KR0128544B1 - 2.3-dihydro-3-nethyel-2-substituted phenyl-1h-one derivatives - Google Patents

Abstract

Title derivatives(I; R1, R2= same or not, H, fluro, chlorro, bromo, C1-3 alkyl, C1-3 alkoxy; R1 and R2 are formed a fused ring such as -CH=CH-CH=CH-; R3= H, C1-4 alkyl, C3-6 alkenyl, etc.), useful as herbicides were prepared. Thus, 3.03 g 4-fluorophenol was reacted with 1.9 ml ethyl chloride, followed by addition of 4.0 g anhydrous aluminium chloride at 180 deg.C for 30 minutes to give 2.71 g 2-hydroxy-5-fluoroacetophenone(III). III and 1.05 g ethyl carbamate were refluxed for 20- 30 hours in 50 ml n-propanol to give ethoxycarbonylhydrazone derivatives IV. 2.41 g IV was dissolved in 100 ml tetrahydrofuran, adding 4.44 g (CH3COO)4Pb as an oxidation agent at room temperature for 3- 5 hours to give ethyl 0-acetylarylcarboxylate derivatives(V). 2.1 g V and 0.83 g 4-chloro-2-fluoro-5-hydroxyaniline were refluxed for 20- 30 hours in a mixed solvent of 50 ml o-dichlorobenzene and acetic acid to give 2,3-dihydro-3-methylene- 2-(4-chloro-2-fluoro-3-hydroxyphenyl)-1H-isoindol-1-one(VII). VII was refluxed for 20 hours to give 2,3-dihydro-3-methylene-2- (3-propagyloxy-4-chloro-2-fluorophenyl)-1H-isoindol-1-one(I).

Description

2,3-dihydro-3-methylene-2-substituted phenyl-1H-isoindol-1-one derivative

The present invention relates to a 2,3-dihydro-3-methylene-2-substituted phenyl-1H-isoindol-1-one derivative represented by the following structural formula (I) having herbicidal activity.

In the above formula,

R ¹ and R ² are the same as or different from each other, and hydrogen, florol, chloro, bromo, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy group or R ¹ and R ² are -CH = CH-CH Connected to = CH- to form a fused ring,

R ³ is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkylyl, C ₃ -C ₆ haloalkenyl, C ₃ -C ₆ alkynyl, C ₂ -C ₄ cyanoalkyl group Or benzyl group.

Conventional herbicidally active compounds, 1-phenyl-2-oxo-5-methylenepinolidine derivatives represented by the following structures (A) are effective as herbicides or plant growth regulators, and their preparation and herbicidal activity It has already been described [Japanese Patent No.63039-859; European Patent Nos. 420-810-A, 403-891-A and 305-333-A.

Thus, the inventors of the present invention, unlike the conventional structural formula (A) compound is connected to R ₁ and R ₂ so as to be part of the phenyl ring to form a fused ring (fusedrlng), by introducing a substituent to the phenyl ring thus obtained strong weeding The present invention has been completed by preparing a compound represented by the above formula (I) having excellent effects and selectivity between weeds and crops.

Accordingly, an object of the present invention is to provide a compound of formula (I) having a strong herbicidal activity and excellent selectivity as a plant growth inhibitor, and a method of producing the same.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by a 2,3-dihydro-3-methylene-2-substituted phenyl-1H-isoindol-1-one derivative represented by the following structural formula (I).

Wherein R ¹ , R ² and R ³ are as defined above.

Referring to the present invention in more detail as follows.

The present invention relates to a compound represented by the above formula (I) having strong herbicidal activity and excellent selectivity, and among the compounds of the above formula (I), R ¹ = R ² = H, R ³ is C ₃ the alkynyl group of compound ~C _6, and more preferred compounds are supposed to be represented by the following structural formula (I -a) and (I -b).

In addition, looking at the manufacturing method of the novel compound represented by the structural formula (I) according to the present invention as follows.

[Scheme]

In the above formula,

R ¹ , R ² and R ³ are as defined above,

X is a leaving group and is a chloro, bromo, iodine, tosyloxy or mesyloxy group.

