JPS62132804A - Plant growth regulator - Google Patents

Abstract

PURPOSE:A plant growth regulator usable for various crops without causing phytotoxicity, showing extremely improved effects on growth of rooting and promotion of rapid growth in blooming season and in time of harvesting, comprising a specific itaconic acid derivative as an active ingredient. CONSTITUTION:A plant growth regulator containing a compound selected from a group consisting of an alkylitaconic acid containing 1-8C (except 6C) alkyl group at a side chain, 1-5C alkyl monoester thereof, exo-methylene of itaconic acid containing 1-8C alkyl group at the side chain and 1-5C alkyl ester thereof as an active ingredient. The compound such as (+ or -)-ethylitaconic acid is obtained from 2-propene-1,1,2-triethyltricarboxylate as a starting substance by a reaction according to the reaction formula.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to plant growth regulators. More specifically, the present invention relates to an alkyl itaconic acid having an alkyl group having 1 to 8 carbon atoms (excluding 6 carbon atoms) in a side chain, an alkyl monoester of the above alkyl itaconic acid having an alkyl group having 1 to 5 carbon atoms, One or more compounds selected from the group consisting of the exomethylene of itaconic acid having an alkyl group having 1 to 8 carbon atoms in the side chain and the alkyl monoester of the exomethylene of the above-mentioned itaconic acid having an alkyl group having 1 to 5 carbon atoms. The present invention relates to a plant growth regulator as an active ingredient.

Prior Art In the field of plant growth regulators, for example, "Chemical Regulation in the Field of Orchard Horticulture" (Plant Chemistry Regulation, Vol. 13, No. 1, 1978) and "Uses and Future Directions of Plant Growth Regulators" (Research Journal, Vol. 8, 7
(No., 1985) reviews the current state of practical use and future problems of plant growth regulators in the fields of horticulture and paddy rice, as shown in the article, increasing yield, stabilizing production, improving quality, labor saving, etc. Each applied technology has not yet provided sufficient satisfaction, and there is a great deal of need for future technological innovation. Furthermore, in reality, plant growth regulators account for only about 1% of total agricultural sales in Japan.
The current situation is that it is extremely limited, accounting for only about 1% worldwide.

Next, reference will be made to conventional techniques related to the rooting promotion effect and the early flowering and harvesting periods involving plant growth regulators.

1) Rooting promotion effect By promoting rooting and raising young seedlings, it is possible to improve seedling quality and increase yield. In addition, maintaining the physiological vitality of roots at a high level until the late stage of growth is an effective means of increasing yield and preventing rice lodging. Conventional 2.4-D, NAA
(naphthaleneacetic acid), IBA (indolebutyric acid), etc. are quite effective in promoting alarm, but they are still far from being sufficient, and depending on the conditions, so-called hormonal drug damage may occur.
The drawback is that it lacks safety.

2) Early flowering and harvesting conventional plant growth regulators that increase yield by promoting flowering (fruit) include, for example, 4-chlorophenoxyacetic acid and 2-naphthoxyacetic acid. Ethephon (manufactured by Union Carbide Co., Ltd., chloroethylphosphonic acid) is known as a drug that promotes the establishment of female cucumber flowers, but it is difficult to put to practical use because it causes phytotoxicity such as defoliation and leaf burn. Ethephon also has the effect of accelerating the ripening period, so it is possible to hasten the harvest period of fruit trees, etc., but its widespread use is particularly hindered by defoliation.

In this way, compounds that can specifically accelerate the flowering period or the harvest period have hardly been found in practical use, and effective and safe drugs for this purpose are extremely valuable, especially for horticultural crops that have high cash value. Therefore, the creation of such a plant growth regulator has been strongly desired.

Problems to be solved by the invention It greatly accelerates the rooting, flowering (fruit) period, and harvesting period of crops, leading to early harvest and increased yield, and eliminating the drawbacks of conventional plant growth regulators. It is an object of the present invention to create an effective and safe plant growth regulator that does not contain any harmful substances.

Means for Solving the Problems The present inventors have previously developed Aphpergillus niger K-88 (
We focused on the unique plant physiological activity of hexylitaconic acid produced by Aspergillus niger K-88), studied this, and filed a patent application as a plant regulator (Japanese Patent Application No. 12055'O, 1982). .

The present inventors continued to study the synthesis and physiological activity of hexylitaconic acid related substances, and as a result,
The present invention was completed by discovering that itaconic acid derivatives having an alkyl group with 1 to 8 carbon atoms in the side chain in addition to hexyl groups have remarkable plant physiological activity comparable to hexylitaconic acid, for which a patent application was previously filed. .

