JP2685266B2 - Herbicides containing benzoxazinone derivatives as active ingredients - Google Patents

Description

TECHNICAL FIELD The present invention relates to a herbicide containing a novel benzoxazinone derivative as an active ingredient. More specifically, the present invention has the general formula [In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² represents a hydrogen atom, an alkyl group, a cyanoalkyl group, an alkenyl group, an alkynyl group or an aralkyl group. ] The herbicide which contains the benzoxazinone derivative shown by these as an active ingredient.

Heretofore, various derivatives having a substituent at the 5-position of the oxazolidinedione ring have been known, but most of them have been reported so far because it is difficult to synthesize an oxazolidinedione derivative having a substituted methylidene group at the 5-position. It has not been. Further, although many heterocyclic compounds having a herbicidal activity have been synthesized and put into practical use until now, no oxazolidinediones having a practical herbicidal activity have been known so far.

[Problems to be Solved by the Invention] Among conventionally known oxazolidinedione derivatives, derivatives having a substituted or unsubstituted phenyl group on the nitrogen atom at the 3-position and an alkylidene group at the 5-position can be used in various weeds. In contrast, there is a description that it has herbicidal activity (JP-A-62
No. 174065), compounds having a bicyclic substituted phenyl group such as a benzoxazine ring, and biological activities of these compounds are not described.

The present invention provides a herbicide containing, as an active ingredient, a novel compound having both high selectivity against a variety of strong weeds and a strong herbicidal activity.

[Means for Solving the Problems] As a result of extensive studies on various oxazolidinedione derivatives, the present inventors have an isopropylidene group at the 5-position and a 3-position nitrogen as shown in the general formula (I). The inventors have found that a novel oxazolidinedione having a substituted benzoxazine ring on an atom, that is, a novel benzoxazinone derivative, exhibits strong herbicidal activity at a low dose and can be a sufficiently practical herbicide, and completed the present invention. .

The novel benzoxazinone derivative which is the active ingredient of the herbicide of the present invention, when used in a paddy field, is also effective against annual weeds such as millet, eel, scutellaria, and perennial weeds such as Cyperus communis, Firefly, Urikawa and Matsubais. Shows a good herbicidal effect. Also in the field, it is possible to selectively kill field weeds such as dog bream, crabgrass, enokorogusa, shiroza, kade, aobille, purslane and plantain.

Further, the novel benzoxazinone derivative according to the present invention has a strong weed-killing activity, and not only the initial effect can be obtained even in a small amount, but the phytotoxicity to useful cultivated plants is extremely low. That is, the novel benzoxazinone derivative kills grass weeds such as millet, crabgrass, and Enocorogusa, but does not cause phytotoxicity to rice crops such as transplanted rice, wheat, and corn. . Similarly, almost no phytotoxicity was observed on soybeans, cotton, etc., which are crops other than gramineae.

The amount of the herbicide containing the novel benzoxazinone derivative as an active ingredient varies depending on the application method, time, type of target plant, etc., but the compound amount is 10 to 500 per 10 are.
g, preferably about 30 to 300 g.

The novel benzoxazinone derivative according to the present invention represented by the general formula (I) can be produced, for example, by the following Production Method 1 or 2.

[In the above reaction formula, R ¹ has the same meaning as described above. R ² ′ represents an alkyl group, a cyanoalkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and R ³ represents a hydrogen atom or a lower alkyl group. Y is a leaving group. The <Production method 1> will be described in more detail. That is, the oxazolidinedione derivative represented by the general formula (II) is reduced in the acetic acid solution with a nitro group using, for example, reduced iron, and then condensed with an ester group. Accordingly, in the general formula (I ′) [in the formula, R ¹ has the same meaning as described above. This is a compound when R ¹ is a hydrogen atom in the above general formula (I). ] The benzoxazinone derivative represented by these can be obtained. The reaction is preferably carried out in an acetic acid solvent, but it can also be carried out in a mixed solvent system with another solvent such as ethyl acetate. The reaction temperature is selected from the range of room temperature to 150 ° C., but it is preferable to carry out the reaction at acetic acid reflux temperature. In this reaction, the product can be isolated as crystals by a usual post-treatment after the completion of the reaction, but if necessary, it is purified by silica gel column chromatography or recrystallization.

