JP2714671B2 - Thiadiazabicyclononane derivatives and herbicides - Google Patents

Description

The present invention relates to a 9-phenylimino-8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one derivative, and a derivative thereof as an active ingredient. It relates to herbicides.

(Prior Art) In recent years, many herbicides have been developed and put into practical use, and have contributed to labor saving of agricultural work and improvement of productivity. 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 (Agrochemical Handbook 1985 Edition 385
Oxadiazone is liable to cause chemical damage when used in paddy fields, and cannot be expected to be effective in controlling perennials, especially Urikawa.
Also, when used in fields, it has low safety against crops such as corn and soybeans, but has the disadvantage of low herbicidal effects against difficult-to-control weeds such as corn fir and noasagao, and low herbicidal effects on Aoubiyu and Shiroza. In view of the above, the emergence of a herbicide which has been further improved has been desired.

(Problems to be Solved by the Invention) The present inventors have realized the following conditions in order to fulfill the above demands: (1) being effective at an extremely low dose, (2) weeds in paddy fields and / or (3) It is also effective against perennial weeds and / or difficult-to-control weeds; (4) It is effective over a wide range of times from germination to growth. (5) Excellent residual effect and stable effect can be expected; (6) High safety for useful crops; However, they have found that these requirements are satisfied and completed the present invention.

(Technical Means for Solving the Problems) The 9-phenylimino-8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one derivative of the present invention has the general formula (In the formula, X represents a hydrogen atom or a halogen atom, R ¹ represents a hydrogen atom or an alkyl group, R ² is an alkenyloxy group, an alkynyloxy group, an alkylthio group, a halogen-substituted alkoxy group, an alkoxycarbonylalkoxy group,
α, α-dimethylbenzylamino group, group —OC ₂ H ₄ S (O) nR ³
(Wherein, R ³ represents an alkyl group or a phenyl group;
Or an integer of 2. ), (Wherein, Y represents a halogen atom, an alkyl group, an alkoxy group or a nitro group, R ⁴ represents a hydrogen atom or an alkyl group, and n ¹ and n ^{2 each} represent 0 or an integer of 1, 2). −OC
₂ H ₄ OR ⁵ (wherein R ⁵ represents a phenyl group, a benzyl group or a methoxyalkyl group), a group —OCH ₂ R ⁶ (wherein R ⁶ is a styryl group, a cyanoalkyl group, and tetrahydrofuran-2-
Represents an yl group, a thienyl group or a pyridin-2-yl group. ), Group (Wherein, R ⁷ represents an alkyl group or a phenyl group) or a group Is shown. ].

The compounds of the present invention represented by the general formula (I) are exemplified in Table 1. The compound numbers will be referred to in the following description.

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

(In the formula, X, R ¹ and R ² have the same meanings as described above.) In this method, a compound represented by the chemical formula (II) and a compound represented by the general formula (III) are reacted in the presence of a base. It is performed by reacting.

Examples of the base include aliphatic tertiary amines such as triethylamine and trimethylamine, aromatic tertiary amines such as pyridine, picoline and quinoline, and inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate. Can be used.

The above reaction is desirably performed in a solvent. Examples of the solvent include chlorinated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; ethers such as diethyl ether, tetrahydrofuran and dioxane;
Hydrocarbons such as hexane, benzene, and toluene, aliphatic ketones such as acetone and methyl ethyl ketone, dimethyl sulfoxide, and N, N-dimethylformamide can be used.

The above reaction is carried out in a temperature range from -20 ° C to the boiling point of the solvent, and is completed in 1 to 7 hours.

The compound represented by the general formula (II) can be synthesized, for example, according to the method shown in the following reaction formula.

(In the formula, A represents a halogen atom, and R ¹ , R ² and X have the same meaning as described above.) A compound represented by the general formula (IV) and a compound represented by the general formula (V) Formula (VI) by reacting in the presence of a base
Is obtained in good yield. In this case, examples of the solvent include lower fatty acid amides such as acetonitrile, N, N-dimethylformamide (DMF) and N, N-dimethylacetamide, dimethyl sulfoxide, water, ethers such as tetrahydrofuran and dioxane, and fatty acid esters such as ethyl acetate. Alcohols such as methanol, ethanol, propanol and glycol, and ketones such as acetone, methyl ethyl ketone and cyclohexanone. Also, as the base, potassium carbonate,
Inorganic bases such as sodium hydrogen carbonate, alcoholates of alkali metals and alkali metals, and organic bases such as pyridine, trimethylamine, triethylamine, diethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene can be used. The reaction temperature can be from 0 ° C. to the boiling point of the solvent, and the reaction time can be from 30 minutes.
It may be performed within a range of up to 24 hours, preferably 1 hour to 4 hours.

