JPH0583555B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to 9-phenylimino-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one derivatives useful as herbicides and herbicides containing these as active ingredients. It is related to. (Prior Art) In recent years, many herbicides have been developed and put into practical use, contributing to labor savings and improved productivity in agricultural work. As a herbicide having a heterocycle, oxadiazone [5-t-butyl-3-[2,4-
dichloro-5-isopropoxyphenyl)-1,
3,4-oxadiazolin-2-one] is widely used. When oxadiazone is used in paddy fields, it is likely to cause chemical damage, and furthermore, it cannot be expected to be effective in controlling perennials, especially irikawa. In addition, when used in the field, it has the disadvantage of low safety against crops such as corn and soybeans, and low herbicidal effect against difficult-to-control weeds such as Japanese fir tree and Japanese locust, as well as against weeds such as blueberry and whiteweed. It is desired that a herbicide that is further improved in these respects be developed. (Problems to be Solved by the Invention) In order to realize the above-mentioned desire, the present inventors have set the following conditions: (1) Effectiveness at extremely low doses; (2) Paddy field weeds and/or (3) Effective against perennial weeds and/or difficult-to-control weeds; (4) Effective when treated over a wide range of periods from germination to growth. The present invention was developed as a result of intensive research aimed at developing a herbicide that satisfies the following: (5) It has excellent residual efficacy and can be expected to have a stable effect; and (6) It is highly safe for useful crops. 9-Phenylimino-8-thia-1,6-diazabicyclo[4.3.0]nonane-
The present invention was completed by discovering that a 7-one derivative satisfies these needs. (Technical means for solving the problems) 9-phenylimino-8-thia-1 of the present invention,
The 6-diazabicyclo[4.3.0]nonan-7-one derivative has the general formula

[In the formula, X and Y represent a hydrogen atom or a halogen atom, and Z represents a group

[Formula] (where R represents a hydrogen atom or an alkyl group,
R ¹ represents an alkyl group, a cycloalkyl group, or an alkoxyalkyl group. However, when R is a methyl group, R ¹ represents an alkoxyalkyl group. ) is shown. In addition, Y and Z are groups

[Chemical formula] (Here, R ² represents a hydrogen atom or an alkyl group,
R ³ represents an alkyl group, an alkenyl group, or an alkynyl group. ) and can be bonded to the phenyl ring. ]. Next, representative examples of compounds represented by the general formula () are shown in Table 1. In addition, compound numbers are referred to in the following description. general formula

[ka]

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[Table] The compound of the present invention can be produced by the following method.