Next, the benzoxazinone derivative represented by the general formula (I ′) is represented by the general formula (III) in the presence of a base.
R ² ′ -Y [In the formula, R ² ′ represents an alkyl group, a cyanoalkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and Y is a leaving group. ]] On the nitrogen atom
By introducing the R ² ′ group, the compound of the general formula (I ″) [wherein
R ¹ and R ² ′ have the same meanings as described above. This is a compound when R ² is other than a hydrogen atom in the above general formula (I). ] The benzoxazinone derivative represented by the following formula can be easily produced. As the leaving group Y, Cl, B
A halogen atom such as r and I and a substituted sulfonyloxy group such as a tolylsulfonyloxy group, a phenylsulfonyloxy group and a methylsulfonyloxy group can be used. The reaction is preferably performed in an organic solvent. As the organic solvent, tetrahydrofuran, diethyl ether, dimethoxyethane, dimethylformamide, dimethylsulfoxide, acetonitrile, propionitrile, acetone,
Mention may be made of solvents such as methyl ethyl ketone, benzene and toluene. The reaction is carried out in the presence of a base, and examples thereof include alkyl lithium such as n-butyl lithium, sec-butyl lithium and methyl lithium, alkali metal hydrides such as sodium hydride and potassium hydride, sodium carbonate and potassium carbonate. Basic inorganic compounds such as sodium hydrogen carbonate, sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide and calcium hydroxide can be used. The reaction temperature varies depending on the base and solvent used, but is selected from the range of -78 to 150 ° C. In this reaction, the product can be isolated as a crystal by a usual post-treatment after the completion of the reaction, but if necessary, it is purified by silica gel column chromatography or recrystallization.

The oxazolidinedione derivative represented by the general formula (II), which is a raw material for producing the novel benzoxazinone derivative according to the present invention, can be produced, for example, by the method shown below.

[In the above reaction formula, R ¹ and R ³ have the same meanings as described above. That is, the oxazolidinedione derivative represented by the general formula (IV), which can be produced by a known method (see JP-A-62-174065), can be prepared by reacting the oxazolidinedione derivative represented by the general formula ( It can be produced by reacting with 2-hydroxycarboxylic acid represented by V) or its ester. Examples of the base used in this reaction include tertiary aliphatic and aromatic amine compounds such as triethylamine, tributylamine, N-methylmorpholine, pyridine and lutidine, potassium carbonate, sodium carbonate and sodium acetate.
An inorganic base such as potassium acetate can be used.
The reaction can be carried out in the absence of a solvent, but can also be carried out in an ordinary organic solvent. Furthermore, by carrying out this reaction under high pressure, the reaction can proceed efficiently. The 2-hydroxycarboxylic acid represented by the general formula (V) or its ester, which is a raw material, can be easily obtained or can be easily prepared from a commercially available raw material, and examples thereof include glycolic acid, lactic acid, and 2-hydroxy. Valeric acid, 2-hydroxy-3-methylpentanoic acid,
Methyl glycolate, ethyl glycolate, methyl lactate, butyl glycolate, ethyl lactate, butyl lactate, 2
-Methyl hydroxyvalerate, methyl 2-hydroxyisovalerate, methyl 2-hydroxy-3-methylpentanoate, methyl 2-hydroxy-4-methylpentanoate, 2
-Methyl hydroxyhexanoate, 2-hydroxy-3-
Methyl methyl heptanoate or the like can be used.

[In the above reaction formula, R ¹ and R ² have the same meanings as described above, and R ⁴ represents a lower alkyl group. In order to describe <Production method-2> in more detail, the benzoxazinone derivative represented by the general formula (I) according to the present invention is obtained by treating the carbamic acid ester represented by the general formula (VI) with a base. It can be easily obtained. The reaction is preferably carried out in an ordinary organic solvent at room temperature or under reflux. Examples of the base used include tertiary ethylamine, tripropylamine, tributylamine, N-methylmorpholine and dimethylaniline.
Aromatic amines such as primary amines, pyridine, lutidine and pyrimidine, sodium methoxide, sodium ethoxide, alkali metal alkoxides such as potassium t-butoxide, sodium hydride, alkali metal hydrides such as potassium hydride or sodium carbonate, Potassium carbonate,
Basic inorganic compounds such as sodium hydroxide and potassium hydroxide, and carboxylic acid metal salts such as sodium acetate and potassium acetate can be used. The amount of the base used is not particularly limited, but a catalytic amount is generally sufficient.

