND Ohkanikov, Yu.N.Ivanchenko, VD
Thachev, VD Rusakova, AF Kolomiets, and AV
Fokin, Khim. Geterotsikl, Soedin., 1987, 1200-120
1 .; VA Soloshonok and VP Kukhar, Zh.Org.Khi
m., 26, 419-425 (1990).

When the compound represented by the formula (I) is used as a plant growth regulator, it may be used as it is depending on the purpose of use, or may be used together with an auxiliary usually used in pesticides to promote or stabilize its effect. Mix, liquid, powder,
It can also be used in the form of preparations such as granules, wettable powders, flowables or emulsions.

These preparations can be used directly in actual use, or can be used after being diluted to a predetermined concentration with water or a solvent.

The compound represented by the formula (I) is usually 1 × 10
It can be used in a concentration range of ^-9 M to 1 × 10 ^-2 M, but is not limited to this range.

[0021]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. Production Example 1 Methyl 3,3,3-trifluoro-3- (indole-3-) propionate
(Formula (III), X ¹ = H, X ² = H, R = CH ₃ : corresponding to X ¹ = H, X ² = H, Y = CH ₃ in the formula (I))
Preparation of Methyl 3,3,3-trifluoro synthesized in Reference Example 1
-2-hydroxy-2- (indole-3-) propionate (Formula (II), X
^{1 = H, X 2 = H} , R = CH 3) (1.37g, with 5.02 mmol) was dissolved in DMF (10 ml) under an argon atmosphere, under ice-cooling thionyl chloride (1.47 g, 12.4 mmol) at 5 minutes added. Then after 1 hour, an excess of sodium borohydride (1.00 g,
(26.3 mmol) was added over 10 minutes while maintaining the temperature below 30 ° C. in an ice-water bath. After the reaction, the product was put into ice water and extracted with ether. The obtained ether extract was washed with water, dried over anhydrous sodium sulfate. After removing the anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain an oily crude methyl carboxylate (formula (III), X ¹ = H, X ² = H, R = C
H ₃₎ was obtained. Methyl 3,3,3-trifluoro-2- (indole-3-) propio was recrystallized from ethyl acetate / hexane to give plate-like crystals.
0.874 g (68.0% yield) of nate was obtained.

M. p. : 107.0-108.5 ° C IRν ^KBr _max (cm ^-1 ): 3376, 1734, 146
4, 1439, 1359, 1253, 1155, 111
4, 1008, 750 MS (20 ev): 257 (M ⁺ , 35%), 198
(100), 148 (15) ¹ H-NMR (90 MHz, TMS, Acetone-
d ₆ ): 3.73 (3H, s), 4.99 (1H, q,
J = 8.8 Hz), 6.95 to 7.85 (5H, m),
10.48 (1H, brs) ¹⁹ F-NMR (86.46 MHz, TMS, Aceto)
_{ne-d 6): 9.25 (} 3F, d, J = 8.7Hz)

Production Example 2 Methyl 3,3,3-trifluoro-3- (2-methylindole-3-) propio
nate (Formula (III), X ¹ = CH ₃ , X ² = H, R =
CH ₃ : X ¹ = CH ₃ , X ² = H, Y = CH of the formula (I)
₃ ) Methyl 3,3,3-trifluoro-2-hydro synthesized in Reference Example 2
xy-2- (2-methylindole-3-) propionate (Formula (II), X
^{1 = H, X 2 = H} , R = CH 3) (2.87g, 10.0mmol) and under an argon atmosphere, and dissolved in DMF (25 ml), thionyl chloride (3.77 g, 31.7 mmol) and ice-water bath (11 The mixture was added from a dropping funnel over 12 minutes while stirring at a temperature of not more than ℃. After 1 hour, sodium borohydride (2.15 g, 56.6 mmol) was added in 3 hours while maintaining the temperature below 12 ° C. in an ice water bath. After the reaction, the product was put into ice water and extracted with ether. Next, the ether extract was washed with water, dried by adding anhydrous sodium sulfate. After removing the anhydrous sodium sulfate, ether was distilled off with an evaporator, and silica gel column chromatography (developing solution: ether / hexane = 2 /
Separated by 1) and recrystallized with ethanol / water to obtain plate-like crystals of Methyl 3,3,3-trifluoro-3- (2-methylindole-3-)
2.20 g (yield 81.2%) of propionate was obtained.