[Chemical formula] (In the above reaction formula, X, Y and Z are the same as above.) In this method, a compound represented by the general formula () and a compound represented by the general formula () are combined in the presence of a base. This is done by reacting with As the base, aliphatic tertiary amines such as trimethylamine and triethylamine, pyridine,
Aromatic tertiary amines such as picoline and quinoline or inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate can be used. Note that the above reaction is preferably performed in a solvent. Examples of solvents include chlorinated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride;
Ethers such as diethyl ether, tetrahydrofuran and dioxane, hydrocarbons such as n-hexane, benzene and toluene, aliphatic ketones such as acetone and methyl ethyl ketone, dimethyl sulfoxide, N,N-dimethylformamide, etc. can be used. . The above reaction is carried out at a temperature ranging from -20°C to the boiling point of the solvent and is completed in 1 to 7 hours. Next, the manufacturing method will be specifically explained with reference to Examples. Example 1 9-{4-chloro-2-fluoro-5-[1-
Production of (2-methoxyethoxycarbonyl)ethylthio]phenylimino}-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one 1,2-tetramethylene-1-
{4-chloro-2-fluoro-5-[1-(2-methoxyethoxycarbonyl)ethylthio]phenylaminothiocarbonyl}hydrazine 2.8g
(6 mmol), 1.2 g (15 mmol) of pyridine, and 20 ml of dichloromethane were added thereto, and a dichloromethane solution containing 0.8 g (8 mmol) of phosgene was added dropwise thereto while cooling with ice water. After the dropwise addition, the reaction mixture was further stirred at room temperature for 1 hour. After the reaction was completed, the reaction solution was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain a crude product. This crude product was purified by silica gel column chromatography to obtain 1.5 g (yield 50%) of a colorless candy-like substance. Refractive index n ²⁰ _D 1.5814. Example 2 9-(4-chloro-3-ethoxycarbonylmethylthiophenylimino)-8-thia-1,6
-Production of diazabicyclo[4.3.0]nonan-7-one 1,2-tetramethylene-1-
(4-chloro-3-ethoxycarbonylmethylthiophenylaminothiocarbonyl)hydrazine
1.2 g (3 mmol) of pyridine, 0.6 g (7 mmol) of pyridine, and 20 ml of dichloromethane were added thereto, and a dichloromethane solution containing 0.4 g (4 mmol) of phosgene was added dropwise thereto while cooling with ice water. After the dropwise addition, the reaction mixture was further stirred at room temperature for 1 hour. After the reaction was completed, the reaction solution was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain a crude product. This crude product was purified by silica gel column chromatography to obtain 0.6 g (yield: 47%) of a colorless candy-like substance. Refractive index n ²⁰ _D 1.6201 Example 3 9-(4-chloro-2-fluoro-5-propoxycarbonylmethylthiophenylimino)-
8-Thia-1,6-diazabicyclo [4.3.0]
Production of nonan-7-one Add 1,2-tetramethylene-1- to the reaction flask.
(4-chloro-2-fluoro-5-propoxycarbonylmethylthiophenylaminothiocarbonyl)hydrazine 1.6g (3.9mmol), pyridine 0.8g
(10 mmol) and 20 ml of dichloromethane were added thereto, and a dichloromethane solution containing 0.5 g (5 mmol) of phosgene was added dropwise thereto while cooling with ice water. After dripping,
The mixture was further stirred at room temperature for 1 hour to allow reaction. After the reaction was completed, the reaction solution was washed with water, dried over magnesium sulfate, and the solvent was distilled off to obtain a crude product. This crude product was purified by silica gel column chromatography to obtain 1.0 g (yield 59%) of a colorless candy-like substance. Refractive index n ²⁰ _D 1.6040 Example 4 9-(4-propargyl-7-fluoro-2H-benzoxazine-3(4H)-one-6-ylimino)-8-thia-1,6-diazabicyclo[4.3.0 ] Production of nonan-7-one Add 1,2-tetramethylene-1- to the reaction flask.
(4-propargyl-7-fluoro-2H-benzoxazin-3(4H)-one-6-ylaminothiocarbonyl)hydrazine 0.8g (2mmol), pyridine
Add 0.6g (7mmol) and 20ml of dichloromethane, and while cooling with ice water, add 0.3g (3mmol) of phosgene.
A dichloromethane solution of was added dropwise. After the dropwise addition, the reaction mixture was further stirred at room temperature for 1 hour. After the reaction was completed, the reaction solution was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain a crude product. This crude product was purified by silica gel column chromatography to obtain 0.4 g of white crystals (yield: 46%). Melting point 162-165℃. Example 5 Preparation of 9-(4-chloro-2-fluoro-5-pentyloxycarbonylmethylthiophenylimino)-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one 1 in a reaction flask ,2-tetramethylene-1-
(4-chloro-2-fluoro-5-pentyloxycarbonylmethylthiophenylaminothiocarbonyl)hydrazine 1.6g (3.7mmol), pyridine
Add 0.8g (10mmol) and 20ml of dichloromethane, and while cooling with ice water, add 0.5g (5mmol) of phosgene.
A dichloromethane solution of was added dropwise. After the dropwise addition, the reaction mixture was further stirred at room temperature for 1 hour. After the reaction was completed, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product. This crude product was purified by silica gel column chromatography to obtain 1.0 g of white crystals (yield 59%). Melting point 39-41℃. Example 6 9-(4-chloro-3-butoxycarbonylmethylthiophenylimino)-8-thia-1,6