In more detail describing the process for preparing a compound of formula (I) of the present invention according to the above reaction scheme, first, the phenol derivative represented by the formula (II) is mixed with acetyl chloride, and then anhydrous aluminum chloride is added thereto and the reaction temperature The reaction was raised to about 180 ℃ for 30 minutes. Thereafter, separation is carried out in a conventional manner to obtain the compound of formula III in 65 to 100% yield.

The compound of formula (III) and ethyl carbazate are then refluxed with n-propane in a solvent for 20-30 hours and cooled to room temperature to obtain the compound represented by formula (IV) in solid form. The yield at this time is 70 to 92%.

The compound of formula (IV) was dissolved in tetrahydrofuran and (CH ₃ COD) ₄ P b was added thereto, followed by reaction at room temperature for 3 to 5 hours, and then the resulting (CH ₃ COD ₂ ) Pb was filtered off. . The filtrate is distilled under reduced pressure and purified by chromatography to obtain the compound of formula (V) in 40-72% yield.

The compound of the above formula (V) and 2-fluoro-4-chloro-5-hydroxyaniline represented by the above formula (VI) are dissolved in a mixed solvent of dichlorobenzene and acetic acid 10: 1% by volume for 20 to 30 hours. Reflux. Then, after carrying out the usual operation, the residue is separated by chromatography to obtain the methyleneisoindole derivative represented by the above formula (VII) in 26 to 69% yield.

In addition, the compound of formula (I) and R ³ X represented by the formula (I) are dissolved in anhydrous acetone solvent and refluxed for 20 to 30 hours in the presence of a base. It synthesize | combines with high yield of 81-100%. At this time, anhydrous potassium carbonate (K ₂ CO ₃ ) is used.

Representative examples of the compound represented by Structural Formula (I) of the present invention prepared by the above preparation method are shown in Table 1 below.

TABLE 1

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.

Example: Preparation of 2,3-dihydro-3-methylene-2- (3-propazyloxy-4-chloro-2-fluorophenyl) -1H-isoindol-1-one (I) 6, when R ¹ = 5-F, R ² = H, R ³ = -CH ₂ C≡CH)

Attyl chloride (1.9 ml, 27 mmol) is added to 4-fluorophenol (III, 3.03 g, 27 mmol) and the reaction is slowly heated to react until no gas is generated. Anhydrous aluminum chloride (4.0 g, 30 mmol) was slowly added thereto, reacted at 180 ° C. for 30 minutes, cooled to room temperature, and diluted aqueous chloride solution was slowly added thereto and stirred for about 20 hours. The resulting white solid was filtered, washed with distilled water and dried to obtain 2.71 g of 2-hydroxy-5-fluoroacetophenone (III) as a white solid.

Yield = 2.71 g (65%)

Melting Point: 52 ~ 53 ℃

¹ H NMR (DMSO-d ₆ ): δ 11.0-12.0 (brs, 1H, OH), 7.65-7.40 (m, 3H), 2.60 (s, 3H).

2-hydroxy-5-fluoroacetophenol (III, 1.54 g, 10 mmol) prepared above was dissolved in 50 ml of n-propane and ethyl carbazate (1.05 g, 10 mmol) was added thereto for 20 to 30 hours. Reflux for a while. The resulting solid was filtered and dried to obtain an ethoxycarbonyl hydrazone derivative (IV, R ¹ = 5-F, R ² = H) as a target compound. The filtrate was distilled under reduced pressure to obtain a residue, which was further obtained by the chromatograph separation method.

Yield: 1.97 g (82%)

Melting Point: 156 ~ 158 ℃

¹ H NMR (DMSO-d ₆ ): δ 12.75 (brs, OH), 10.95 (brs, NH), 7.22 to 6.95 (m, 3H), 4.25 (q, 2H), 2.35 (s, 3H), 1.32 ( t, 3H).