Further, by reacting the compound represented by the general formula (VI) with thiophosgene in a two-phase system of an aqueous phase and an organic phase, the intermediate represented by the general formula (VII) can be obtained in good yield. . At that time, as the solvent, for example, a halide such as dichloromethane, chloroform, carbon tetrachloride, toluene,
Aromatic hydrocarbons such as benzene and fatty acid esters such as ethyl acetate can be used. The reaction can be carried out at a temperature ranging from 0 ° C. to the boiling point of the solvent, and the reaction time can range from 30 minutes to 24 hours, preferably from 1 hour to 4 hours.

Further, the compound represented by the chemical formula (VII) and the general formula (V
By reacting the compound represented by III) in the presence of a solvent, the intermediate represented by the general formula (II) can be obtained in good yield. At this time, as the solvent, halides such as dichloromethane, chloroform and carbon tetrachloride, water, ethers such as tetrahydrofuran and dioxane, and fatty acid esters such as ethyl acetate can be used. The reaction can be carried out at a temperature ranging from 0 ° C. to the boiling point of the solvent, and the reaction can be carried out within a range of 30 to 24 hours, preferably 1 to 4 hours.

The intermediate represented by the chemical formula (VIII) is referred to as Bull. Soc.
It was synthesized according to the method described in the literature such as m.France (1957) 704.

The compound of the present invention represented by the general formula (I) can also be synthesized as a separate synthesis method according to the method shown in the following reaction formula.

(In the formula, R ¹ , R ² and X have the same meaning as described above.) A compound represented by the general formula (IX) and a compound represented by the general formula (X) are reacted in the presence of a halogenating agent and a base. To give the compound of the present invention represented by the general formula (I). At that time, N, N-dimethylformamide, N, N-
Lower fatty acid amides such as diethylformamide, and chlorinated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride can be used. Further, as the halogenating agent, phosphorus oxychloride, thionyl chloride, oxalyl chloride, phosgene and the like can be used. further,
Examples of the base include inorganic bases such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, and alcoholates of alkali metals, pyridine, trimethylamine, triethylamine, diethylaniline, and 1,8-diazabicyclo [5.4.0].
Organic bases such as -7-undecene can be used. The reaction can be carried out at a temperature in the range of -30 ° C to 30 ° C, and the reaction time can be in the range of 30 minutes to 24 hours, preferably 4 hours to 14 hours.

 Next, the manufacturing method will be specifically described with reference to examples.

Example 1 Production of 9- (4-chloro-3-propargyloxycarbonylmethylthiophenylimino) -8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one (Compound No. 1) 0.7 g of 1,2-tetramethylene-1- (4-chloro-3-propargyloxycarbonylmethylthiophenylaminothiocarbonyl) hydrazine
ol), 0.5 g (6 mmol) of pyridine and 20 ml of dichloromethane were added, and a dichloromethane solution containing 0.3 g (3 mmol) of phosgene was added dropwise while cooling with ice water. After dropping, the mixture was further stirred for 1 hour at room temperature to react. After completion of the reaction, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 0.3 g of the target substance as white crystals (yield:
41%). Melting point 105-107 ° C Example 2 of 9- (4-chloro-3-benzyloxycarbonylmethylthiophenylimino) -8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one (Compound No. 7) Production In a reaction flask, 1.4 g (3.2 mmol) of 1,2-tetramethylene-1- (4-chloro-3-benzyloxycarbonylmethylthiophenylaminothiocarbonyl) hydrazine was added.
l), 0.8 g (10 mmol) of pyridine and 20 ml of dichloromethane were added, and a dichloromethane solution containing 0.5 g (5 mmol) of phosgene was added dropwise while cooling with ice water. After dropping, the mixture was further stirred for 1 hour at room temperature to react. After completion of the reaction, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography to give 1.0 g of the target compound as a colorless candy.
(67% yield). Refractive index n _D ²⁰ 1.6158.