Further, as the organic solvent used, benzene, toluene, aromatic solvents such as xylene, dioxane, tetrahydrofuran, ether solvents such as dimethoxyethane,
Alcohol solvents such as methanol, ethanol, isopropanol, or ethyl acetate, acetonitrile,
Organic solvents such as dimethylformamide and dimethylsulfoxide can be mentioned.

Further, the carbamic acid ester represented by the general formula (VI) as a raw material is, for example, a known compound described in JP-A-61-76486, aminobenzoxazinone derivative (VII).
By converting its amino group to an isocyanato group or a carbamoyl chloride group using phosgene or phosgene dimer, and then adding 2-hydroxy-3-methyl-3-butenoic acid ester represented by the general formula (IX) as the case may be. Can be produced by reacting in the presence of a base. (See reaction formula below) [In the above reaction formula, R ¹ , R ² and R ⁴ have the same meanings as described above. Z represents an isocyanato group or a carbamoyl chloride group. In carrying out the present production method, the carbamic acid ester (VI) obtained by the reaction of the general formulas (VIII) and (IX) is treated with a base as it is, without isolation from the reaction system. The benzoxazinone derivative represented by the general formula (I) can be produced. Further, in carrying out this reaction, the reaction mixture obtained after completion of the reaction can be separated and purified using column chromatography or the like, but it may be necessary to add an appropriate solvent such as methyl alcohol, ethyl alcohol, ether or hexane. The pure benzoxazinone derivative can be easily isolated by separating the precipitated crystals by cooling depending on the conditions.

In the novel benzoxazinone derivative represented by the general formula (I) according to the present invention which can be produced in this manner, the alkyl group represented by R ¹ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, isobutyl group, sec-butyl group, tert-butyl group,
Examples thereof include a pentyl group, an isopentyl group, a hexyl group, and an isohexyl group. The lower alkyl group represented by R ² includes a methyl group, an ethyl group, a propyl group,
Examples thereof include an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, an isopentyl group, a hexyl group and an isohexyl group. The carbon number of the alkyl part of the cyanoalkyl group is preferably 1 to
4, more preferably 1-2. The cyano group may be substituted at the terminal of the alkyl group or at a position other than the terminal. As the cyanoalkyl group, a cyanomethyl group, 1-
Examples thereof include a cyanoethyl group, a 2-cyanoethyl group and a 3-cyanopropyl group. The alkenyl group preferably has 3 to 6 carbon atoms, and more preferably 3 to 4 carbon atoms. Examples of the alkenyl group include allyl group, methallyl group, crotyl group, 1-methylallyl group, prenyl group, 3-methyl-3-butenyl group, 3-pentenyl group and the like. The carbon number of the alkynyl group is preferably 3 to
6, more preferably 3-4. As the alkynyl group, a propargyl group, a 1-methylpropargyl group, a 1-
Ethylpropargyl group, 2-butynyl group, 1-methyl-
2-butynyl group, 3-pentynyl group, 3-butynyl group,
A 2-pentynyl group etc. can be illustrated. Also,
The carbon number of the aralkyl group is preferably 7-10, more preferably 7-8. The aromatic ring may be unsubstituted or substituted with halogen, a lower alkyl group or the like. Examples of the aralkyl group include a benzyl group, a phenethyl group, a p-fluorobenzyl group and a p-chlorobenzyl group.

Representative examples of the novel benzoxazinone derivatives of the present invention are shown in Table 1.

Hereinafter, the production of the active compound of the present invention will be described in detail with reference to production examples. Further, with respect to the compounds synthesized based on the production examples, melting points, elemental analysis values, respective spectrum data, etc. are summarized in Tables 2 and 3.

