KR100477892B1 - Herbicidal 9-(5-isoxazolemethoxyphenyl)imino-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one derivatives - Google Patents

Abstract

The present invention provides novel 9- (5-isoxazolmethoxyphenyl) imino-8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one derivatives represented by the following general formula (1) and these It relates to a herbicide containing as a component.

In Chemical Formula 1, R is a C ₁ to C ₅ alkyl group, a phenyl group or a substituted phenyl group, wherein the substituted phenyl group is a C ₁ to C ₃ alkyl group, a C _{1 to} C ₃ alkoxy group, a halogen atom, a cyano group, The substituent selected from a nitro group, a carboxyl group, and a carboxylic acid ester group is a phenyl group substituted with 1 to 3 single or complex.

Description

9- (5-isoxazolemethoxyphenyl) imino-8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one derivative having herbicidal activity {Herbicidal 9- (5-isoxazolemethoxyphenyl) imino -8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one derivatives}

The present invention provides novel 9- (5-isoxazolmethoxyphenyl) imino-8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one derivatives represented by the following Chemical Formula 1 It relates to a herbicide containing as an active ingredient.

[Formula 1]

In Chemical Formula 1, R is a C ₁ to C ₅ alkyl group, a phenyl group or a substituted phenyl group, wherein the substituted phenyl group is a C ₁ to C ₃ alkyl group, a C _{1 to} C ₃ alkoxy group, a halogen atom, a cyano group, The substituent selected from a nitro group, a carboxyl group, and a carboxylic acid ester group is a phenyl group substituted with 1 to 3 single or complex.

 As a material having a structure similar to that of the compound according to the present invention, some of the compounds having a thiadiazabicyclononane structure, for example, methyl [[2-chloro-4-fluoro-5-[(tetrahydro-3- Oxo-1H, 3H- [1,3,4] thiadiazolo [3,4-a] pyridazine-1-ylnidene) amino] phenyl] thio] acetate [European Patent No. 273,417, European Patent No. 611,768] , US Pat. No. 4,885,023 and US Pat. No. 4,906,279 are known to be effective as herbicides used in corn and soybeans. However, the compound has many points that still need to be improved in herbicidal effect and selectivity, and in particular, it is not used as a rice herbicide.

Accordingly, the inventors of the present invention have tried to develop a new material having better herbicidal effects and selectivity compared to existing herbicidal compounds. As a result, 8-chia-1,6-diazabicyclo having a novel structure in which various kinds of 9- (5-isoxazolemethoxyphenyl) imino groups are substituted in the C-9 position as represented by Chemical Formula 1 4.3.0] Nonane-7-one derivatives were synthesized, and the novel compounds described above were very excellent herbicidal activity and showed better selectivity than known similar herbicides for useful crops, including rice, as herbicides and growth regulators. The present invention has been completed by knowing that it is useful.

It is therefore an object of the present invention to provide novel compounds and their use as herbicides.

The present invention provides a 9- (5-isoxazolmethoxyphenyl) imino-8-chia-1,6-diazabicyclo [4.3.0] nonan-7-one derivative represented by the following Chemical Formula 1 as an active ingredient A herbicide containing is characterized by the above-mentioned.

[Formula 1]

In Chemical Formula 1, R is a C ₁ to C ₅ alkyl group, a phenyl group or a substituted phenyl group, wherein the substituted phenyl group is a C ₁ to C ₃ alkyl group, a C _{1 to} C ₃ alkoxy group, a halogen atom, a cyano group, The substituent selected from a nitro group, a carboxyl group, and a carboxylic acid ester group is a phenyl group substituted with 1 to 3 single or complex.

Referring to the present invention in more detail as follows.

9- (5-isoxazolmethoxyphenyl) imino-8-chia-1,6-diazabicyclo [4.3.0] nonan-7-one derivative represented by Formula 1 according to the present invention It is also useful as a rice herbicide because of its high stability and excellent blood control effect.

In addition, the 9- (5-isoxazolmethoxyphenyl) imino-8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one derivative represented by Chemical Formula 1 according to the present invention is asymmetric. Where carbon is present, the present invention includes each isolated isomeric compound or racemic mixture.