Example 3 9- [4-Chloro-3- (2-methylthioethoxycarbonylmethylthio) phenylimino] -8-thia-1,
Preparation of 6-diazabicyclo [4.3.0] nonan-7-one (Compound No. 16) 1,2-tetramethylene-1- [4-chloro-3- (2-methylthioethoxycarbonylmethylthio) phenylaminothio Carbonyl] hydrazine 1.4g
(3.3 mmol), 0.8 g (10 mmol) of pyridine and 20 ml of dichloromethane, and while cooling with ice water, 0.5 g (5 mmol) of phosgene
mol) was added dropwise. After dropping, the mixture was further stirred for 1 hour at room temperature to react. After completion of the reaction, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 0.7 g (yield 47%) of a target product as white crystals. 57-58 ° C.

Example 4 9- (4-Chloro-2-fluoro-5-isopropylideneaminooxycarbonylmethylthiophenylimino) -8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one (Compound No. 106 Preparation of 9- (4-chloro-2-fluoro-)
2.5 g of 5-carboxymethylthiophenylimino) -8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one
(8.4 mmol) and DMF (10 ml) were added, and 0.8 g (6.7 mmol) of thionyl chloride was added dropwise while cooling with salt ice. After the dropwise addition, the mixture was stirred at 0 ° C for 30 minutes, 50 ml of dichloromethane was added, and a dichloromethane solvent (10 ml) containing 0.5 g (6.8 mmol) of acetone oxime was further added dropwise at 0 ° C. Next, 1 g of pyridine (1
2.8 mmol) was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the reaction solution was dissolved in ethyl acetate, washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 1.2 g of a light brown viscous liquid (yield: 42.1
%). Refractive index n _D ²⁰ 1.5975.

Example 5 9- [4-Chloro-2-fluoro-5-thenyloxycarbonylmethylthiophenylimino) -8-thia-1,
Production of 6-diazabicyclo [4.3.0] nonan-7-one (Compound No. 102) 1,2-tetramethylene-1- (4-chloro-2-fluoro-5-thenyloxycarbonylmethylthiophenylaminothio was added to a reaction flask. 1.0 g of carbonyl) hydrazine
(2.2 mmol), 0.5 g (6 mmol) of pyridine and 20 ml of dichloromethane, and 0.5 g of phosgene (5 mm
ol) in dichloromethane solution was added dropwise. After dripping,
The mixture was further stirred at room temperature for 1 hour to be reacted. After the reaction is over,
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. White crystalline target 0.
8 g (74.8% yield) was obtained. 82-84 ° C.

To use the compound of the present invention represented by the general formula (I) as a herbicide in paddy fields, uplands, orchards, non-agricultural lands, and the like,
It is preferable to use the active ingredient in an appropriate dosage form according to the purpose. Usually, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, a surfactant and the like are added thereto, and the active ingredient is used in the form of powders, wettable powders, emulsions, granules and the like. Further, the herbicide of the present invention can be mixed with an insecticide, a fungicide, another herbicide, a plant growth regulator, a fertilizer, and the like, if necessary.

Next, the formulation method will be specifically described with reference to formulation examples. In the following formulation examples, "part" means "part by weight".

Formulation Example 1 wettable powder 10 parts of compound (1), 0.5 parts of Emulgen (registered trademark of Kao Corporation) 810, 0.5 parts of Demol (registered commercial law of Kao Corporation) N, kunilite (registered by Kunimine Industries Co., Ltd.) 20 parts of Trademark 201) and 69 parts of Ziglite (registered trademark of Ziglite) CA are mixed and pulverized to obtain a wettable powder.

Formulation Example 2 wettable powder 10 parts of compound (2), 0.5 part of Emulgen 810, 0.5 part of Demol N, 20 parts of Kunilite 201, Carplex 80
Are mixed and pulverized to obtain a wettable powder.

Formulation Example 3 Emulsion To 30 parts of compound (3), add 60 parts of an equal mixture of xylene and isophorone, and 10 parts of surfactant Solpol (registered commercial method of Toho Chemical Industry Co., Ltd.) 800A, and mix well. An emulsion is obtained.

