JPS5837281B2 - Shinkinadjiyosouzai - Google Patents

Description

[Detailed Description of the Invention] Is the present invention a general formula? In the formula, R and R represent a lower alkyl group, and R2 represents a lower alkenyl group.

) as an active ingredient.

The object of the present invention is to obtain these compounds industrially advantageously and to provide a simple and highly effective herbicide.

The inventors discovered a number of 2-acyl-3-hydroxy-2
- Cyclohexen-1-one derivatives have been synthesized and biological tests have been conducted. By reacting the compounds with 〇-lower alkenyl hydroxyamine, a new compound [■] (in the formula, R1R1 and R2 are Compounds (III) and (IV) identical to those shown are tautomers.

) was obtained in good yield.

The present inventors have found that the compound represented by the general formula CI) can be industrially advantageously obtained by further reacting the compound CII) with terephthalic acid dichloride, and that the compounds can be applied to both soil treatment and foliar spraying on Psyllium annuus.
It has an extremely excellent herbicidal effect on regular weeds such as sparrowweed, crabgrass, and purslane, and is said to be almost harmless to leguminous crops such as azuki beans, soybeans, and sugar beet, which are susceptible to chemical damage caused by many other herbicides. After discovering that it has selectivity and conducting further biological and physical research, the present invention was completed.

A herbicide containing a 4-acetoxy-6-methyl-α-pyrone derivative having an (N-alkoxy or alkenyloxy) acetimidoyl group as an active ingredient is known from Patent Application Publication No. 1983-30533. One of the drawbacks of this herbicide is that a considerably large amount of the herbicide is required in order to completely kill off the above-mentioned weeds.

Surprisingly, the compounds of the present invention exhibit sufficient herbicidal effects even at lower doses than known compounds.

Furthermore, the compounds of the present invention exhibit excellent herbicidal efficacy against weeds even when treated at any growth period, whether before or after germination.

The compound of the present invention has no effect on broad-leaved crops such as radish, adzuki beans, soybeans, peas, spinach, beets, etc., even at a dose that completely kills the weed grasshopper, which is a weed belonging to the Physcomitraceae family, when sprayed on foliage. In addition, even at a dose that completely inhibits the germination of crabgrass in pre-emergence soil treatment, there is no effect on the seeds of broad-leaved crops, indicating that herbicides are extremely safe against damage caused by herbicides on broad-leaved crops. Its application is also very wide in terms of application time, application location and application concentration.

Furthermore, the compounds of the present invention do not necessarily cause residual toxicity in soil or plants, or acute toxicity to animals, fish, etc., and can be used safely.

In producing the compound of the present invention, the compound represented by the general formula (ID) is dissolved in a suitable solvent, and an alkali such as caustic soda or caustic potash is added to form an alkali metal salt.

This is once separated from the reaction mixture or reacted as it is with terephthalic acid dichloride.

Common organic solvents such as acetone, ether, alcohol, benzene, toluene, chloroform, and ethyl acetate are used as the reaction solvent, and the reaction temperature is from -20°C to the boiling point of the solvent used, preferably at a temperature below room temperature. .

After a reaction time of about 15 minutes to 3 hours, if necessary, replace the solvent, wash with alkali, then wash with water, dry, and distill off the solvent under reduced pressure. A compound of the present invention represented by the general formula CI,) is obtained.

In addition, the product is purified by recrystallization or column chromatography, and then subjected to elemental analysis, IR spectrum, NMR analysis, etc.
The structure was confirmed by analysis results such as spectra.

Compound [■], which is a raw material for the compound of the present invention, is produced, for example, according to the following reaction formula.

(In the formula, R1, R2 and R have the same meanings as shown above.

) Next, the method of the present invention will be explained with reference to Examples.

Example 1 2-(1-N-allyloxyaminobutylidene)-4-
Methoxycarbonyl-5,5-dimethynorecyclohexane-1,3-dione (n"4-."1.5063) 10
f! was dissolved in 80 ml of acetone.

To this was added 1.23 f of caustic soda dissolved in 8 ml of water, and then, under cooling, a solution of 3.142 ml of terephthalic acid dichloride dissolved in 30 ml of acetone was added dropwise.

*After stirring at room temperature for 1 hour, the reaction mixture was filtered through a door to remove precipitates.

Acetone was distilled off, and the residue was extracted with chloroform.

The chlorophonolem layer was washed with 5% aqueous sodium hydroxide solution and then with water.

After drying the chloroform layer with Glauber's salt, the chlorophonolem was distilled off to obtain 8.4 fl of a viscous oil with a weight of 1.5 2 1 5.
I got it.

As a result of redundancy analysis, this product was bis(2) having the following structural formula.
-(N-7!J-ruoxybutynoreimitoinore) = 4-
It was confirmed that it was methoxycarbonyl-5,5-dimethynole-3-oxo-1-cyclohexene=1-ynole]terephthalate.

Example 2 BisC2-(N-allyloxyglopionimidoyl)
-4-methoxycarbonyl-5-5-dimethyl-3-oxo-1-cyclohexen-1-yl]terephthalate 2-(1-N-allyloxypropyritene)-4-methoxycarbonyl-5,5-dimethylcyclohexane-1
-3-dione 2.5? A solution of 0.32 f of caustic soda dissolved in 1 yrtl of water was added to a solution of 0.32 f of caustic soda dissolved in 30 ml of acetone, and the mixture was stirred for about 30 minutes.

