JP2526411B2 - Dividing promoter for gramineous plants - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel parting promoter for promoting parting of gramineous plants and increasing the fresh weight to increase the yield of crops.

[0002]

Indole-3-acetic acid and its derivatives,
For example, indole-3-methyl acetate, indole-3-
It has long been known that acetamide promotes plant growth, and also 4,7-dichloroindole-
It is also known that 3-acetic acid and 5,7-dichloroindoleacetic acid have an anti-auxin effect ["planta" No. 140.
Vol. 89 (1978)].

Recently, fluorine-containing β-indolebutyric acids have been developed, among which 4,4,4-trifluoro-
3- (indole-3-) butyric acid, 4,4,4-trifluoro-2-hydroxy-3- (indole-3-) butyric acid and 4,4,4-trifluoro-3- (indole-3)
-) Butyronitrile was found to have a strong plant root elongation promoting activity (JP-A-5-279331), and 4,4,4-trifluoro-3- (indole-3-) butyric acid was found in paddy rice. It has been reported that it is effective for increasing the number of divisions and the fresh weight of grasses such as wheat and wheat that greatly contribute to the harvest [Plant Chemistry Control Society, 1993 Conference, Research Papers No. 46] Page, Published by The Society of Phytochemical Regulation and Report of Nagoya Institute of Industrial Technology, Volume 42,
Pp. 215-223 (1994)].

By the way, as the world population has increased in recent years,
As a result of an important issue, it has become an important task to increase the yield of crops used as food, especially grasses such as wheat and paddy rice, which are positioned as major cereal plants in the world.
There is a demand for the development of a substance that causes an increase in the number of divisions and an increase in fresh weight that influence the increase in the yield of grasses.

The above-mentioned 4,4,4-trifluoro-3-
It is known that (indole-3-) butyric acid promotes division of gramineous plants and is effective in increasing the body weight, but this action is not always sufficient, and it requires a large amount of use. Therefore, in order to use it as a practical revenue-increasing agent, it was necessary to develop a substance showing higher activity even when used in a small amount.

[0006]

DISCLOSURE OF THE INVENTION The present invention can significantly promote the division of grasses by using a small amount,
Moreover, the purpose of the present invention is to provide a substance effective for increasing the body weight.

[0007]

Means for Solving the Problems As a result of various studies on the growth promoting substance of grasses, the present inventors have found that 4,4,4-trifluoro-3- (indole-3
-) Butyric acid esterified or amidated carboxylic acid was found to be significantly effective in promoting division of gramineous plants, and was also found to be effective in increasing the number of living organisms, and the present invention is based on this finding. It came to eggplant.

That is, the present invention has the general formula

Embedded image (R ¹ and R ² in the formula are a hydrogen atom or an alkyl group, and Y is an alkoxyl group or an amino group) A fluorine-containing indolebutyric acid derivative as an active ingredient is there.

Particularly preferred as the active ingredient of the present invention is
In the general formula (I), R ¹ and R ² are hydrogen atoms and Y is an alkoxyl group, that is, an alkyl ester of 4,4,4-trifluoro-3- (indole-3-) butyric acid. The alkyl group may be linear or branched and preferably has 1 to 8 carbon atoms.

In addition, one or both of R ¹ and R ² having an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, or a compound having Y as an amino group, that is, a substituted butyric acid amide is also used. You can The amino group in the amide group at this time may be a primary amino group, a secondary amino group or a tertiary amino group.

Next, the fluorine-containing indolebutyric acid derivative represented by the general formula (I) can be produced, for example, according to the following steps.

[0012]

Embedded image (However, R ³ is an alkyl group, R ⁴ and R ⁵ are each a hydrogen atom or an alkyl group, and Et is an ethyl group.)

That is, diethyl malonate is dissolved in, for example, toluene or benzene, sodium metal is added thereto, and the mixture is preferably refluxed under heating to give a compound represented by the formula (III), and then represented by the general formula (II). 2,
2,2-trifluoro-1- (substituted indole-3-)
Ethanol is added and the mixture is heated under reflux again to obtain the diester represented by the general formula (IV). Next, the diester represented by the general formula (IV) is dissolved in a lower alcohol (for example, methanol), and then an aqueous solution of alkali, preferably alkali carbonate (for example, potassium carbonate) is added and heated to reflux to give the general formula (V). A carboxylic acid represented by Further, by heating the compound represented by the general formula (V) in the presence of an alcohol and a catalyst, preferably an acid, a compound represented by the general formula (VI) [corresponding to Y = OR ³ of the formula (I)] is obtained. An ester can be obtained and also
The amide represented by the general formula (VII) is obtained by heating the compound represented by the general formula (VI) with an amine.