Formulation Example 4 Granules 10 parts of compound (4), 80 parts of a bulking agent obtained by mixing talc and bentonite in a ratio of 1: 3, 5 parts of white carbon
Parts, 5 parts of surfactant Solpol 800A and 10 parts of water,
The kneaded paste is extruded through a sieve hole having a diameter of 0.7 mm, dried, and then cut to a length of 0.5 to 1 mm to obtain granules.

(Effects of the Invention) The herbicide of the present invention is used against annual perennial weeds such as barnyardgrass, magpies, oaks, kakashigusa, azena and abnomé, and perennial weeds such as fireflies, pine flies, spoongrass, urikawa and mizugatsuri which occur in paddy fields. By treating over a wide range from the time of germination to the growing season, it exerts an excellent herbicidal effect at an extremely low dose and has high safety against rice. In addition, various weeds that are problematic in the field, for example, broadleaf weeds such as polygonum, aobil, white rose, Inoufuguri, mustard, onamamomi, noasagao, tsunoxanem, ichibi, as well as cyperaceae weeds such as kogonagayatsuri, hie, meenoshiba, and echinogora. It has the characteristics of showing a high herbicidal effect on grass weeds such as soybeans, corns, upland rice, wheat and the like while exhibiting a high herbicidal effect by soil treatment or foliage treatment.

Furthermore, since the herbicide of the present invention has excellent residual effect, it exhibits a long-term stable effect in the field.
It can also be used in orchards, pastures, lawns, and non-agricultural lands.

Next, the effects of the compound of the present invention will be described with reference to Test Examples.

Test Example 1 (Test of herbicidal effect by treatment of paddy field soil) Paddy field soil was filled in a porcelain pot having a diameter of 10 cm, and after scraping, various varieties of red snapper, tamayatsuri, konagi and firefly were sown and submerged to a depth of 3 cm.

The next day, the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped on the water surface. The application rate is 400 g per 10 ares of the active ingredient. Thereafter, the plants were grown in a greenhouse, and 21 days after the treatment, the herbicidal effect was investigated according to the criteria in Table 2. As a result, all of the present compounds 1 to 114 showed an index of 5.

Test Example 2 (Herbicidal Effect Test by Upland Field Soil Treatment) In a plastic pot (surface area: 120 cm ² ), field soil was filled, and seedlings of polypium, Aoyuyu, Shiroza and Kogomegayatsuri were sowed and covered with soil. The prepared wettable powder was diluted with water, and 100 l per 10 ares (400 g of active ingredient per 10 ares) was evenly sprayed on the soil surface with a small sprayer. After the treatment, the plants were grown in a greenhouse for 21 days, and the herbicidal effect was investigated according to the criteria shown in Table 2. The results are shown in Tables 3 and 4.

Test Example 3 (Test of herbicidal effect by field foliage treatment) In a plastic pot (surface area: 120 cm ² ), field soil was filled, and various seeds of barnyard grass, barnyard grass, aoville, shiroza and Kogomegayatsuri were sown. Cultivated in a greenhouse. A wettable powder prepared according to Formulation Example 1 was diluted with water at the 3rd leaf stage of the millet, and 100 l per 10 ares (active ingredient 400 g per 10 arels) was sprayed with foliage from above the whole plant using a small sprayer. . Grow in the greenhouse for 21 days after treatment,
The herbicidal effect was investigated according to the criteria in Table 2. The results are shown in Tables 5 and 6.

Test Example 4 (Pharmaceutical efficacy and phytotoxicity test by paddy soil treatment) Paddy field soil was filled in a 1/5000 arel Wagner pot, and after water entry and scraping, sprouting tubers of budding urikawa were buried in the soil surface layer by three individuals per pot. Seeds, and 2.5-leaf rice at a transplanting depth of 2 cm.
The two strains were transplanted and submerged at a depth of 3 cm. The next day, a predetermined amount of the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped on the water surface. Thereafter, the plants were grown in a greenhouse, and on the 30th day of the treatment, the herbicidal effect and the phytotoxicity were investigated according to the criteria in Table 2. The results are shown in Tables 7 and 8.