 In the compound represented by the formula (1) according to the invention, preferably in the case of a compound in which R is a phenyl group or a substituted phenyl group.

On the other hand, the present invention includes a method for producing a compound represented by the formula (1). Briefly showing the preparation method according to the present invention as shown in the following scheme 1, by the addition reaction between the compound represented by the formula (2) and the nitrile oxide represented by the following formula (3) or a precursor thereof to 1,3-dipolar cyclo This desired compound represented by the formula (1) can be prepared.

In Scheme 1, R is as defined above.

As the reaction solvent, dichloromethane, tetrahydrofuran, benzene, ethyl ether, C ₁ -C ₄ alcohol, etc. are suitable as the reaction solvent. Preferably, the solvent is purified in anhydrous state. Good to do.

In addition, the compound represented by the formula (2) used as a starting material in the above production method is a known compound, can be prepared according to the method exemplified in European Patent No. 273,417, the present invention is not limited thereto. It can also be synthesized by the method. As an example of the method for preparing the compound represented by Chemical Formula 2, the compound of Chemical Formula 4 may be reacted with hexahydropyridazine, and then reacted with phosgene and synthesized as shown below.

On the other hand, the compound represented by the formula (1) has excellent herbicidal activity, in particular in the environment of freshwater non-conditioning conditions and showed a very good safety against the transferred rice. Paddy field weeds, such as ECHOR, MOOVA, CYPSE, etc. show excellent herbicidal activity against paddy weeds and excellent safety against rice paddies. Useful as a weed herbicide. In addition, it shows great safety against rice and can be used as a herbicide for straight rice.

In order to formulate the compound represented by Formula 1 according to the present invention, a solid carrier or a liquid carrier may be used. Solid carriers include inorganic powders (kaolin, bentonite, montmorillonite, chalcopyrite, diatomaceous earth, mica, gypsum, carbon carbonate, apatite, silicon hydroxide), plant powder (soybean flour, flour, sawdust, tobacco powder, starch powder, Crystalline cellulose) polymer materials (petroleum resin, vinyl chloride resin, ketone resin), alumina, beeswax and the like can be used. Liquid carriers include alcohols (methanol, ethanol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (toluene, benzene, xylene, methyl naphthalene), halogenated hydrocarbons (chloroform, carbon tetrachloride, chlorobenzene), ethers (dioxane, tetrahydrofuran ), Ketones (acetone, methyl ethyl ketone, cyclohexanone), esters (ethyl acetate, butyl acetate, ethylene glycol acetate), amides (dimethylformamide), nitriles (acetonitrile), ether alcohols (ethylene glycol, Ethyl ether), water, and the like.

As the type of surfactant that can be used in the present invention, all cationic, anionic and nonionic surfactants can be used. Cationic surfactants include long-chain alkylammonium salts such as bromocetyltrimethylammonium salts, and anionic surfactants include salts of the following types: alkylarylsulfonic acids such as dodecylbenzenesulfonic acid and lauryloxy. Alkyloxysulfonic acids such as sulfonic acids, arylsulfonic acids such as ligninsulfonic acids, naphthalenesulfonic acids and dibutylnaphthalenesulfonic acids, lauryl ether sulfates, alkali metal salts such as sulfated aliphatic alcohols, fatty acids, alcohol ethers, alkaline earth metal salts or ammonium salts. And the type of nonionic surfactant is a condensation of castor oil, naphthalene or naphthalene sulfonic acid with phenol or formaldehyde containing aliphatic alcohols such as oleyl alcohol and cetyl alcohol, phenol, alkylphenol, ethylene oxide or propylene oxide.

