JPH08198862A - Methyl crotonate derivative and herbicide containing the same as an effective ingredient - Google Patents

Abstract

PURPOSE: To obtain a new methyl crotonate derivative, an effective ingredient in a herbicide useful for controlling weeds harmful for producing farm products such as orange, tea, etc., for which weeds growing is harmful and unwanted from the standpoint of scenery, and expressing herbicidal activities against weeds such as Eclipta alka Hassk., Amaranthus retroflexus L., etc. CONSTITUTION: This methyl crotonate derivative is expressed by the formula. A compound of the formula can be obtained by dehydrating (A) N-acetylvaline and (B) a monoene-alcohol. In the reaction, it is preferable to use 0.5-10 times mole, preferably 1-5 times mole of the component B against the component A and 1-5 times mole, preferably 1-2 times mole, of a dehydrating agent (preferably dicyclohexylcarbodiimide) against the component A. It is preferable to carry out the reaction at 10-50 deg.C for 3-5 hours.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a methyl crotonic acid derivative and a herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art To date, many physiologically active natural products having herbicidal activity have been found in plants, and some of them have been put to practical use as herbicides. Eg tetrahedron
Letters, 23, 4469-4472 (198
Altern causing pear black spot disease disclosed in 2)
toxin AK-produced by aria kikuchiana
It is known that toxin I and II have a hydroxyepoxytricarboxylic acid in the molecule and necrosis the cell tissues of plants to cause the plants to die. However, these natural products are not suitable for large-scale synthesis due to their complicated chemical structure, and their herbicidal activity in practice is weak, so that they have not been put into practical use.

[0003]

DISCLOSURE OF THE INVENTION The methyl crotonic acid derivative of the present invention is a novel compound not described in the literature and is represented by the following formula (1).

[0004]

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The compound of the present invention represented by the above formula (1) is a compound useful as a herbicide for agricultural and horticultural use, as shown below.

The compound of the present invention is produced according to the following reaction formula.

[0007]

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That is, the compound of the present invention is produced by dehydrating N-acetylvaline (2) and monoene alcohol (3). This reaction can be carried out in a solvent, for example, using a suitable dehydrating agent. As the dehydrating agent, for example, dicyclohexylcarbodiimide (DC
C) is preferably used, and examples of the solvent include ethers such as diethyl ether, dibutyl ether and tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and aromatics such as benzene, toluene and xylene. Hydrocarbons, ethyl acetate and the like can be mentioned.

In the above reaction, the ratio of the compound (2) to the compound (3) used is not particularly limited and may be appropriately selected from a wide range. Usually, the latter is 0.5 to 0.5 with respect to the former. It is advisable to use a 10-fold molar amount, preferably a 1- to 5-fold molar amount. The dehydrating agent is usually used in an amount of 1 to 5 times, preferably 1 to 2 times the molar amount of the compound (2).

A catalyst may be added to the reaction system of the above reaction. Examples of the catalyst include tertiary amines such as 4-dimethylaminopyridine and triethylamine. The amount of the catalyst used is 0.01 per mol of the dehydrating agent.
It may be about 0.5 mol.

The above-mentioned reaction can be carried out at room temperature, under heating or under cooling, but it usually proceeds suitably under a temperature condition of about 0 to 100 ° C, preferably 10 to 50 ° C, and generally 3 to 5 The reaction is completed in about time.

In the above reaction, the compound (2) and the compound (3) used as starting materials are both known compounds, for example, Heterocycles, 29 (6),
It is easily manufactured by the method described in 1023-1027 (1989). That is, the compound (2) is produced by reacting commercially available valine with acetic anhydride in the presence of sodium hydroxide, and the compound (3) is produced from D-fructose by an 8-step reaction.

The reaction product obtained by the above reaction can be separated by an ordinary separation means such as a solvent extraction method, a solvent dilution method, a recrystallization method,
It can be isolated and purified by a column chromatography method or the like, but it is preferably partially purified using silica gel column chromatography and further purified by normal phase high performance liquid chromatography to obtain the target compound of the present invention in high purity. You can

The compound of the present invention shows herbicidal activity against weeds such as Takasaburo, Aobiyu, Kusanem, Astragalus chinensis, Polygonum japonica, Artemisia angustifolium, Rumex communis, Azena, Rhododendron japonicus, Novie, Meshishiba, Ohashiba, Cyperaceae, and the like. It is useful for the production of agricultural products such as mandarin oranges, apples, soybeans, corn, tea, paddy rice and the like, which are harmful to the growth of plants, and for controlling weeds that are harmful to the landscape.