Production Example 1 3- (2,4-difluoro-5) in a 100 ml eggplant-shaped flask
-Nitrophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (4.1 g, 13.6 mmol) and ethyl glycolate (20 ml) were added and triethylamine (4 ml) was added dropwise with stirring at room temperature. After stirring at room temperature overnight, 1N acetic acid was added to the reaction mixture. This was extracted with ethyl acetate (20 ml x 3) and the organic layer was washed with water (10 ml x 3). The obtained ethyl acetate solution was dried over anhydrous magnesium sulfate. The desiccant was removed and the solvent was evaporated under reduced pressure to give a yellow oil (6.5 g). This was isolated and purified using silica gel column chromatography to give a white solid (3.
68g) was obtained. This product was analyzed by ¹ H-NMR, IR spectrum and the like, and as a result, 3- (2-fluoro-4-ethoxycarbonylmethyloxy-5-nitrophenyl) -5-isopropylidene-1,3-oxazolidine-2,4 was obtained. -Confirmed to be Zion. ¹ H-NMR (CDCl ₃ ): δ1.28 (3H, t, J = 7.5Hz), 2.03 (3
H, s), 2.26 (3H, s), 4.25 (2H, q, J = 7.5Hz), 4.78 (2H,
s), 6.88 (1H, d, J _HF = 11.1Hz), 8.00 (1H, d, J _HF = 7.5H
z), ppm 300c equipped with stirrer, dropping funnel and jim funnel
Reduced iron (6.8 g) was placed in the three-necked flask of c, acetic acid (20 ml) was added, and the mixture was heated under reflux until it became a white suspension.
3- (2-Fluoro-4-ethoxycarbonylmethyloxy-5-nitrophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (2.76) obtained in (a)
A solution of g, 7.2 mmol) in ethyl acetate (10 ml) was added dropwise under reflux. After completion of dropping, the mixture was further stirred under reflux for 1 hour, and after cooling, insoluble matter in the system was removed. 1N hydrochloric acid (50 ml) was added to the resulting solution.
Was added and extracted with ethyl acetate (50 ml × 3). The organic layer was washed with water (10 ml x 3) and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was removed under reduced pressure to obtain a light brown solid (2.1 g). This is ¹ H-NMR,
From the results of analysis such as IR spectrum, 3- (7-fluoro-
2H-1,4-benzoxazin-3 (4H) -one-6-yl) -5-isopropylidene-1,3-oxazolidine-
It was confirmed to be 2,4-dione (Compound 1).

Production Example 2 3- (2,4-difluoro-5) in a 100 ml eggplant-shaped flask
-Nitrophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (3.0 g, 10 mmol) and (-)-ethyl lactate (15 ml) were added and triethylamine (4 ml) was added dropwise with stirring at room temperature. did. After stirring at room temperature overnight, 1N hydrochloric acid was added to the reaction mixture. This was extracted with ethyl acetate (10 ml x 3) and the organic layer was water (5 ml x 3).
And washed. The obtained ethyl acetate solution was dried over anhydrous magnesium sulfate. The desiccant was removed and the solvent was evaporated under reduced pressure to give a yellow oil (5.7 g). This was recrystallized from ethyl acetate-hexane to obtain a yellow transparent solid (1.16 g). Recrystallization from the mother liquor gave a yellow solid (752 mg). This product was analyzed by ¹ H-NMR, IR spectrum and the like, and was found to be (+)-3- {2-fluoro-4- (1-ethoxycarbonyl) ethyloxy-5-nitrophenyl} -5-
It was confirmed to be isopropylidene-1,3-oxazolidine-2,4-dione. ¹ H-NMR (CDCl ₃ ): δ1.27 (3H, t, J = 6.6Hz), 1.71 (3
H, d, J = 6.3Hz), 2.06 (3H, s), 2.28 (3H, s), 4.23 (2H,
q, J = 6.6Hz), 4.82 (1H, q, J = 6.3Hz), 6.82 (1H, d, J _HF
= 11.1Hz), 8.31 (1H, d, J _HF = 8.1Hz), ppm. 300c equipped with stirrer, dropping funnel and jim funnel
Reduced iron (3.8 g) was placed in the three-necked flask of c, then acetic acid (30 ml) was added, and the mixture was heated under reflux until it became a white suspension.
(+)-3- {2-Fluoro-4- (1-) obtained in (a)
Ethoxycarbonyl) ethyloxy-5-nitrophenyl} -5-isopropylidene-1,3-oxazolidine-
A solution of 2,4-dione (1.1 g, 2.8 mmol) in ethyl acetate (20 ml) was added dropwise under reflux. After completion of dropping, the mixture was further stirred under reflux for 1 hour, and after cooling, insoluble matter in the system was removed. 1N Hydrochloric acid (50 ml) was added to the obtained solution, and the mixture was extracted with ethyl acetate (50 ml × 3). The organic layer was washed with water (10 ml x 3) and then dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give a light brown solid (0.91g). This one is ¹ H-N
From the results of analysis of MR and IR spectra, etc.
-Fluoro-2-methyl-2H-1,4-benzoxazin-3 (4H) -one-6-yl) -5-isopropylidene-1,3-oxazolidin-2,4-dione (Compound 2) It was confirmed.