M. p. : 124.0 to 127.0 ° C IRν ^KBr _max (cm ^-1 ): 3416, 2956, 174
3, 1453, 1437, 1360, 1231, 115
4, 1117, 751 MS (20 ev): 271 (M +, 33), 212 (1
00), 143 (10) ¹ H-NMR (90 MHz, TMS, Acetone-
d ₆ ): 2.48 (3H, s), 3.68 (3H, s)
s), 4.92 (1H, q, J = 9.0 Hz), 6.9
0 to 7.70 (4H, m), 10.30 (1H, br)
s) ¹⁹ F-NMR: (86.46 MHz, TMS, Acet
_{one-d 6): 9.85 (} 3F, d, J = 9.3H
z)

Production Example 3 Ethyl 3,3,3-trifluoro-2- (indole-3-) propionate (Formula (III), X ¹ = H, X ² = H, R = C ₂ H ₅ : Formula (I) ) Of X ¹ = H, X ² = H, Y = C ₂ H ₅ ) Ethyl 3,3,3-trifluoro-2- produced in the same manner as in Reference Example 1.
hydroxy-2- (indole-3-) propionate (Formula (II), X ¹
= H, X ² = H, R = C ₂ H ₅ ) (1.15 g, 4.01 mmol) was dissolved in DMF (10.0 ml) under a stream of argon, and thionyl chloride (1.47 g, 12.4 mmol) was added from a dropping funnel. In addition, the mixture was added dropwise over 3 minutes while stirring in an ice water bath (14 ° C. or lower).
1.5 hours later, sodium borohydride (0.626 g, 16.5 m
mol) was added in an ice water bath over 1 hour while maintaining below 19 ° C. After the reaction, the product was put into ice water and extracted with ether. The obtained ether extract was washed with water, dried by adding anhydrous sodium sulfate, and then the ether was distilled off by an evaporator. The residue was separated by silica gel column chromatography (developing solution: ether / hexane = 3/2), and ethanol / ethanol was removed. Recrystallized with water to form plate-like crystals of Ethyl 3,3,3-tr
0.935 g of ifluoro-2- (indole-3-) propionate (83.
5%).

M. p. : 89.4-90.0 ° C IRν ^KBr _max (cm ⁻¹ ): 3379, 1726, 155
0, 1459, 1371, 1240, 1148, 110
7, 1017, 743 MS (20 ev): 271 (M ⁺ , 36%), 198
(100), 148 (11) ¹ H-NMR (90 MHz, TMS, Acetone-
d ₆ ): 1.20 (3H, t, J = 7.0 Hz);
21 (2H, q, J = 7.2 Hz), 4.96 (1H,
q, J = 8.9 Hz), 6.95-7.85 (5H,
m), 10.53 (1H, brs) ¹⁹ F-NMR (90 MHz, TMS, Acetone-
d ₆ ): 9.36 (3F, d, J = 9.3 Hz)

Production Example 4 3,3,3-Trifluoro-2- (indole-3-) propionic acid (Formula (IV), X ¹ = H, X ² = H, R = H: X of the formula (I)
Production of ¹ = H, X ² = H, Y = H) Methyl 3,3,3-trifluoro-2- (indo synthesized in Production Example 1
le-3-) propionate (Formula (III), X ¹ = H, X ² =
(H, R = CH ₃ ) (1.21 g, 4.71 mmol) was added to 12 ml of concentrated hydrochloric acid, and the mixture was refluxed for 4 hours. After the reaction, the product was put into ice water and extracted with ethyl acetate. The obtained ethyl acetate extract was washed with water, dried over anhydrous sodium sulfate. After removing the anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized with ethanol / water to give columnar crystals of 3,3,3-
0.810 g (yield 70.6%) of Trifluoro-2- (indole-3-) propionicacid was obtained.

M. p. : 166.0 to 168.0 ° C IRν ^KBr _max (cm ^-1 ): 3482, 1733, 146
7, 1426, 1250, 1159, 1120, 759 MS (20 ev): 243 (M ⁺ , 53%), 198
(100), 151 (11), 148 (19) ¹ H-NMR (90 MHz, TMS, Acetone-
d ₆ ): 1.55 (1H, s), 5.03 (1H, q,
J = 8.5 Hz), 7.10 to 7.85 (5H, m),
8.23 (1H, brs) ¹⁹ F-NMR (86.46 MHz, TMS, Aceto)
_{ne-d 6): 9.32 (} 3F, d, J = 8.7Hz)

The fluorine-containing α-indolepropionic acids represented by the formula (I) are novel compounds which have not been described in the literature, and the yields and melting points of typical fluorine-containing α-indolepropionic acids are shown in Table 1. Show.