Test Example 5 (Soybean selectivity test) A plastic pot (120 cm ^{2 in} surface area) was filled with field soil, and seeds of soybean, Naomi fir and Noasagao were sown.
After growing at room temperature for 14 days, a predetermined amount of the wettable powder prepared according to Formulation Example 1 was diluted with water, and 100 l per 10 ares was sprayed with foliage from above the whole plant using a small sprayer. After the treatment, the plants were grown again in a greenhouse, and on the 21st day of the treatment, the herbicidal effect and the phytotoxicity were investigated according to the criteria shown in Table 2. The results are shown in Tables 9 and 10.

Test Example 6 (Medicinal effect and phytotoxicity test by field foliage treatment) A field pot was filled with plastic soil (a surface area of 330 cm ² ), and rice, wheat, corn, and various seeds of Aoyuyu, Shiroza and Ichibai were sown. Cultivated in a greenhouse until A predetermined amount of the wettable powder prepared according to Formulation Example 1 was diluted with water at the third leaf stage of rice, and 100 l per 10 ares were sprayed with foliage from above the whole plant using a small sprayer. After the treatment, the plants were grown again in a greenhouse, and on the 21st day of the treatment, the herbicidal effect and the phytotoxicity were investigated according to the criteria shown in Table 2. The results are shown in Tables 11 and 12.

[Brief description of the drawings]

FIGS. 1, 2, 3 and 4 show the infrared spectrum curves of compound 7, compound 10, compound 63 and compound 111, respectively.

 ──────────────────────────────────────────────────続 き Continuation of the front page Examiner Shunichi Yokoo (56) References JP-A-62-91 (JP, A)

Claims (2)

(57) [Claims] (1) General formula [In the formula, X represents a hydrogen atom or a halogen atom, R ¹ represents a hydrogen atom or an alkyl group, R ² represents an alkenyloxy group, an alkynyloxy group, an alkylthio group, a halogen-substituted alkoxy group, an alkoxycarbonylalkoxy group,
α, α-dimethylbenzylamino group, group —OC ₂ H ₄ S (O) nR ³
(Wherein, R ³ represents an alkyl group or a phenyl group;
Or an integer of 2. ), (Wherein, Y represents a halogen atom, an alkyl group, an alkoxy group or a nitro group, R ⁴ represents a hydrogen atom or an alkyl group, and n ¹ and n ^{2 each} represent 0 or an integer of 1, 2). −OC
₂ H ₄ OR ⁵ (wherein R ⁵ represents a phenyl group, a benzyl group or a methoxyalkyl group), a group —OCH ₂ R ⁶ (wherein R ⁶ is a styryl group, a cyanoalkyl group, and tetrahydrofuran-2-
Represents an yl group, a thienyl group or a pyridin-2-yl group. ), Group (Wherein, R ⁷ represents an alkyl group or a phenyl group) or a group Is shown. A thiadiazabicyclononane derivative represented by the formula: 2. The general formula (In the formula, X represents a hydrogen atom or a halogen atom, R ¹ represents a hydrogen atom or an alkyl group, R ² is an alkenyloxy group, an alkynyloxy group, an alkylthio group, a halogen-substituted alkoxy group, an alkoxycarbonylalkoxy group,
α, α-dimethylbenzylamino group, group —OC ₂ H ₄ S (O) nR ³
(Wherein, R ³ represents an alkyl group or a phenyl group;
Or an integer of 2. ), (Wherein, Y represents a halogen atom, an alkyl group, an alkoxy group or a nitro group, R ⁴ represents a hydrogen atom or an alkyl group, and n ¹ and n ^{2 each} represent 0 or an integer of 1, 2). −OC
₂ H ₄ OR ⁵ (wherein R ⁵ represents a phenyl group, a benzyl group or a methoxyalkyl group), a group —OCH ₂ R ⁶ (wherein R ⁶ is a styryl group, a cyanoalkyl group, and tetrahydrofuran-2-
Represents an yl group, a thienyl group or a pyridin-2-yl group. ), Group (Wherein, R ⁷ represents an alkyl group or a phenyl group) or a group Is shown. ] The herbicide which contains the thiadiazabicyclononane derivative represented by these as an active ingredient.