Production Example 3 In a 25 ml eggplant-shaped flask, 3- (7-fluoro-2-1,
4-benzoxazin-3 (4H) -one-6-yl)-
5-isopropylidene-1,3-oxazolidine-2,4-dione (130 mg, 0.42 mmol) and potassium carbonate (130 mg)
Was added and dissolved in N, N-dimethylformamide (5 ml). While stirring the solution at room temperature, methyl iodide (500
μ) was added dropwise. The mixture was further stirred at room temperature for 3 hours. After completion of the reaction, 1N hydrochloric acid was added thereto, and the mixture was extracted with ethyl acetate (2 ml × 3). The organic layer was washed with water (1 ml × 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a brown oil (250mg). This was isolated and purified using silica gel column chromatography to obtain a white solid (123 mg).
This product is 3 from the result of analysis such as ¹ H-NMR and IR spectrum.
-(7-Fluoro-4-methyl-2H-1,4-benzoxazin-3 (4H) -one-6-yl) -5-isopropylidene-1,3-oxazolidin-2,4-dione (Compound 3 ) Was confirmed.

Production Example 4 In a 25 ml eggplant-shaped flask, 3- (7-fluoro-2H-1,
4-benzoxazin-3 (4H) -one-6-yl)-
5-isopropylidene-1,3-oxazolidine-2,4-dione (200 mg, 0.65 mmol) and potassium carbonate (200 mg)
Was added and dissolved in N, N-dimethylformamide (2 ml). While stirring the solution at room temperature, hexyl iodide (50
0 μ) was added dropwise. The mixture was further stirred at room temperature for 5 hours. After completion of the reaction, 1N hydrochloric acid was added thereto, and the mixture was extracted with ethyl acetate (2 ml × 3). The organic layer was washed with water (1 ml × 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a brown oil (102 mg). This was isolated and purified using silica gel column chromatography to obtain a white solid (79 mg).
This product is 3 from the result of analysis such as ¹ H-NMR and IR spectrum.
-(7-Fluoro-4-hexyl-2H-1,4-benzoxazin-3 (4H) -one-6-yl) -5-isopropylidene-1,3-oxazolidin-2,4-dione (Compound 4 ) Was confirmed.

Production Example 5 In a 25 ml eggplant-shaped flask, 3- (7-fluoro-2H-1,
4-benzoxazin-3 (4H) -one-6-yl)-
5-Isopropylidene-1,3-oxazolidine-2,4-dione (200 mg, 0.64 mmol) and potassium carbonate (200 mg)
Was added and dissolved in N, N-dimethylformamide (5 ml). While stirring the solution at room temperature, allyl bromide (500
μ) was added dropwise. Further, this mixture was stirred at room temperature for 4 hours, 1N hydrochloric acid was added after the reaction was completed, and ethyl acetate (2 ml x
Extracted in 3). The organic layer was washed with water (1 ml × 3) and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure to give a brown oil (138 mg). This was isolated and purified using silica gel column chromatography to obtain a white solid (97 mg). This product was analyzed by ¹ H-NMR, IR spectra, etc. to show 3- (4-allyl-7-fluoro-2H-1,4-benzoxazin-3 (4H) -one-6-
It was confirmed to be (yl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (Compound 5).

Production Example 6 In a 25 ml eggplant-shaped flask, 3- (7-fluoro-2H-1,
4-benzoxazin-3 (4H) -one-6-yl)-
5-Isopropylidene-1,3-oxazolidine-2,4-dione (200 mg, 0.64 mmol) and potassium carbonate (200 mg)
Was added and dissolved in N, N-dimethylformamide (2 ml). While stirring the solution at room temperature, benzyl bromide (50
0 μ) was added dropwise. The mixture was further stirred at room temperature for 6 hours. After the reaction was completed, 1N hydrochloric acid was added, and ethyl acetate (2 ml
× 3). The organic layer was washed with water (1 ml x 3),
It was dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a brown oil (240 m
g) was obtained. This was isolated and purified using silica gel column chromatography to obtain a white solid (153 mg). This product was analyzed by ¹ H-NMR, IR spectra, etc.
(4-Benzyl-7-fluoro-2H-1,4-benzoxazin-3 (4H) -one-6-yl) -5-isopropylidene-1,3-oxazolidin-2,4-dione (Compound 6) Was confirmed.