[0030]

[Table 1]

Reference Example 1 Methyl 3,3,3-trifluoro-2-hydroxy-2- (indole-3-) prop
ionate (Formula (II), X ¹ = H, X ² = H, R = C
Production of H ₃ ) Indole (3.51 g, 30.0 mmol) and chloroform (12.0 ml) were added to a three-necked flask equipped with a Dimroth condenser under a stream of argon. Then, chloroform (5.0 ml)
Methyl trifluoropyruvate dissolved in water (7.58g, 48.6mmo
l) was dropped from the dropping funnel in an ice-water bath (15 ° C. or lower) while stirring and reacting for 30 minutes. After the reaction, hexane is added to precipitate Methyl 3,3,3-trifluoro-2-hydroxy-2
5.82 g (71.0% yield) of-(indole-3-) propionate was obtained.
Recrystallization from chloroform / hexane gave white plate crystals.

M. p. : 92.0-93.1 ° C IRν ^KBr _max (cm ^-1 ): 3419, 3340, 175
6, 1620, 1550, 1466, 1443, 134
5, 1263, 1182, 1175, 1105, 100
1, 757 MS (20 ev): 273 (M ⁺ , 38), 214 (1
00), 204 (10), 144 (79), 117 (8
4) ¹ H-NMR (90 MHz, TMS, Acetone-
d ₆ ): 3.87 (3H, s), 6.00 (1H,
s), 6.90 to 8.00 (5H, m), 10.44
(1H, brs) ¹⁹ F-NMR: (86.46 MHz, trifluoroacetic acid (external standard), Acetone-d6): 0.93 (3
F, s)

Reference Example 2 Methyl 3,3,3-trifluoro-2-hydroxy-2- (2-methylindole
-3-) propionate (Formula (II), X ¹ = CH ₃ , X ² =
Preparation of H, R = CH ₃ ) In a three-necked flask equipped with a Dimroth condenser, 2-methylindole (3.93 g, 30.0 mmol) was dissolved in chloroform (12.0 ml) under a stream of argon, and chloroform (5.0 ml) was added.
Methyl trifluoropyruvate dissolved in water (7.84g, 35.0mmo
l) was added in an ice-water bath from a dropping funnel while stirring and reacting for 30 minutes. After the reaction, hexane is added to precipitate Methyl 3,3,3-trifluoro-2-hydroxy-2- (2-methylin
7.84 g (yield 91.0%) of dole-3-) propionate was obtained. Recrystallization from chloroform / hexane gave plate crystals.

M. p. : 76.0 to 84.0 ° C IRν ^KBr _max (cm ⁻¹ ): 3376, 2956, 173
2,1551,1459,1436,1180,109
0, 1040, 748 MS (20 ev): 287 (M ⁺ , 43), 228 (1
00), 158 (61), 131 (71) ¹ H-NMR (90 MHz, TMS, Acetone-
d ₆ ): 2.52 (3H, s), 3.81 (3H, s)
s), 6.32 (1H, s), 6.90 to 7.70 (4
H, m), 10.35 (1H, brs) ¹⁹ F-NMR: (86.46 MHz, trifluoroacetic acid (external standard), Acetone-d ₆ ): 0.15 (3
F, s)

Test Example 1 Formula (II) (X ¹ = H, X ² = H, R = CH ₃ ) and Formula (I) (X ¹ = H, X ² = H, Y = CH ₃ and Y = H )
Is used as a sample to prepare a drug solution having a predetermined concentration, and α of the formula (II)
-The activity of the compound of formula (I) of the present invention prepared by substituting a hydroxy group with hydrogen was examined. 5 ml of each medicinal solution was added to a 6 cm diameter petri dish, and germinated seeds of Chinese cabbage (variety: Kinshu) were placed on a filter paper (5.5 cm diameter) in the dish, and the temperature was 25 ° C.
After incubation for 3 days at 6,000 lux for 16 hours, the root length and hypocotyl length were examined. Table 2 shows the results.