The compound represented by the general formula (II), which is a raw material for producing the compound represented by the general formula (I), can be prepared by a known method [for example, "J. Fluorine Chemistry".
m. ), 39, 47-59 (1988)
), "Nagoya Industrial Research Institute Report," Vol. 41, No. 18
The method described in pages 5-195 (1992) and the like] can be used for the production. In addition, the general formula (IV)
The intermediate represented by can also be produced by utilizing the method described in JP-A-5-279331.

To use the parting promoter of the present invention, it is dissolved in a solvent such as water, alcohol or a mixed solvent thereof at a concentration of 0.1 to 10 ppm, and seeds of grasses are soaked in this solution. After that, spray on the field. The processing time at this time may be about 1 to 10 seconds.

[0016]

The dividing promoter of the present invention contains a fluorinated indolebutyric acid derivative as an active ingredient, and when it is used especially for grasses, it significantly increases the number of divided pieces and the fresh weight. , Increase yields.

[0017]

Next, the present invention will be described in more detail with reference to examples.

Reference Example 1 4,4,4-trifluoro-3- (indole-3-)
Butyric acid [corresponding to Y = OH, R ¹ = H, R ² = H in formula (I)]
2.3 g of sodium metal was added to a solution of 16.0 g (100 mmol) of diethyl malonate in 50 ml of toluene,
After heating under reflux for 1.5 hours, 2,2,2-trifluoro-1- (indole-3-) ethanol 4.3 g (2
0 mmol) was added. After heating under reflux for a further 4 hours, water was carefully added, and the mixture was extracted 3 times with ethyl acetate. The ethyl acetate layer was washed with water and saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the crude dicarboxylic acid diester. A toluene solution was obtained. This solution is hexane /
After partitioning with acetonitrile, the acetonitrile layer was concentrated under reduced pressure, and the resulting crude diester was added to 100 m of methanol.
dissolved in 1 and then an aqueous solution of 25.7 g of potassium carbonate 80
ml was added, and the mixture was heated under reflux for 90 hours.

Next, the mixture was neutralized with hydrochloric acid, concentrated under reduced pressure to remove methanol, made alkaline with a 4N sodium hydroxide aqueous solution, and then extracted with ethyl acetate. The aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude carboxylic acid obtained was purified by silica gel column chromatography. Then, 4.2 g of 4,4,4-trifluoro-3- (indole-3-) butyric acid
(Yield 82.0%) was obtained.

The melting point of this product is 117 to 119 ° C., and the infrared absorption spectrum, mass spectrum and ¹
The measurement results of 1 H-NMR are as follows. IR ν _max ^KBr (cm ⁻¹ ): 3430, 1722, 1460, 1438, 1422,
1380, 1326, 1313, 1296, 1280,
1155, 1117, 962, 823, 745, 66
4,618 MS (70 ev): 257 (M ⁺ , 86%), 237 (30), 198 (1).
00), 188 (22) ¹ H-NMR (200 MHz, TMS, acetone-
_{d 6): 2.95~3.25 (3H,} m), 4.35 (1H,
m), 7.00 to 7.25 (2H, m), 7.40 to
7.55 (2H, m), 7.69 (1H, d, J = 7.
0Hz)