When the compound of the present invention is applied as a herbicide, the compound of the present invention may be used as it is, but generally, it is used as a mixture with an auxiliary agent which is usually used in the formulation of agricultural chemicals. Although the dosage form is not particularly limited,
The form of powders, emulsions, wettable powders, flowables and granules is preferred. As the auxiliary agent, those usually used in this field can be widely used, for example, diatomaceous earth, kaolin, clay, bentonite, white carbon, extenders such as talc, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, sodium alkylbenzene sulfonate, sodium lignin sulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate,
Surfactants such as salts of naphthalene sulfonic acid formalin condensate, and organic solvents such as benzene, toluene, xylene, acetone, cyclohexanone, methanol, ethanol, isopropyl alcohol, dioxane, dimethylformamide, dimethylsulfoxide, carbon tetrachloride and the like.

The amount of the compound of the present invention to be incorporated in the herbicide of the present invention is not particularly limited, but the active ingredient is usually about 0.1 to 90% by weight, preferably about 5 to 70% by weight. It is preferable to appropriately add the above-mentioned auxiliary agent to

In using the herbicide of the present invention, it may be sprayed as it is without dilution, or 500-1.
You may dilute about 0000 times and spray. The appropriate application amount varies depending on the drug form, application method, application time, type of target crop, weather conditions and soil conditions that are likely to affect the herbicidal effect, etc., but cannot be generally stated, but usually the amount of the active ingredient is 50 to 1 are. About 3000g, preferably 50-400
It is recommended to spray so that it is about g.

[0018]

EXAMPLES The present invention will be further clarified with reference to production examples, formulation examples and test examples below.

Production Example 1 (4R, 5S) methyl-4-hydroxy-5,6-epoxy-5-methylhexe-2 (E) -enoate 7 g
In a solution of (40 mmol) in 200 ml of anhydrous ethyl acetate, 6.4 g (40 mmol) of N-acetylvaline, 8.1 g (40 mmol) of dicyclohexylcarbodiamide and 0.49 g (4.0 mmol) of 4-dimethylaminopyridine were added. The mixture was added sequentially and stirred at room temperature for 4 hours. After removing the precipitate by suction filtration, the solvent was distilled off under reduced pressure.

The reaction product was subjected to silica gel column chromatography (developing solvent; chloroform: ethyl acetate = 5).
Partial purification with 0: 1), and then high performance liquid chromatography (column; Cosmosil 5SL, mobile phase; 20% n)
-Hexane, 1% tetrahydrofuran and 0.1% ethanol in ethyl acetate, flow rate; 3 ml / min) purification was performed to obtain two target diastereomers eluting with retention times of 12.4 minutes and 15.2 minutes, respectively. 4.6 as an oil
g (1a) and 4.3 g (1b) were obtained. Specific diopter of each diastereomer, NMR spectrum (CDCl
₃ ) and mass spectrum (EI-MS) are as follows.

(1a): Compound of the formula (1) in which 2'-position is R-form [α] _D ¹⁶ = + 4.2 ° (c = 1, CDCl ₃ ) ¹ H-NMR δ (ppm); 93 (3H, d, J
= 6.2 Hz), 0.98 (3H, d, J = 6.2H)
z), 1.35 (3H, s), 2.05 (3H, s),
2.1-2.4 (1H, m), 2.62 (1H, d, J
= 4.6 Hz), 2.80 (1H, d, J = 4.6H)
z), 3.77 (3H, s), 4.62 (1H, dd,
J = 7.7 Hz, J = 3.9 Hz), 5.28 (1H,
dd, J = 5.1 Hz, J = 2.0 Hz), 6.12
(1H, dd, J = 15.4Hz, J = 2.0Hz),
6.89 (1H, dd, J = 15.4Hz, J = 5.1
Hz) EI-MS (70 eV) m / z; 313 (M ⁺ ), 25
4,228,172,170,155,142.