Then, under cooling, terephthalic acid dichloride? 0.81
After adding, the mixture was stirred at room temperature for 2 hours.

After filtering the reaction mixture and removing the precipitate, acetone was distilled off and the residue was extracted with chloroform.

The chloroform layer was washed with 5% aqueous sodium hydroxide solution and then with water.

After drying the chloroform layer with MgSO, the chloroform was distilled off to obtain the desired product as a viscous oil.

ndo 1.5282 Next, Table 1 shows examples of compounds produced by the method of the present invention.

The herbicide of the present invention contains one or more of the compounds represented by the above general formula [■] as an active ingredient.

The active ingredient compound is generally used by mixing an appropriate amount with a carrier and preparing it in the form of a wettable powder, emulsion, powder, granule, or the like.

Examples of solid carriers include Merck, bentonite, clay, and carbon dioxide, and examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, dimethylformamide, and the like.

If necessary, a surfactant may be added in order to obtain a uniform and stable form in these preparations.

The concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the formulation mentioned above, but for example,
5 to 80% in wettable powders, preferably 10 to 60%
: 5 to 70% in emulsions, preferably 20 to 60%
:0.5-30% for powders and granules, preferably 1
A concentration of ~10% is used.

The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion; powders and granules can be sprayed or mixed into the soil before weed germination; Alternatively, foliar spray treatment is applied after weed germination.

When actually applying the herbicide of the present invention, an appropriate amount of the active ingredient is applied in an amount of 101 or more, preferably 251 or more per 10 ares.

In addition, the herbicide of the present invention is a known bactericide, insecticide, acaricide,
It can also be used in combination with herbicides, plant growth regulators, etc.

In particular, when used in combination with a herbicide, not only the amount of chemicals used can be reduced and labor savings can be achieved, but even greater effects can be expected due to the synergistic action of both chemicals.

Chemicals suitable for use in combination with the herbicide of the present invention include triazine herbicides such as simazine, propazine and promethrin, carbamate herbicides such as betanal, urea herbicides such as linuron and tribunyl, and bentazone. Examples include heterocyclic herbicides such as pyrazone agents, pyrazone agents, and renacil agents.

Next, some examples regarding the herbicide of the present invention will be shown, but the active ingredient compounds, additives, and addition ratios are not limited to these examples and can be varied within a wide range.

Example 3 Emulsion Compound of Example 1 40 parts xylene
35 parts dimethylformamide
15 parts polyoxyethylene phenyl ether At least 10 parts were mixed and dissolved to obtain an emulsion containing 40% of the active ingredient.

Example 4 Granules 7 parts, 38 parts, 38 parts, 10 parts or more of the compound talcum clay pentonite alkyl sulfate in Example 7 are mixed uniformly and pulverized finely, and the resulting powder has a diameter of 0.5 to 1.
The mixture was granulated into granules containing 7% of the active ingredient.

Next, test examples regarding the effect of the herbicide of the present invention will be shown.

Test Example 1 Flooded soil treatment test A 60 ca pot is filled with soil, and about 6 millet seeds are placed on top of it.
After sowing 0 seeds and lightly covering the soil, the soil was flooded with water to the extent that the soil surface was moistened.

10 cc of a chemical solution of a predetermined concentration prepared by diluting an emulsion of each test compound with water was poured into the pot.

Three weeks later, the growth status of the barnyard grass was investigated.

The growth status was expressed on a scale of 0 to 506, with 0 representing the same level of growth as without treatment and 5 representing withering or non-germination, and the results shown in Table 2 were obtained.

Test Example 2 One-leaf stage treatment A 60 ca pot was filled with soil, and approximately 50 grains of Japanese millet were sown thereon, covered lightly with soil, and grown in a greenhouse.

When the Japanese millet grows to the one-leaf stage, the water depth is 3 cTL.
A chemical solution of a predetermined concentration prepared by diluting an emulsion of each compound with water was poured into each pot.

Two weeks later, the growth status of the Japanese millet was investigated.

Expressing the growth status according to the same criteria as Test Example 1,
The results shown in Table 3 were obtained.

Test Example 3 Stalk and Leaf Treatment Test A pot was filled with soil, and seeds of crabgrass were sown, lightly covered with soil, and grown in a greenhouse.

When the crabgrass grows at the 2- to 4-leaf stage, a chemical solution of a prescribed concentration prepared by diluting each test compound emulsion with water is added to 1007
The foliage was sprayed at a rate of /10a.

Three weeks later, the growth status of the crabgrass was investigated, and the growth status was expressed according to the same criteria as Test Example 1, and the results shown in Table 4 were obtained.

Test Example 4 Soil surface treatment test Soil mixed with crabgrass seeds was packed into a honopot with a surface area of 100 cm and grown in a greenhouse.

Before germination of crabgrass, 5 cc of a chemical solution of a predetermined concentration prepared by diluting an emulsion of each test compound with water was sprayed onto the soil surface, and 21 days later, the growth state of crabgrass was investigated.

Expressing the growth state according to the same criteria as Test Example 1,
The results shown in Table 5 were obtained.

Claims (1)

[Scope of Claims] 1. Containing as an active ingredient one or more compounds represented by the general formula (in which R and R1 represent a lower alkyl group and R2 represents a lower alkenyl group). herbicide.