When the compound of the present invention is prepared as a herbicide, the content of the substance represented by the formula (1) can be variously changed, but when prepared as a humectant, a granule, or an emulsifier, it is preferably included in an amount of 1 to 50% by weight. In the case of preparation by chemical granulation, it is preferable that 2 to 40 wt% is included. In addition, the formulation may be prepared by mixing with known insecticides, fungicides, nematicides, plant growth regulators, fertilizers or other pesticides commonly applied as needed, and in some cases to improve the herbicidal effect and broaden the scope of application. It can also be used with other types of herbicides. Another class of herbicides that may be used with the compounds of the present invention is 3-isopropyl- (methyl-2,1,3-benzothiadiazine-4 (3H) -one-2, commonly used as bentazone. , Methyl 2- [3- (4,6-dimethoxypyrimidin-2-yl) commonly used as N- (heteroarylaminocarbonyl) benzenesulfonamide herbicide, Londax Ureidosulfonyl] benzoate or ethyl 5- [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -1-methylpyrazole-4-carboxylate, commonly used as NC-311 Etc.

As described above, specific examples of 9- (5-isoxazolmethoxyphenyl) imino-8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one derivatives represented by Chemical Formula 1 above Synthesis Example and herbicidal activity will be described in more detail based on the following Examples and Experimental Examples, but the present invention is not limited thereto.

Example 9- [4-Chloro-5- (3-phenyl-5-methylisoxazol-5-yl) methoxy-2-fluorofluoroimino] -8-chia-1,6-dia Synthesis of Xabicyclo [4.3.0] nonan-7-one (Compound No. 1, R = phenyl group)

9- [4-Chloro-5-propazoloxy-2-fluorofluoroimino] -8-thia-1,6-diazabicyclo [4.3.0] nonan-7-one in dichloromethane solvent 2) (0.3 g, 0.8 mmol) and benzohydroxymoyl chloride (0.13 g, 0.8 mmol) were dissolved and triethylamine (0.1 g, 1.0 mmol) was added thereto, followed by stirring at room temperature for 12 hours. The reaction solution was poured into iced water, extracted with dichloromethane, the organic layer was washed with brine, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to remove the solvent. The residue was collected and separated and purified by silica gel column chromatography (ethyl acetate / hexane, 1/3) to obtain 0.33 g of the title compound.

Yield 85%; ¹ H NMR (CDCl ₃ ) δ7.71-7.15 (6H, m), 6.81 (1H, s), 6.59 (1H, d, J = 7.4 Hz), 5.16 (2H, s), 3.80-3.61 (4H, m), 2.02-1.87 (4H, m).

 By the method of the above Example, the derivatives listed in Table 1 below were synthesized. The compounds listed in Table 1 below are all racemic mixtures.

Compound number R ¹ H NMR (CDCl ₃ ): δ One Phenyl group 7.71-7.15 (6H, m), 6.81 (1H, s), 6.59 (1H, d, J = 7.4 Hz), 5.16 (2H, s), 3.80-3.61 (4H, m), 2.02-1.87 (4H, m). 2 2-fluorophenyl group 7.95-7.06 (5H, m), 6.77 (1H, s), 6.58 (1H, d, J = 7.3 Hz), 5.15 (2H, s), 3.75-3.62 (4H, m), 1.87-1.64 (4H, m). 3 4-fluorophenyl group 7.23 (2H, m), 7.07 (3H, m), 6.57 (1H, s), 6.55 (1H, d, J = 7.4 Hz), 5.13 (2H, s), 3.74-3.61 (4H, m), 1.88 -1.70 (4H, m). 4 2,4-dichlorophenyl group 7.59 (1H, d, J = 8.3 Hz), 7.40 (1H, d, J = 1.9 Hz), 7.23 (1H, m), 6.73 (1H, s), 6.54 (1H, d, J = 7.1 Hz), 5.12 (2H, s), 3.71-3.59 (4H, m), 1.90-1.71 (4H, m). 5 2-chlorophenyl group 7.79-7.17 (5H, m), 6.87 (1H, s), 6.69 (1H, d, J = 7.4 Hz), 5.26 (2H, s), 3.81-3.61 (4H, m), 2.11-1.87 (4H, m). 6 3-chlorophenyl group 7.77-7.18 (5H, m), 6.84 (1H, s), 6.67 (1H, d, J = 7.4 Hz), 5.24 (2H, s), 3.79-3.60 (4H, m), 2.12-1.97 (4H, m).