Reference Example 2 4,4,4-trifluoro-3- (2-methylindole-3-) butyric acid [Y = OH, R ¹ = H, R ² = of the formula (I)]
Metallic sodium 12.7g added to toluene 300ml A solution of diethyl malonate 16.0 g (555 mmol) of equivalent] in CH _3, after heating under reflux for 2 hours, 2,2,2-trifluoro-1- (2 -Methylindole-3-) ethanol 4
2.3 g (185 mmol) was added. After heating under reflux for a further 20 hours, methanol was added to decompose unreacted sodium, and the reaction mixture was neutralized with 4N-hydrochloric acid. The neutralized solution was concentrated and the resulting aqueous solution was acidified with 4N-hydrochloric acid and extracted 4 times with ethyl acetate. The ethyl acetate layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give an oily crude dicarboxylic acid diester. This crude diester was dissolved in 200 ml of methanol and dissolved in 100 ml of water, potassium carbonate 127.6.
g (925 mmol) was added to the methanol solution, and the mixture was heated under reflux for 48 hours. The solution was cooled to room temperature, neutralized with 4N-hydrochloric acid, and concentrated in vacuo to give an aqueous solution. 4 aqueous solution
The mixture was made alkaline with N-sodium hydroxide solution, treated with ethyl acetate three times, acidified with 4N-hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over anhydrous sodium sulfate, and concentrated in vacuo to give crude indolebutyric acid, which was separated by silica gel column chromatography and recrystallized from ethyl acetate / hexane to give 4,4,4-trifluoro -3- (2-methylindole-3-) butyric acid 3
8.8 g (yield 77.4%) was obtained.

The melting point of this product is 148 to 149 ° C., and the infrared absorption spectrum, mass spectrum and ¹
The measurement results of 1 H-NMR are as follows. IR ν _max ^KBr (cm ⁻¹ ): 3475, 3420, 3060, 2930, 1713,
1460, 1430, 1310, 1260, 1150,
1110, 1020, 750, 630, 465 MS (70 ev): 271 (M ⁺ , 85%), 251 (6), 226.
(5), 212 (100), 202 (39), 160
(10), 156 (12), 130 (12) ¹ H-NMR (200 MHz, TMS, acetone-
_{d 6): 2.95~3.25 (3H,} m), 4.35 (1H,
m), 7.00 to 7.25 (2H, m), 7.40 to
7.55 (2H, m), 7.69 (1H, d, J = 7.
0Hz)

Reference Example 3 4,4,4-trifluoro-3- (indole-3-)
Ethyl butyrate [Y in formula (I) = OC ₂ H ₅ , R ¹ = H, R ² =
Equivalent to H] 4,4,4-trifluoro-3-obtained in Reference Example 1
5.1 g (20 mmol) of (indole-3-) butyric acid was dissolved in 300 ml of ethanol and saturated with hydrochloric acid gas,
After refluxing overnight, ethanol and hydrochloric acid were distilled off and the mixture was dried to dryness.
The obtained residue was separated by silica gel column chromatography and recrystallized from hexane to give 4,
5.5 g (yield 96%) of ethyl 4,4-trifluoro-3- (indole-3-) butyrate was obtained.

This product has a melting point of 57 to 58 ° C., and has infrared absorption spectrum, mass spectrum and ¹ H-NMR.
The measurement results of are as follows. IR ν _max ^KBr (cm ⁻¹ ): 3430, 1725, 1468, 1390, 1263,
1161, 1020, 963, 821, 750 MS (70 ev): 285 (M ⁺ , 100%), 265 (32), 237.
(51), 198 (75) ¹ H-NMR (90 MHz, TMS, acetone-d ₆ ): 1.07 (3 H, t, J = 7.0 Hz), 4.00 (2
H, q, J = 7.0 Hz), 3.02 and 3.1.
1 [2H, AB-d, J = 15.7 and 9.8
(4.7) Hz], 4.35 (1H, d-d-q J =
9.8, 4.7 and 9.3 Hz, 7.68 (1
H, m), 7.09 (1H, m), 7.15 (1H,
m), 7.43 (1H, m), 7.44 (1H, d, J
= 2.4 Hz)

Reference Example 4 Ethyl 4,4,4-trifluoro-3- (2-methylindole-3-) butyrate [Y = OC ₂ H ₅ , R ^{1 of the} formula (I)]
= H, R ² = CH ₃ ]] 4,4,4-trifluoro-3-obtained in Reference Example 3
2.21-g (2-methylindole-3-) butyric acid (8.
(18 mmol) was dissolved in 50 ml of ethanol, 0.05 ml of concentrated sulfuric acid was added, and the mixture was heated under reflux for 11 hours, poured into ice water and extracted with ether three times, and then the ether layer was washed with water and saturated brine, The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude ethyl ester obtained was separated by silica gel column chromatography and recrystallized from carbon tetrachloride / hexane to give ethyl 4,4,4-trifluoro-3- (2-methylindole-3-) butyrate. 2.40 g (yield 98.1%) was obtained.