[0036]

[Table 2]

Test Example 2 Formula (I) (X ¹ = H and C ₆ H ₅ , X ² = H, 5-C
H ₃ , 5-CH ₃ O and 5-Cl, Y = H, CH ₃ and C ₂
Using H ₅ ) as a sample, a drug solution having a predetermined concentration was prepared, and the activity due to various substituents was examined. 5 ml of each medicinal solution was added to a 6 cm diameter petri dish, and germinated seeds of Chinese cabbage (variety: Kinshu) were placed on filter paper (5.5 cm diameter) in the dish, and the mixture was placed at 25 ° C and 6,000.
After incubating for 3 days at 0 lux for 16 hours, the root length and hypocotyl length were examined. Table 3 shows the results.

[0038]

[Table 3]

Test Example 3 Formula (I) (X ¹ = H and C ₆ H ₅ , X ² = H, 5-C
H ₃ , 5-CH ₃ O and 5-Cl, Y = H, CH ₃ and C ₂
Using H ₅ ) as a sample, a drug solution having a predetermined concentration was prepared, and the activities of various substituents in a dark place were examined. Add 5 ml of each chemical solution to a 6 cm diameter petri dish, and filter paper (5.5 cm diameter)
Put germinated seeds of Chinese cabbage (variety: Kinshu) on the top, 25 ℃,
After incubation in the dark for 3 days, root length and hypocotyl length were examined. Table 4 shows the results.

[0040]

[Table 4]

Test Example 4 Formula (I) (X ¹ = H, X ² = H, Y = CH ₃ ) and IAA
Using a methyl ester as a sample, a drug solution having a predetermined concentration was prepared, and the effect of introducing a trifluoromethyl group on the activity in a dark place was comparatively investigated. Ten germinated seeds of black mappe were placed on a filter paper (5.5 cm in diameter) impregnated with a chemical solution in a petri dish of 6 cm in diameter and incubated at 25 ° C. in the dark for 3 days. investigated. Table 5 shows the results.

[0042]

[Table 5]

As is clear from the results of Test Example 1, α-
Wherein the compound of formula (II) having a hydroxy group at the position has no growth-promoting effect or exhibits an inhibitory effect under normal light-dark cycle growth conditions, whereas the hydroxy group at the α-position is replaced with hydrogen. Formula (I) of the present invention produced by
, Ie, fluorine-containing α-indolepropionic acids, showed a promoting effect on the growth from plant seeds in both root and hypocotyl. The results of Test Example 2 also show that the introduction of a substituent to the indole ring promotes the growth of the root or hypocotyl, and particularly the introduction of a phenyl group at the 2-position significantly promotes the growth of the root even at a low concentration of a chemical solution. showed that. Under the growth conditions in a dark place shown in Test Example 3, by introducing a substituent into the indole ring, the root growth promoting effect was exhibited.
In contrast to the growth of the black mappe in the dark place shown in Test Example 4, the growth of the root part is remarkably promoted in the low concentration region of 10 ^-6 to 10 ^-7 M, but the growth of the root portion is as high as 10 ^-4 to 10 ^-3 M. In the concentration region, root swelling similar to that of the IAA ester was observed. Thus, 2-
Α-indolepropionic acids, which are produced by reducing the hydroxy group at the 1-position, form a new group of compounds that promote the growth of one or both of the root and hypocotyl by selecting the substituent or the concentration of the drug solution used. provide.

[0044]

According to the present invention, there are provided novel fluorine-containing α-indolepropionic acids represented by the above formula (I) and a method for producing the same. The fluorine-containing α-indolepropionic acids of the present invention have an action of promoting the growth of one or both of the root and the hypocotyl, and are useful as an active ingredient of a plant growth promoter.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 5, 1999

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction contents]

[0038]

[Table 3]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction contents]

[0040]

[Table 4]

Claims (3)

[Claims] 1. A compound represented by the following formula (I): (Wherein, Y represents hydrogen or an alkyl group; X ¹ and X ²
One or both of them represents hydrogen, an alkyl group, an alkoxy group, an aryl group, or a halogen group. ) Fluorine-containing α-indolepropionic acids. 2. A compound represented by the following formula (II): (Wherein, R represents hydrogen or an alkyl group. X ¹ and X ²
One or both of them represents hydrogen, an alkyl group, an alkoxy group, an aryl group, or a halogen group. A plant comprising reacting 3,3,3-trifluoro-2-hydroxy-2- (indole-3-) propionic acid ester with a chlorinating agent, and then reducing and, if necessary, hydrolyzing the plant. The method for producing a fluorine-containing α-indolepropionic acid according to claim 1, which is a growth regulator. 3. One or two of the fluorine-containing α-indolepropionic acids according to claim 1, which is a plant growth regulator.
A plant growth regulator containing at least one species as an active ingredient.