-Production of diazabicyclo[4.3.0]nonan-7-one 1,2-tetramethylene-1-
(4-chloro-3-butoxycarbonylmethylthiophenylaminothiocarbonyl)hydrazine
1.5 g (3.7 mmol) of pyridine, 0.8 g (10 mmol) of pyridine, and 20 ml of dichloromethane were added thereto, and a dichloromethane solution containing 0.5 g (5 mmol) of phosgene was added dropwise thereto while cooling with ice water. After the dropwise addition, the reaction mixture was further stirred at room temperature for 1 hour. After the reaction was completed, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product. This crude product was purified by silica gel column chromatography to produce white crystals.
0.8g (yield 50%) was obtained. Melting point 58-60℃. Further, the herbicide of the present invention contains a 9-phenylimino-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one derivative represented by the general formula () as an active ingredient. In order to use the compound of the present invention represented by the general formula () as a herbicide in rice fields, fields, orchards, non-agricultural lands, etc., it is preferable to use the active ingredient in an appropriate dosage form depending on the purpose. . Generally, the active ingredient is diluted with an inert liquid or solid carrier, a surfactant and other substances are added as necessary, and used in the form of a powder, wettable powder, emulsion, granule, or the like. Furthermore, the herbicide of the present invention may contain insecticides, fungicides,
It can also be used in combination with other herbicides, plant growth regulators, fertilizers, etc. Next, the formulation method will be specifically explained with reference to Examples. In the following examples, parts mean parts by weight. Example 7 Wettable powder 10 parts of Compound (1), 0.5 part of Emulgen (registered trademark of Kao Corporation) 810, 0.5 part of Demol (registered trademark of Kao Corporation) N, Kunilite (registered trademark of Kunimine Industries Co., Ltd.) Trademark) 201, 20 copies of Zeeklite (registered trademark of Zeeklite Co., Ltd.) CA
Mix and grind 69 parts to obtain a wettable powder. Example 8 Wettable powder 10 parts of Compound (2), 0.5 parts of Emulgen 810, 0.5 parts of Demol N, 20 parts of Kunilite 201, 5 parts of Carplex 80, and 64 parts of Sickleite CA were mixed and ground. Obtain a hydrating powder. Example 9 Emulsion To 30 parts of compound (3), 60 parts of an equal mixture of xylene and isophorone and 10 parts of the surfactant Solpol (registered trademark of Toho Chemical Industry Co., Ltd.) 800A were added, and the mixture was stirred well. to obtain an emulsion. Example 10 Granules: 10 parts of compound (4), 1 part of talc and bentonite.
80 parts of filler, 5 parts of white carbon, 5 parts of surfactant Solpol N800A mixed in the proportion of 3 parts
Add 10 parts of water to the mixture, mix well to make a paste, extrude it through a sieve hole with a diameter of 0.7 mm, dry it, and then cut it into lengths of 0.5 to 1 mm to obtain granules. (Effects of the Invention) The herbicide of the present invention is effective against the germination of annual weeds such as Japanese barnyard grass, Japanese cypress, Japanese cypress, Japanese azalea, Japanese azalea, and Japanese aphrodisiac, as well as perennial weeds such as bulrush, Japanese cypress, Japanese cypress, Japanese cypress, and other annual weeds that occur in rice fields. It exhibits excellent herbicidal effects at extremely low dosages over a wide range of growing seasons, and is highly safe for paddy rice. In addition, various weeds that cause problems in upland fields, such as broad-leaved weeds such as knotweed, blueberry, whiteweed, dogfish, mustard, Japanese fir, noasagao, and American hornwort, as well as cyperaceous weeds such as cyperus cyperus, barnyard grass, blackberry, and foxtail grass, etc. It exhibits a high herbicidal effect against grass weeds when treated with soil or foliage, and is also highly safe against upland rice, wheat, soybeans, corn, etc. Furthermore, the herbicide of the present invention has excellent residual efficacy, and thus exhibits stable effects over a long period of time in the field. It can also be used in orchards, pastures, lawns, non-agricultural lands, etc. Next, the effects of the herbicide of the present invention will be explained with reference to test examples. Test 1 (Herbicidal effect test by paddy soil treatment) A magnetic pot with a diameter of 10 cm was filled with paddy soil, and after plowing, seeds of Japanese millet, Japanese cypress, Japanese cypress, and bulrush were sown, and the pots were submerged in water to a depth of 3 cm. The next day, a wettable powder prepared according to Example 7 was diluted with water and dropped onto the water surface. The amount of application depends on the active ingredient.
It is 400g per 10 are. Thereafter, they were grown in a greenhouse, and 21 days after treatment, the herbicidal effect was investigated according to the criteria in Table 2. The results are shown in Table 3.