The melting point of this product is 71 to 71.5 ° C., and the infrared absorption spectrum, mass spectrum and ¹ H-
The NMR measurement results are as follows. IR ν _max ^KBr (cm ⁻¹ ): 3360, 1710, 1460, 1420, 1315,
1295, 1265, 1230, 885, 718, 65
0 MS (70 ev): 299 (M ⁺ , 100%), 254 (10), 230.
(25), 212 (92), 157 (14) ¹ H-NMR (90 MHz, TMS, acetone-d ₆ ): 1.03 (3 H, t, J = 7.0 Hz), 2.46 (3
H, s), 3.16 (2H, d, J = 7.2 Hz),
4.01 (2H, q, J = 7.0Hz), 4.27 (1
H, t-d, J = 10.5 and 7.2 Hz),
6.9 to 7.6 (4H, m), 10.05 (1H, br
s)

Reference Example 5 4,4,4-Trifluoro-3- (2-methylindole-3-) butyric acid amide [Y = NH ₂ , R ¹ = of the formula (I)]
Equivalent to H, R ² = CH ₃ ] 4,4,4-trifluoro-3-obtained in Reference Example 4
(2-Methylindole-3-) ethyl butyrate 0.60 g
(2.0 mmol) was dissolved in 5 ml of methanol to give 28
Add 20 ml of wt% ammonia water and stir 6
The mixture was heated (35 ° C.) for a period of time and reacted. After cooling with ice, saturated brine was added, the mixture was extracted 4 times with ethyl acetate, the ethyl acetate layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give an almost pure amide compound. Recrystallisation from ethyl acetate / hexanes gave 0.34 g (71.9%) of 4,4,4-trifluoro-3- (2-methylindole-3-) butyric acid amide.

The melting point of this product is 177 to 177.5 ° C., and the infrared absorption spectrum, mass spectrum and
The measurement results of ¹ H-NMR are as follows. IR ν _max ^KBr (cm ⁻¹ ): 3500, 3380, 3250, 1685, 1675,
1465, 1340, 1260, 1155, 1105,
1025, 755, 445 ¹ H-NMR (90 MHz, TMS, acetone-d ₆ ): 2.40 (3H, s), 3.18 (2H, s), 4.3
8 (1H, m), 6.29 (1H, brs), 6.9-
7.1 (3H, m), 7.2-7.6 (2H, m), 1
0.08 (1H, brs) MS (70ev): 271 (M ⁺ , 14%), 270 (M ⁺ , 93%), 25
0 (34), 226 (17), 213 (14), 212
(100), 211 (21), 201 (9), 158
(25), 157 (14)

Examples 1 to 5 and Comparative Example Biological test on wheat Seeds of wheat (variety: 50:50) by instantaneously soaking in a mixed solution of alcohol and water containing the drug shown in Table 1 at a predetermined concentration (weight ratio: 50:50) Norin 61) on the field (1993 1
It was cultivated on January 6th. Thirty-five days after sowing, when the number of stalks per strain became about 3, the average fresh weight and the number of splits / strain were investigated and expressed as a percentage relative to the control (untreated). Table 1 shows the results.

[0030]

[Table 1]

As is clear from this table, the parting promoter of the present invention is superior to 4,4,4-trifluoro-3- (indole-3-) butyric acid in both the parting number and the fresh weight. There is.

Example 6 A 0.1 ppm solution of the compounds obtained in Reference Examples 4 and 5 was prepared in the same manner as in Examples 1 to 5, and wheat seeds treated with the solution were scattered and tested. , Both 105
It showed an increase in the number of splits of ~ 113%.

Claims (2)

(57) [Claims] 1. A compound of the general formula ( ¹⁾ wherein R ¹ and R ² in the formula are hydrogen atoms or alkyl groups, and Y is an alkoxyl group or amino group, and a fluorinated indole butyric acid derivative as an active ingredient. 2. A dividing promoter for gramineous plants containing 4,4,4-trifluoro-3- (indole-3-) butyric acid alkyl ester as an active ingredient.