The ethoxycarbonyl hydrazone derivative (IV, 2.41 g, 10 mmol) prepared above was dissolved in tetrahydrofuran (100 ml), and when oxidizing agent (CH ₃ COO) ₄ Pb (4.44 g, 100 mmol) was slowly added, N It can be observed that ₂ gases are generated slowly. After reacting for 3 to 5 hours at room temperature, the resulting (CH ₃ COO) ₂ Pb is filtered off and distilled under reduced pressure to remove the solvent. The oil thus obtained was separated and purified by chromatography, to obtain an ethyl ortho-acetylaracarboxylate derivative (V, R ¹ = 5-F, R ² = H).

Yield: 1.51 g (72%)

¹ H NMR (CDCl ₃ ): δ 7.95 to 7.02 (m, 3H), 4.35 (q, 2H), 2.52 (s, 3H), 1.33 (t, 3H).

The ethyl ortho-acetylaricarboxylate derivative (V, 2.1 g, 5 mmol) and 4-chloro-2-fluoro-5-hydroxyaniline (VI, 0.83 g, 5.1 mmol) prepared in the above were prepared from ο-dichlorobenzene. (50 ml) and acetic acid (ml) in a mixed solvent. The reaction solution was refluxed for 20 to 30 hours and then cooled to room temperature, distilled with dichloromethane (100 ml) and washed with distilled water. The organic layer is dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent. The residue was separated and purified by chromatography to give 2,3-dihydro-3-methylene-2- (4-chloro-2-fluoro-3-hydroxyphenyl) -1H-isoindol-1-one (Ⅶ, R ¹ = 5-F, R ² = H).

Yield: 0.46 g (30%)

Melting Point: 178 ~ 180 ℃

¹ H NMR (CMSO-d ₆ ): δ 10.65 (brs, OH), 8.1 to 7.0 (m, 5H), 5.85 and 4.80 (t + d, 2H, methylene).

2,3-dihydro-3-methylene-2- (4-chloro-2-fluoro-3-hydroxyphenyl) -1H-isoindol-1-one prepared above (Ⅶ, R ³ : -CH ₂ C≡CH, X: the case of Br, dissolved 0.37g, 2.5 mmol) in anhydrous acetone (70ml) is refluxed for 20 hours. After cooling to room temperature, the solid was filtered off, the filtrate was distilled under reduced pressure, and then purified by chromatography. 2,3-dihydro-3-methylene-2- (3-propazyloxy-4-chloro-2-fluorophenyl ) -1H-isoindole-1-one (I) is obtained.

Yield: 0.28 g (81%)

Melting Point: 122 ~ 124 ℃

¹ H NMR (CDCl ₃ ): δ 7.1 to 7.9 (m, 5H), 5.25 and 4.75 (m, 2H, methylene), 4.75 (m, 2H), 2.55 (m, 1H).

In using the compound of this invention represented by said structural formula (I), it can be used as it is, or it can also be used in manufacturing forms, such as a hydrating agent, an emulsion, a granule, a liquid, or a powder. Solid carriers or liquid carriers can be used to make the preparations described below.

Solid carriers include inorganic powder (kaolin, bentonite, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, synthetic 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 (methane, ethane, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (toluene, benzene, xylene, methylnaphthalene), halogenated hydrocarbons (chloroform, carbon tetrachloride, chlorobenzene), ethers (dioxane, Terahydrofuran), ketones (acetone, methyl ethyl ketone, cyclohexanone), esters (ethyl acetate, butyl acetate, ethylene glycol acetate), amides (dimethylformamide), nitriles (acetonitrile), ethers Alcohols (ethylene glycol, ethyl ether), water and the like.

Nonionic, anionic, cationic or amphoteric substances may be used as the surfactant used in the emulsification or dispersion. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, oxyethylene oxypropylene resins, polyoxyethylene alkyl phosphates, fatty acid salts, alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates , Alkyl phosphates, polyoxyethylene alkyl sulfates, quaternary ammonium salts and the like. However, the surfactants that can be used are not limited to these. If necessary, glue, casein, starch, agar, polyvinyl alcohol, lignin sulfonic acid may be used as a supplement.

When preparing the compound represented by the formula (I) as a herbicide, the content may be used in a weight ratio of about 1 to 95%, preferably 3 to 80% by weight. And in order to improve the herbicidal effect can be used with other types of herbicides, in some cases synergism is expected.