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[Table] Compounds 7-21 and 26-71 of the present invention also completely killed the test weeds. Test Example 2 (Herbicidal effect test by treating upland soil) Fill a plastic pot (surface area 120 cm ² ) with upland soil, sow seeds of Japanese barnyard grass, Japanese knotweed, Japanese knotweed, Japanese cypress, and Japanese cypress and cover with soil according to Example 7. Dilute the hydrating powder prepared with water and add 10
100 per are (active ingredient 400g per 10 are)
was evenly spread over the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 21 days, and the herbicidal effect was investigated according to the standards in Table 2. The results are shown in Tables 4 and 5.

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[Table] Test Example 3 (Herbicidal effect test by field soil stem and leaf treatment) Field soil was filled in a plastic pot (surface area 120 cm ² ), and seeds of Japanese millet, crabgrass, knotweed, blueberry, whiteberry, and cypress were sown.
The barnyard grass was grown in a greenhouse until it reached the three-leaf stage. At the three-leaf stage of barnyard grass, the hydrating agent prepared according to Example 7 was diluted with water, and 100 per 10 ares (400 g of active ingredient per 10 ares) was sprayed on the entire plant from above using a small sprayer. . After treatment, the plants were grown in a greenhouse for 21 days, and the herbicidal effect was investigated according to the standards in Table 2. The results are shown in Tables 6 and 7.

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[Table] Test Example 4 (Medical efficacy and toxicity test by paddy soil treatment) Paddy soil was filled in a 1/5000 are Wagner pot, and after watering and puddling, sprouted Urikawa tubers were buried in the soil surface layer, three individuals per pot. ,
Seeds of Helaomodaka were sown, and 2 plants of rice at the 2.5 leaf stage were transplanted at a transplant depth of 2 cm, and the water depth was 3 cm.
flooded to cm. The next day, a predetermined amount of the wettable powder prepared according to Example 7 was diluted with water and dropped onto the water surface. Thereafter, they were grown in a greenhouse, and on the 30th day of treatment, the herbicidal effect and phytotoxicity were investigated according to the standards in Table 2. The results are shown in Table 8.

[Table] Test example 5 (soybean selectivity test) Fill a plastic pot (surface area 120 cm ² ) with field soil, sow soybean, Japanese scallion, and Noassagao seeds, grow in a greenhouse for 14 days, and then use Example 7. Dilute the specified amount of the hydrating agent prepared in the same manner with water, and add 10
100 ml per area was sprayed on the entire foliage from above the plant using a small sprayer. After the treatment, the plants were grown again in the greenhouse, and on the 21st day of treatment, the herbicidal effect and phytotoxicity were investigated according to the criteria in Table 2. The results are shown in Table 9.

[Table] Test Example 6 (Medicinal efficacy and chemical damage test by field soil stem and leaf treatment) Field soil was filled in plastic pots (surface area 330 cm ² ), and corn, blueberry, white locust, and
Each type of corn was sown and grown in a greenhouse until the corn reached the three-leaf stage. Corn 3
At the leaf stage, a predetermined amount of the hydrating agent prepared according to Example 7 was diluted with water, and 100 per 10 are was sprayed onto the entire plant from above using a small sprayer. After the treatment, the plants were grown again in the greenhouse, and on the 21st day of treatment, the herbicidal effect and phytotoxicity were investigated according to the criteria in Table 2. The results are shown in Table 10.

【table】 [Brief explanation of the drawing]

FIG. 1 shows the infrared spectral curve of compound 6.

Claims (1)

[Claims] 1 General formula: [Formula, X and Y represent a hydrogen atom or a halogen atom, and Z represents a group [Formula] (where R represents a hydrogen atom or an alkyl group,
R ¹ represents an alkyl group, a cycloalkyl group, or an alkoxyalkyl group. However, when R is a methyl group, R ¹ represents an alkoxyalkyl group. ) is shown. In addition, Y and Z are the group [Chemical formula] (where R ² represents a hydrogen atom or an alkyl group,
R ³ represents an alkyl group, an alkenyl group, or an alkynyl group. ) and can be bonded to the phenyl ring. ] 9-phenylimino-8-thia-1,6-diazabicyclo [4.3.0]
Nonan-7-one derivative. 2 General formula [formula] [wherein X and Y represent a hydrogen atom or a halogen atom, Z is a group [formula] (where R represents a hydrogen atom or an alkyl group,
R ¹ represents an alkyl group, a cycloalkyl group, or an alkoxyalkyl group. However, when R is a methyl group, R ¹ represents an alkoxyalkyl group. ) is shown. In addition, Y and Z are the group [Chemical formula] (where R ² represents a hydrogen atom or an alkyl group,
R ³ represents an alkyl group, an alkenyl group, or an alkynyl group. ) and can be bonded to the phenyl ring. ] 9-phenylimino-8-thia-1,6-diazabicyclo [4.3.0]
A herbicide characterized by containing a nonan-7-one derivative as an active ingredient.