In a series of studies related to the search for useful plant growth regulators, the present inventors have found that one or more compounds selected from the group consisting of, for example, have extremely excellent effects on promoting rooting, flowering, and harvesting. It has been found that it can be used on various crops without any phytotoxicity.

Next, a method for synthesizing these itaconic acid derivatives according to the present invention will be explained.

These compounds can be produced by the following reaction method.

While cooling with ice water, add 6 to 2.5 ml of DMF.
Add 96 mg of 0% sodium hydride and 1 ml of DMF.
Add dropwise 516 mg of 2-propene-1,1,2-triethyltricarboxylate (2) above dissolved in
Stir for 1 hour. Next, 375 mg of ethyl iodide dissolved in 1 ml of DI'IF was added dropwise, and the mixture was stirred at room temperature for 30 hours. The reaction solution was poured into IQml of diluted hydrochloric acid and extracted twice with ether. The ether layer is washed with saturated aqueous sodium bicarbonate solution and dried over anhydrous sodium sulfate. After distilling off the ether, crude 1-pentene-2,3,3-)ethyltricarboxylate is obtained. This was dissolved in 3 ml of acetic acid and 1 ml of concentrated hydrochloric acid without purification, and refluxed for 10 hours. After cooling the reaction solution, 50 ml of water was added and extracted three times with ethyl acetate. Combine the ethyl acetate extracts and dry with anhydrous sodium sulfate. After distilling off the acetic acid, the residue was purified by silica gel chromatography to give 85 mg.
(±)-Ethyl itaconic acid of (■) is obtained. Yield 27
% CI-MS m/z 159 (M+1)” Acetone-
d6'H-NMRδn O,92(311,t
+J=8Hz).

1.80 (2H, m), 3.40 (IH, t.

J=7Hz), 5.74(18,s), 6.25(
IH,s), 9.50 (211,5)48.8(
d), 127.6(t), 139.4(s),
168.6(s), 175.7(s).

Production example 2 (±)-propyl itaconic acid 516 mg
1 and 410 mg of n-propyl iodide in the same manner as in Production Example 1 to obtain crude 1-hexene-2,3,
3-Triethyltricarboxylate was obtained, which was purified by silica gel chromatography to give pure 1
-Hexene-2,3,3-1-ethyltricarboxylate (400.3 mg) is obtained. Yield 66.7%E
T-MS m/z 300 (M") (118, m),
2.10 (28, m) + 4.16 (6H, q, J
=7Hz), 5.80 (1B.

s), 6.34 (III, 5) 14.3 (q), 18.5 (t), 36.5 (t)
.

60.9(s), 61.0(t), 61.4(2c
.

t), 126.6 (t), 138.4 (s).

166.0 (s), 169.7 (2c, s) ■
■ Concentrated 11+1-C as in the case of production example 1 of ■(±)-propyl itaconic acid 300g
94. by hydrolysis and decarboxylation with H,COOH.
8 mg of (±)-propyl itaconic acid are obtained. Yield 55.1% CI-MS m/z 173(M+1)”1.2-2
．． 1 (4H, m), 3.48 (IH.

t, J=7Hz), 5.76 (18,s).

6.28 (18, s), 10.10 (2H, 5) 33
．． 8(t), 46.8(d), 127.2(t).

139.8(s), 168.3(s), 175.4
(s) Production example 3 (±)-butyl itaconic acid ■■
■516mg■ and 44
Using 2 mg of n-butyl iodide in the same manner as in Production Example 2, 509.5 mg of 1-heptene-2,3°3-triethyltricarboxylate (2) was obtained. Yield 81.8% El-MS m/z 314 (M”) (1311, m
), 2.12 (2tl, m), 4.16 (611,
q, J=7Hz), 5.80 (IH.

s), 6.35 (01,5) 22.8 (t), 27.1 (t), 34. o(t)
.

60.7(s), 60.7(t), 61.2(t)
.

126.4(t), 138.2(s), 165.8
(s), 169.4 (2c, s) ■ ■ Same as in Production Example 2 from 360 mg of (±)-butyl itaconic acid? a HCl −
When hydrolyzed with CH5COOH and decarboxylated, (±)
-129.3 mg of butyl itaconic acid are obtained. Yield 60.6% El-MS m/z 186 (M”) 1.35 (4t
l, m) + 1.85 (2B, m).

3.48 (IH, t, J=7Hz), 5.78 (I
H,s), 6.30(IH,s), 10.30(2
8,5) 30.3(t), 31.4(t), 47.0(d)
.