In addition, the compound (I) of the structural formula (I) may be used together with insecticides, nematicides, fungicides, plant growth regulators or fertilizers if necessary.

The dosage of the compound of formula (I) varies depending on the type of compound, the type of crop, the treatment method, and the like. Generally, the dosage is about 60 g to 500 g per 3000 pyeong, and preferably about 125 g.

The herbicidal activity evaluation of the novel compounds of the present invention as described above is illustrated in the following test examples.

Test Example 1: Biological Evaluation Test

Sand loam mixed with an appropriate amount of fertilizer is sterilized and put in a test pot (field condition: 348 cm 2, rice field condition: 115 cm 2). The number of pots used at this time is 2 pots of field conditions and 1 pot of paddy conditions per compound. Later crops and weeds were T. aestivum, soybean (G. max), corn (Z.mays), D. sanguinalis, A. indica, C. japonica, and American dogs. Seeds or subterranean seeds of P. dichotomiflorum, S. nigrum, A. avicennae, X. thium, etc. in pots of field conditions and O. sativa as crops and weeds. ), E. oryzieola, C. difforis, M. vaginalis, S. juncoides, C. serotinus, and S. pygmaea Seeds, etc.) are sown in pots of non-condition, and then poured into fine soil and placed in a greenhouse. Dissolve 4 kg / ha of test compound (field condition: 14 mg / pot, paddy condition: 4 mg / pot) in acetone solvent, and then mix the same amount with water added with a nonionic surfactant (Tween 20). Spray 14 ml of netting and 4 ml of potting net for non-conditioning. The amount used below 4kg / ha is diluted and sprayed in an appropriate amount according to the ratio.

Soil treatment before germination is treated with the preparation prepared on day 1 after sowing, and foliage treatment after germination 9-14 days after sowing. After treatment with the drug, grow in a greenhouse for 2-3 weeks, and their manufacturing effects are examined by the form and physiological evidence. That is, 0% means no herbicidal effect, 10-20% slightly herbicidal effect, 40-60% moderate effect, 70-90% severe effect, and 100% means full herbicidal effect.

The herbicidal effect before germination and the herbicidal effect after germination of the representative compounds of formula (I) of the present invention are shown in Tables 2 and 3 below.

TABLE 2

TABLE 3

Test Example 2: Freshwater Condition Test

The search for rice herbicides in freshwater conditions is O. sativa, E. oryzieola, S. Juncoides, M. vaginalis, C. difformis, and Olmi ( S. pygmaea) and the like. The herbicide effect was searched 2 days after the treatment as in the case of dry herbicide search, and the results are shown in Table 4 below.

TABLE 4

As described above, the novel compound represented by the structural formula (I) according to the present invention has strong herbicidal activity. It also has a wide range of properties between crops and weeds, and is particularly stable in corn and soybeans during germination and can control a wide range of other weed varieties.

Claims (6)

2,3-dihydro-3-methylene-2-substituted phenyl-1H-isoindol-1-one derivative represented by the following structural formula (I). Wherein R ¹ and R ² are the same as or different from each other, and hydrogen, fluoro, chloro, bromo, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy group or R ₁ and R ₂ are each -CH = CH-CH = CH- is linked to form a fused ring, R ³ is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ haloalkenyl , C ₃ -C ₆ alkynyl, C ₂ -C ₄ cyanoalkyl group or benzyl group. The compound of claim 1, wherein R ¹ and R ² are hydrogen and R ³ is C ₃ -C ₆ alkynyl. The compound of claim 1, wherein the compound of formula (I) is represented by the following formula (I -a). The compound of claim 1, wherein the compound of formula (I) is represented by the following formula (I-b). A herbicide using as an active ingredient a 2,3-dihydro-3-methylene-2-substituted phenyl-1H-isoindol-1-one derivative represented by the following structural formula (I). Wherein R ¹ , R ² and R ³ are each as defined in claim 1 above. The method of claim 5, wherein the herbicide is used in the cultivation of corn, soybeans or wheat in the germination process.