Production Example 7 In a 25 ml eggplant-shaped flask, 3- (7-fluoro-2H-1,
4-benzoxazin-3 (4H) -one-6-yl)-
5-Isopropylidene-1,3-oxazolidine-2,4-dione (200 mg, 0.64 mmol) and potassium carbonate (200 mg)
Was added and dissolved in N, N-dimethylformamide (2 ml). The 2-chlorobutene (60
0 μ) was added dropwise. The mixture was further stirred at room temperature for 12 hours. After the reaction was completed, 1N hydrochloric acid was added and ethyl acetate (2 ml x
Extracted in 3). The organic layer was washed with water (1 ml × 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a brown oil (10
5 mg). This was isolated and purified using silica gel column chromatography to obtain a white solid (74 mg). This one
^From the results of analysis of ¹ H-NMR, IR spectrum, etc., 3- {4-
(E) -Crotyl-7-fluoro-2H-1,4-benzoxazin-3 (4H) -one 6-yl} -5-isopropylidene-1,3-oxazolidin-2,4-dione (Compound 7) Was confirmed.

Production Example 8 In a 25 ml eggplant-shaped flask, 3- (7-fluoro-2H-1,
4-benzoxazin-3 (4H) -one-6-yl)-
5-Isopropylidene-1,3-oxazolidine-2,4-dione (347 mg, 1.13 mmol) and potassium carbonate (100 mg)
Was added and dissolved in N, N-dimethylformamide (30 ml). Propargyl bromide (200 μ) was added dropwise while stirring the solution at room temperature. The mixture was further stirred at room temperature for 5 hours. After the reaction was completed, 1N hydrochloric acid was added thereto, and the mixture was allowed to stand at room temperature and the precipitated crystal (345 mg) was isolated by filtration. This product was analyzed by analysis of ¹ H-NMR, IR spectrum, etc. to give 3- (7-fluoro-4-propargyl-2H-1,4-
Benzoxazin-3 (4H) -one-6-yl) -5-
It was confirmed to be isopropylidene-1,3-oxazolidine-2,4-dione (Compound 8).

Production Example 9 (+)-3- (7-Fluoro-2-methyl-2H-1,4-benzoxazine-3 (4H) in a 25 ml eggplant-shaped flask.
-On-6-yl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (200 mg, 0.62 mmol) and potassium carbonate (200 mg) were added and dissolved in N, N-dimethylformamide (2 ml). Let Methyl iodide (500 μ) was added dropwise while stirring the solution at room temperature. The mixture was further stirred at room temperature for 3 hours. After completion of the reaction, 1N hydrochloric acid was added thereto, the mixture was allowed to stand at room temperature and the precipitated crystal (184 mg) was isolated by filtration. This product was analyzed by ¹ H-NMR, IR spectrum and the like, and was found to be (+)-3- (7-fluoro-2,4-dimethyl-2H-1,4-benzoxazin-3 (4H) -one-6 -Yl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (Compound 9).

Production Example 10 (+)-3- (7-Fluoro-2-methyl-2H-1,4-benzoxazine-3 (4H) in a 25 ml eggplant-shaped flask.
-On-6-yl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (123 mg, 0.4 mmol) and potassium carbonate (130 mg) were added and dissolved in N, N-dimethylformamide (4 ml). Let Hexyl iodide (500 μ) was added dropwise while stirring the solution at room temperature. The mixture was further stirred at room temperature for 3 hours. After completion of the reaction, 1N hydrochloric acid was added thereto and extracted with ethyl acetate (3 ml × 3). The organic layer was washed with water (2 ml × 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a brown oil (108mg). This was isolated and purified using silica gel column chromatography to obtain a white solid (81 mg). This product is (+)-3- (7-fluoro-4-hexyl-2-methyl-2H-1,4-benzoxazine-3 based on the results of analysis such as ¹ H-NMR and IR spectrum.
(4H) -on-6-yl) -5-isopropylidene-1,
It was confirmed to be 3-oxazolidine-2,4-dione (Compound 10).