127.3(t), 139.7(s), 168.5
(s), 175.7 (s) v Preparation example t (±)-Pentyl itaconic acid 0516m
Production example 2 from g of ■ and 475 mg of n-pentyl iodide
In the same manner as above, 252.2 mg of 1-octene-2,3,3-)ethyltricarboxylate of (1) is obtained. Yield 38.4% IEI-MS m/z 32B (
M”) (15H, m) + 210 (28, m), 4.
10 (6B, q, J=7H2), 5.81 (
IH, s) 6.36 (IH, 5) (t), 24.7 (L), 32.0 (t), 34.
3(60.8(s), 60.9(t), 61.3(
2c.

t), 126.6(t), 138.3(a).

165.9(s), 169.6(2c, s)1
Concentrated HCI-CHs was prepared from 75 mg of ■ in the same manner as in Production Example 2.
Hydrolysis with COOH and decarboxylation yield 59.4n+g of (±)-pentyl itaconic acid (1). Yield 55
．． 7% El-MS II/Z 200 (M (611,br
s, ), 1.80 (2N, *).

3.46 (III, tt J=7Hz), 5.81
(ill, s), 6.46 (ill, s).

Ko).

30.5(t), 31.5(t), 46.6(
d).

129.8(t), 137.4(s), 172
．． 0(s), 179.9(s) Production Example 5 (±)-Hebutylitaconic acid [Phase] ■
■ [Stock] (±)-hebutyl itaconic acid 2.58 g of ■ and 2.71 g of n-heptyl iodide were alkylated in the same manner as in Production Example 1, and then concentrated HCl
When CH3COOHte is hydrolyzed and decarboxylated, 267
．． 3m4H of [phase] (±)-hebutyl itaconic acid is obtained. Yield 11.8% CI-MS mHz 229 (M÷1)'' (kfjL
brs:), 3.45 (IH, t, J-7Hz)
, 5.82 (IH,s), 6.48 (IH.

s), 11.60 (2H, s) Production Example 6 (±) Octylitaconic acid O■
■ [ ■ (±)-Octyl itaconic acid 2.56 g of ■ and 2.9 g of n-octyl iodide were alkylated in the same manner as in Production Example 2, and then concentrated H
Hydrolysis with Cl - CHs COOH and decarboxylation yield 267.3B [phase] (±)-octylitaconic acid. Yield 11.8% CI-MS mHz 243 (M+1)” (1211
, brs, ), 3.45 (LH, t+ J-7H2),
5.83 (III, s), 6.48 (III.

s), 11.0 (2H, s) Production Example 7 n-hexylidenesuccinic acid [Phase] 0
East ■ n-hexylidenesuccinic acid 1, 97 g of t-butoxypotassium was mixed with 16 mg of t-
Add to butanol, heat to reflux, and add 1.6
A mixture of g of n-caprylaldehyde and 3.48 g of diethyl succinate is slowly added dropwise and refluxed for 15 hours. The solvent was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with ether using p113. The organic layer is extracted with saturated aqueous sodium bicarbonate solution. The aqueous layer was adjusted to p113 and extracted with ether. After drying the ether extract over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a monoester [phase] of 1.4417
g is obtained.

Of these, 0.5g of ■ is added to 5ml of acetic acid and 1m7 of concentrated hydrochloric acid! Reflux for 15 hours. Add 50 mg of water to the reaction solution and extract with ethyl acetate. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 166.5 mg of [phase] n-hexylidenesuccinic acid. Yield 15% CI-MS mHz 20HM+1)'' (6H, m)
, 2.18 (2H, m), 3.28 (2) 1. s
), 5.70(28,s), 6.86(IH,t,
J = 8 Hz) The itaconic acid derivative according to the present invention is effective for use in each stage of crop seeds, seedlings, and adults, such as soaking treatment of rice and wheat seeds, treatment of seedlings of vegetables, rice, and corn, It can be widely applied to the treatment of mature fruit trees. (Thus, the compounds according to the present invention include, for example, rice, wheat, corn, potato, sweet potato, soybean, adzuki bean, fava bean, beet, tea, tobacco, konnyaku, tomato, eggplant,
It is applied to various crops such as vegetables such as cucurbits and carrots, ornamental plants such as chrysanthemums, carnations, and lilies, and fruit trees such as citrus fruits, apples, pears, and grapes.

The compounds according to the present invention are generally used in the form of formulations such as emulsions, wettable powders, powders, and granules, just like general agricultural chemicals. Next, a detailed explanation will be given by giving examples of formulations.