(1b): Compound of formula (1) in which 2'-position is S-form [α] _D ¹⁶ = + 14.2 ° (c = 1, CDCl ₃ ) ¹ H-NMR δ (ppm); 95 (3H, d, J
= 5.9 Hz), 0.98 (3H, d, J = 5.9H)
z), 1.35 (3H, s), 2.07 (3H, s),
2.0-2.4 (1H, m), 2.62 (1H, d, J
= 4.6 Hz), 2.80 (1H, d, J = 4.6H)
z), 3.79 (3H, s), 4.63 (1H, dd,
J = 7.7 Hz, J = 3.9 Hz), 5.25 (1H,
dd, J = 5.1 Hz, J = 2.0 Hz), 6.09
(1H, dd, J = 15.4Hz, J = 2.0Hz),
6.88 (1H, dd, J = 15.4Hz, J = 5.1
Hz) EI-MS (70 eV) m / z; 313 (M ⁺ ), 25
4,228,172,170,155,142.

Formulation Example 1 (30% emulsion) (parts by weight) Compound (1a) of Production Example 1 30 Polyoxyethylene nonylphenyl ether 10 Dimethylformamide 20 Xylene 40 Formulation Example 2 (50% wettable powder) of Production Example 1 Compound (1b) 50 Sodium lignin sulfonate 1 Sodium dodecylbenzene sulfonate 4 Clay 45 Formulation example 3 (10% granules) Compound (1a) of Production Example 1 10 Sodium lignin sulfonate 0.5 Sodium dodecyl benzene sulfonate 2 Diatomaceous earth 27.5 Bentonite 60 In the case of an emulsion, they can be uniformly mixed and dissolved, and in the case of a wettable powder, each component can be uniformly mixed and pulverized to obtain them. In the case of granules, the respective components are well pulverized and mixed, water is added and sufficiently kneaded, then granulated, then finely cut into granules, and dried.

Test Example 1 (Stem and Leaf Treatment Test) A sterilized alluvial soil was placed in a Wagner pot of 1 / 2000a, and seeds of the test plants shown in Table 1 were sown, and each plant had a substantially constant size (approximately 2). ~ 3 leaf stage), an emulsion containing the compound obtained in Production Example 1 as an active ingredient was prepared according to Formulation Example 1, and the active ingredient was diluted with water to 400 g / a, respectively. This was sprayed so that the entire surface of the foliage of the plant was wet evenly. Three weeks after spraying, the herbicidal activity against each plant was examined. Table 1 shows the results.
The herbicidal activity was evaluated by visual observation using an index in comparison with the untreated case according to the following criteria.

(Index) (Herbicidal activity) 0 No change 1 20% weeding 2 40% weeding 3 60% weeding 4 80% weeding 5 Complete death

[0026]

[Table 1]

Test Example 2 (Soil Treatment Test) A sterilized alluvial soil was put in a Wagner pot of 1 / 2000a, and seeds of test plants shown in Table 2 were sown to obtain about 0.5.
~ 1.0 cm was covered with soil. Next, a wettable powder containing the compound obtained in Production Example 1 as an active ingredient was prepared according to Formulation Example 2, and each active ingredient was diluted with water to 1000 g / a, and the soil surface was wetted uniformly. So that it was sprinkled. Three weeks after spraying, the herbicidal activity against each plant was examined. The results are shown in Table 2. The evaluation criteria are the same as in Test Example 1.

[0028]

[Table 2]

Test Example 3 (Flooding test) Paddy soil was placed in a Wagner pot of 1 / 5000a, and the soil containing the seeds of Novier, Porphyra chinensis, Azena, and Cyperaceae was added to the surface layer, and then 2 Leaf stage paddy rice seedlings were transplanted and the water depth was maintained at 3 cm. Then, a powder containing the compound obtained in Production Example 1 as an active ingredient was prepared according to Formulation Example 3, and the active ingredient was uniformly sprayed so as to be 500 g / a. Three weeks after spraying, the herbicidal activity against each plant was examined. Table 3 shows the results. The evaluation criteria are the same as in Test Example 1.

[0030]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tamio Ueno, 12 Kagaya Honen-in, Sakyo-ku, Kyoto City, Kyoto Prefecture (72) Inventor Yasumasa Kuwahara, Fukakusaikeno, Fukumi-ku, Kyoto City, Kyoto Prefecture

Claims (2)

[Claims] (1) Formula (1) A methyl crotonate derivative represented by. 2. A herbicide containing the methyl crotonate derivative according to claim 1 as an active ingredient.