JPS5933593B2 - Derivatives of hydantoin or thiohydantoin - Google Patents

Description

Detailed Description of the Invention The present invention is based on the general formula (CH2□-R'-Ni (wherein, X represents O or S, n represents 3 or 4, and when X is O, R is group, a phenyl group optionally substituted with at least one nitro, halogen, lower alkyl, lower alkoxy, trifluoromethyl, chlorobenzyloxy; when X is s, R is a naphthyl group, , trifluoromethyl, or a phenyl group optionally substituted with chlorobenzyloxy).

The present inventors have investigated the herbicidal activity of 3-substituted hydantoins, and this time, a new compound having alkylene groups at the 1st and 5th positions of the hydantoin structure as shown in the above formula has been found to have a herbicidal and fungicidal effect. It has been found that the compound has desirable properties such as enhanced compatibility with plants (in other words, an appropriate balance of ribophilicity/hydrophilicity), and an increased tendency for detoxification after application.

The main parts of the structure of the above compound are proline and pipecolic acid. Proline, especially L-proline, is an essential amino acid for humans and is abundant in nature. L-pipecolic acid is also known to be a lysine metabolite, and its presence is known in apples, kidney beans, and other plants. Therefore, the compound of the present invention solves the problem under environmental conditions when proline or pipecolic acid and isothiocyanate are heated under reflux in a suitable solvent (methanol, ethanol, isopropyl ether, THF.DMFl benzene, toluene, etc.). It can be obtained in high yield by adding acid 3. Purification is the same as for X-0. (In the formula, R has the same meaning as described above.) Proline has a large potency depending on its synthesis method.

The present invention was completed based on this knowledge. The hydantoin derivative of the present invention can be obtained, for example, by reacting proline or pipecolic acid with an isocyanate or isothiocyanate in a conventional manner.

The reaction formula for this is as follows. (1) In the case of X-0 (wherein R has the same meaning as described above).

) Salts of proline or pipecolic acid in water and solvent 2 (
(benzene, chlorobenzene, ether, DMF, etc.) and react with isocyanate to obtain hydantoic acid (A). Then this compound (
A) is heated in the presence of an acid (hydrochloric acid, sulfuric acid, etc.) (80-15
``C) causes dehydration and cyclization. The produced hydantoin is purified by methods such as recrystallization, chromatography, and distillation. (11) In the case of X-S, p was dissolved in 20 ml of chlorobenzene while stirring in a solution of 1.947 (0.015 mol) of pipecolic acid, 0.6 y (0.015 mol) of sodium hydroxide, and 25 ml of water.
-Chlorphenyl isocyanate 2.307 (0.01
5 mol) was added.

After 4 hours, the reaction solution was extracted twice with 20 ml of ether, and the aqueous layer was made acidic by adding concentrated hydrochloric acid to precipitate a colorless solid.

This suspension was heated under reflux for 1 hour while stirring, and then cooled to room temperature. The precipitate was collected ▲, washed with water, and then recrystallized from isopropanol to obtain the above 3-(pchlorophenyl)-1.
・5-tetramethylenehydantoin 3,227 (yield 8
1.1%). Melting point 157-8℃ o Pipecolic acid 1
．． 297 (0.01 mol), sodium hydroxide 0.47
(0.01 mol), p-chlorobenzyloxyphenyl isocyanate 2.607 (0.01 mol) in a solution of 20 ml of water.
01 mol) dissolved in DMFIOml was added with stirring.

After 4 hours, concentrated hydrochloric acid was added to the reaction solution to make it acidic, and the mixture was heated to reflux while stirring for 2 hours. After cooling, a lot of precipitate was collected, washed with water, and recrystallized from DMF-ethanol. The above 3-[4-(p-chlorobenzyloxy)phenyl]-1,5-tetramethylenehydantoin 2.937 (
A yield of 79.0% was obtained.

Melting point: 152-3°C. Next, specific examples of the hydantoin compounds according to the present invention are shown in Table 1.

In the table, the elemental analysis values are shown as calculated values in the upper row and actually measured values in the lower row.

The compounds obtained according to the present invention have excellent herbicidal and fungicidal effects as shown in the following test examples, and are expected to be used as agricultural chemicals.

In addition, when using the compound of the present invention as an agricultural chemical, it is preferable to use a carrier as shown in Japanese Patent Application No. 50-16211. Test Example 1 Flooded Soil Treatment Test Paddy soil was placed in a Wagner pot of 1/5000 are. , fill the surface layer with soil mixed with seeds of Japanese wild grass and Kikashigusa, and then transplant rice seedlings (3-leaf stage) to raise the water depth to 3 cm.
After 5 days, the active ingredient amount was 107 and 30% per R.
It was sprayed uniformly on the water surface so that the concentration was 7.

A water reduction depth of 3 CTn/day was applied for 3 days after the treatment, and no water leakage treatment was performed after that, and the herbicidal power and effect on paddy rice seedlings were investigated 25 days after the chemical was sprayed. The results are shown in Table 2. The evaluation criteria are as follows. Test Example 2 Upland Soil Treatment Fill a 1/5000 are Wagner pot with upland soil, sow wheat, soybean, and corn at a depth of 2 to 3 crfL covered with soil, and then sow the seeds of crabgrass, ... and yellowtail on the soil surface, and then do the following. A diluted solution of a hydrating powder of the compound black shown in Table 3 with water was uniformly sprayed on the soil surface so that the active ingredient amount was 107 and 307 per are.

25 days after the treatment, its herbicidal activity was investigated on crabgrass and leafminer. At the same time, we investigated phytotoxicity of wheat, soybeans, and corn. The evaluation was based on the same criteria as in Test Example 1. The results are shown in Table 3. Test Example 3 Filled with field soil in a Wagner pot with a size of 1/5000 are, barnyard grass, crabgrass, and radish were sown and their growth was controlled, and an emulsion of the compound black shown in Table 4 below was diluted with water. Diluted solutions with active ingredient concentrations of 0.1% and 0.3% were sprayed onto foliage using a small pressurized sprayer at a volume of 101 per area.

Twenty days after the treatment, an investigation was conducted according to the herbicidal power criteria of Test Example 1.

The results are shown in Table 4. The growth levels of the test plants at the time of spraying were as follows: barnyard grass and crabgrass were at the 2nd to 3rd leaf stage, and radish was at the first true leaf stage, and the radish in this case was used as a substitute for broad-leaved weeds. Test 1 Test Example 4 A suspension of the black compound shown in Table 5 below (500p
pm) was sprayed on a turntable to green beans grown in a pot with a diameter of 9 cm and at the stage of true leaf development.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents O or S, n represents 3 or 4, and when X is O, R is a naphthyl group, at least Represents a phenyl group optionally substituted with one nitro, halogen, lower alkyl, lower alkoxy, trifluoromethyl, or chlorobenzyloxy, and when X is S, R is a naphthyl group, at least one nitro, trifluoro 1,5-alkylene-hydantoin or 1,5-alkylene-2-thiohydantoin derivative represented by a phenyl group optionally substituted with methyl or chlorobenzyloxy.