1. Emulsion: 15 parts of octyl itaconic acid and 795 parts of Kizilol, 2 parts of polyoxyethylene alkyl ether as an emulsifier,
1.5 parts of polyoxyethylene sorbitan alkylate,
Add 2 parts of alkylbenzene sulfonate and mix to obtain an emulsion emulsifiable in water.

2. Add 20 parts of butyl itaconic acid to 10 parts of wettable powder white carbon and stir. Further, 6 parts of powdered sodium alkyl ether sulfate and 2 parts of sodium tripolyphosphate are added as a dispersant, and mixed with 62 parts of kaolin as a grinding aid.The whole is stirred uniformly and then ground to obtain a hydratable into a suspension preparation.

3. Powder 1 part of propyl itaconic acid and 2 parts of white carbon are thoroughly mixed and pulverized, and this is added to 97 parts of talc with stirring, and the whole is further pulverized to obtain a powder preparation.

Next, the plant growth regulator of the present invention will be explained in more detail with reference to Examples.

Example 1. Rice seed rooting test test method Five germinated seeds of paddy rice (variety: Sasanishiki) with a diameter of 2.5
10 cm of the compound according to the present invention in a tube bottle with a height of 6 cm.
% emulsion was added to solutions 1C and 1C of each concentration, covered with aluminum foil, and cultured for 7 days at 30°C under artificial light and 4,000 lux, and the plant height and number of pairs were investigated. .

Results (numbers in the table indicate average values for 5 plants) While untreated rice produced weak rice seedlings with a small number of phases, treatment with the compound group of the present invention resulted in healthy rice seedlings. can get.

Example 2. Test method for promoting flowering and harvesting of eggplant The following tests were conducted using 10% permanant of each of the compounds according to the present invention.

A predetermined concentration solution was sufficiently sprayed on the stems and leaves of 10 eggplant seedlings in each group at the 8-leaf stage, and the flowering date and yield were observed.

Results The first flowering date and the first fruit harvesting date were compared with the untreated plot, and the difference in the number of days for promotion was expressed in days. In addition, the yield in the second month after spraying was expressed as a percentage.

Example 3. Test method for increasing yield of green pepper The following tests were conducted using 10% emulsions of each of the compounds according to the present invention.

For 10 plants in each section of green pepper seedlings at the leaf stage of 10 to 12 leaves,
A chemical solution of a predetermined concentration was sufficiently sprayed on the stems and leaves, and the final yield was tested.

Results Table 3 Example 4. Test method for soybean yield increase test The following tests were conducted using 10% emulsions of each of the compounds according to the present invention.

When soybean flowers bloom, a chemical solution with a concentration of 30 ppm is applied twice at one week intervals.
Sprayed in sufficient quantity over multiple times. The yield was investigated and the results shown in the table below were obtained.

Results Example 5. Test method for promoting the rooting of turf grass The following test was conducted using each 10% permanant agent of the compound according to the present invention.

Apply chemical solution of each concentration to 2 replicates of 0.5 d in each section of pencross and bent grass from October to November.
Sufficient amounts were sprayed over several times, and at the end of March of the following year, bentgrass mines, stem and leaf types, and number of buds were investigated.

Results Example 61 Seed Soaking Treatment Test Test Method The following tests were carried out using 10% emulsions of each of the compounds according to the invention.

(Test crop) Chinese cabbage Variety: Disease resistant 60 day corn Variety: Delicious 90 cucumber
Variety: Wasumi Hanshiro Seeds of each of the above crops were used to prepare a solution containing a test compound at a predetermined concentration, and immersed for a certain period of time.

(Soaking time) Chinese cabbage, Kirari, 24-hour corn, sown after 48-hour soaking, Kirari, corn, after 7 days.
The Chinese cabbage was dug up after 20, 30, and 45 days, the total type and seed type were determined, and the T/R ratio (all types/mines x100) was calculated. In addition, for the whole type and species type, the weight per individual is ff1
g.

Results Effects of the Invention The plant growth regulator of the present invention exhibits extremely excellent effects on promoting rooting, flowering and harvesting, and can be safely used on various crops without causing any phytotoxicity. I can do it.

Claims (1)

[Claims] Alkyl itaconic acid having an alkyl group having 1 to 8 carbon atoms (excluding 6) in the side chain, an alkyl monoester of the above alkyl itaconic acid having an alkyl group having 1 to 5 carbon atoms,
One or more compounds selected from the group consisting of the exomethylene of itaconic acid having an alkyl group having 1 to 8 carbon atoms in the side chain and the alkyl monoester of the exomethylene of the above-mentioned itaconic acid having an alkyl group having 1 to 5 carbon atoms. A plant growth regulator as an active ingredient.