Herbicidal activity of the compound of the present invention prepared by the preparation process of the above embodiment was carried out in a greenhouse and representative experimental examples are as follows.

Experimental Example: Screening of Blood and Rice of the Compound of Formula 1

First, a soft sandy loam containing 1.2% of organic matter having a pH of 6.0 was contained in a test plastic pot (140 cm 2). 2 ~ 2.5 blades of rice (ORYSA) and pre-germinated rice seeds are transplanted or sown at 2 cm and depth, respectively, in the same pots with ECHOR, tadpoles (SCPJU), goose bee (MOOVA), beetle Seeds of CYPSE and SAGPY were sown. And watered 3 cm deep immediately after sowing or transplanting. After 2 days, the test compound and nonionic surfactant (TW-20) were dissolved in 50% acetone in liquid phase and water was added thereto. At this time, if the test compound was insoluble in the solvent system used, it was used as a wettable powder formulation. The concentration of the test compound or the wettable powder in solution depends on the application rate to the crop, but is generally at or below 4.0 kg / ha. Two to three weeks after the application of the herbicide, the test compound, herbicidal effects on blood and other rice weeds and damage to rice in rice fields were observed directly with the naked eye and expressed as a percentage, where 0 was no herbicidal effect. None indicates that 100 has been killed. Some of the results are shown in Table 2 below.

Herbicidal activity in paddy conditions Compound number  Throughput (Kg / ha) Rice (three seasons) Rice blood Tadpole Water pinnacle Youbangdosan Olme One 1.0 20 100 100 40 100 100 - 0.25 0 70 100 30 100 100 - 0.063 0 - 100 30 100 100 50 0.016 0 0 100 20 100 100 20 2 1.0 10 50 100 50 100 100 70 0.25 0 10 100 30 100 100 60 0.063 0 0 100 30 100 100 50 0.016 0 0 100 20 100 0 20 3 1.0 5 100 100 30 100 100 70 0.25 0 100 100 30 100 100 50 0.063 0 100 100 20 100 100 30 0.016 0 50 100 0 100 50 10 4 1.0 40 100 100 80 100 100 100 0.25 20 100 100 20 100 100 90 0.063 10 100 100 20 100 100 60 0.016 0 20 100 10 90 30 20 5 1.0 20 100 100 20 100 100 - 0.25 10 100 100 20 100 100 - 0.063 0 100 100 10 100 100 - 0.016 0 10 90 0 100 100 30

As described above, the high stability and excellent skin control effect of the compound of the present invention on rice enhances the utility especially in rice farming.

Claims (5)

9- [4-chloro-5- (3-phenyl-5-methylisoxazol-5-yl) methoxy-2-fluorofluoroimino] -8-chia-1 represented by the following Chemical Formula 1, 6-diazabicyclo [4.3.0] nonan-7-one derivatives: [Formula 1] In Chemical Formula 1, R is a C ₁ to C ₅ alkyl group, a phenyl group or a substituted phenyl group, wherein the substituted phenyl group is a C ₁ to C ₃ alkyl group, a C _{1 to} C ₃ alkoxy group, a halogen atom, a cyano group, The substituent selected from a nitro group, a carboxyl group, and a carboxylic acid ester group is a phenyl group substituted with 1 to 3 single or complex. The compound according to claim 1, wherein R is a phenyl group or a phenyl group substituted with halogen. 9- [4-chloro-5- (3-phenyl-5-methylisoxazol-5-yl) methoxy-2-fluorofluoroimino] -8-chia-1 represented by the following Chemical Formula 1, Herbicides characterized in that the 6- diazabicyclo [4.3.0] nonan-7-one derivative as an active ingredient:  In Formula 1, R is as defined in claim 1 above. The compound according to claim 1, wherein R is a phenyl group or a phenyl group substituted with halogen. Method for preparing a compound represented by the following formula (1) characterized in that for the addition reaction between 1,3-dipolar cyclocyclic compound represented by the formula (2) and a nitrile oxide or a precursor thereof represented by the following formula (3): In the above, R is as defined in claim 1 above.