Production Example 11 (+)-3- (7-Fluoro-2-methyl-2H-1,4-benzoxazine-3 (4H) in a 25 ml eggplant-shaped flask.
-On-6-yl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (200 mg, 0.62 mmol) and potassium carbonate (200 mg) were added and dissolved in N, N-dimethylformamide (2 ml). Let Allyl bromide (500 μ) was added dropwise while stirring the solution at room temperature. The mixture was further stirred at room temperature for 3 hours. After completion of the reaction, 1N hydrochloric acid was added thereto and extracted with ethyl acetate (3 ml × 3). The organic layer was washed with water (2 ml × 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a brown oil (252 mg). This was isolated and purified using silica gel column chromatography to obtain a white solid (173 mg). This product was analyzed by ¹ H-NMR, IR spectrum and the like, and was found to be (+)-3- (4-allyl-7-fluoro-2-methyl-2H-1,4-benzoxazine-3 (4
H) -one-6-yl) -5-isopropylidene-1,3-
It was confirmed to be oxazolidine-2,4-dione (Compound 11).

Production Example 12 (+)-3- (7-Fluoro-2-methyl-2H-1,4-benzoxazine-3 (4H) in a 25 ml eggplant-shaped flask.
-On-6-yl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (163 mg, 0.51 mmol) and potassium carbonate (140 mg) were added and dissolved in N, N-dimethylformamide (5 ml). Let Propargyl bromide (300 μ) was added dropwise while stirring the solution at room temperature. The mixture was further stirred at room temperature for 5 hours. After the reaction was completed, 1N hydrochloric acid was added to this, and the mixture was left at room temperature to precipitate crystals (167 m
g) was isolated by filtration. This product was analyzed from the results of ¹ H-NMR, IR spectrum, etc., and was identified as (+)-3- (7-fluoro-2-methyl-4-propargyl-2H-1,4-benzoxazin-3 (4H) -one. -6-yl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (compound
12) was confirmed.

Production Example 13 In a 100 cc eggplant-shaped flask, 6-amino-7-fluoro-4-isopropyl-2H-1,4-benzoxazine-3 was added.
(4H) -one (3.24 g, 14.0 mmol) was added and ethyl acetate (10
0 ml). Phosgene dimer (trichloromethyl chloroformate) (5.0 ml) was added, and ethyl acetate was distilled off while reacting with heating until the solution reached about 10 ml.
After cooling, carbon tetrachloride (30 ml) was added, a slightly precipitated solid was separated, and the solvent was distilled off from the solution under reduced pressure. The light brown solid obtained was almost pure 7-fluoro-6-isocyanato-4-isopropyl-2H-1,4-benzoxazine-.
It was confirmed to be 3 (4H) -one by ¹ H-NMR spectrum. Then the isocyanate (3.4 g, 13.6 mmol) thus obtained and 2-hydroxy-3-methyl-3
-Methyl butenoate (2.3 g, 17.7 mmol) was placed in a 200 cc eggplant-shaped flask and dissolved in a mixed solvent of diethyl ether (70 ml) and tetrahydrofuran (25 ml). Then, triethylamine (2.5 ml) was added and the mixture was stirred at room temperature for 2 hours.
After completion of the reaction, the solution was washed with 1N hydrochloric acid, and the organic layer was dried over anhydrous magnesium sulfate. After separating the drying agent, the solution was concentrated under reduced pressure to obtain a pale yellow oily substance. This was isolated and purified by silica gel column chromatography to obtain a colorless oil (2.99 g). This product was confirmed to be 2- {N- (7-fluoro-4-) from the results of analysis such as ¹ H-NMR and IR spectrum.
Isopropyl-2H-1,4-benzoxazine-3 (4H)
-On-6-yl) carbamoyloxy} -3-methyl-
It was confirmed to be methyl 3-butenoate. ¹ H-NMR (CDCl ₃ ): δ1.51 (6H, d, J = 6.9Hz), 1.82 (3
H, s), 3.68 (3H, s), 4.45 (2H, s), 4.75 (1H, sep, J = 6.
9Hz), 5.14 (1H, brs), 5.22 (1H, brs), 5.51 (1H, s),
6.76 (1H, d, J _HF = 10.8Hz), 7.03 (1H, br), 7.97 (1H, d,
J _HF = 8.1Hz), pmm. 2- {N- (7-fluoro-4-isopropyl-2H-1,4-benzoxazine-3 was added to a 100 ml eggplant-shaped flask.
Methyl (4H) -on-6-yl) carbamoyloxy} -3-methyl-3-butenoate (1.48 g, 3.89 mmol) and potassium carbonate (537 mg, 3.89 mmol) were added and acetonitrile (45
ml)). The solution was stirred at room temperature for 12 hours, 1N hydrochloric acid was added, and the mixture was extracted with ethyl acetate (15 ml × 3).
The organic layer was washed with water (7 ml x 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a pale yellow oil. This was recrystallized from methanol to obtain a white solid (923 mg). This one is ¹ H
-(7-fluoro-4-isopropyl-2H-1,4-benzoxazin-3 (4H) -on-6-yl) -5-isopropylidene-1, from the results of analysis of NMR, IR spectrum, etc. It was confirmed to be 3-oxazolidine-2,4-dione (Compound 13).

Production Example 14 In a 25 ml eggplant-shaped flask, 3- (7-fluoro-2H-1,
4-benzoxazin-3 (4H) -one-6-yl)-
5-Isopropylidene-1,3-oxazolidine-2,4-dione (500 mg, 1.63 mmol) and potassium carbonate (500 mg) were added and dissolved in N, N-dimethylformamide (5 ml). Chloroacetonitrile (135 mg) was added dropwise with stirring the solution at room temperature. Further, this solution was stirred at room temperature for 3 hours, 1N hydrochloric acid was added after completion of the reaction, and ethyl acetate (5 ml x
Extracted in 3). The organic layer was washed with water (2 ml × 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a pale yellow oil (511 mg).
I got This was isolated and purified using silica gel column chromatography to obtain a white solid (353 mg). This product was analyzed by ¹ H-NMR, IR spectra, etc.
Cyanomethyl-7-fluoro-2H-1,4-benzoxazin-3 (4H) -one-6-yl) -5-isopropylidene-1,3-oxazolidin-2,4-dione (Compound 14)
Was confirmed.

Production Example 15 In a 25 ml eggplant-shaped flask, 3- (7-fluoro-2H-1,
4-benzoxazin-3 (4H) -one-6-yl)-
5-Isopropylidene-1,3-oxazolidine-2,4-dione (400 mg, 1.31 mmol) and potassium carbonate (400 mg) were added and dissolved in N, N-dimethylformamide (4 ml). 2-Bromopropionitrile (350 mg) was added dropwise with stirring the solution at room temperature. Add this solution at room temperature to 2
After stirring for 4 hours, 1N hydrochloric acid was added after the reaction was completed, and ethyl acetate (4
ml × 3). The organic layer was washed with water (2 ml × 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the resulting solution was concentrated under reduced pressure to give a pale yellow oil. This was isolated and purified using silica gel column chromatography to obtain a white solid (170 mg). This one is ¹
From the results of analysis such as H-NMR and IR spectrum, 3- {4-
(1-Cyanoethyl) -7-fluoro-2H-1,4-benzoxazin-3 (4H) -one-6-yl} -5-isopropylidene-1,3-oxazolidin-2,4-dione (Compound 15 ) Was confirmed.

Production Example 16 Add 3- (2,4-difluoro-5) to a 50cc eggplant-shaped flask.
-Nitrophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (304 mg, 1.02 mmol) and glycolic acid (203 mg, 2.67 mmol) were added, and the mixture was heated and melted on an oil bath at 100 ° C. Then triethylamine (0.5 ml)
Was added dropwise, and the mixture was further stirred at 100 ° C. for 1 hour. After the reaction, 1N hydrochloric acid (25 ml) and water (25 ml) were added to the mixture and the mixture was extracted with ethyl acetate (25 ml × 3). The organic layer was washed with water (25 ml × 3) and dried over anhydrous magnesium sulfate. The desiccant was removed and the solvent was evaporated under reduced pressure to give a yellow oil (168 mg). This product was analyzed by ¹ H-NMR, IR spectra, etc.
(2-Fluoro-4-hydroxycarbonylmethyloxy-5-nitrophenyl) -5-isopropylidene-1,
It was confirmed to be 3-oxazolidine-2,4-dione. ¹ H-NMR (CDCl ₃ ): δ2.08 (3H, s), 2.30 (3H, s), 4.88
(2H, s), 7.07 (1H, d, J = 10.0Hz), 8.21 (1H, d, J = 7.0H
z), 10.9 (1H, br s), ppm. IR (neat): 1810,1730,1685cm ^-1 . Add 3- (2,4-difluoro-5) to a 50cc eggplant-shaped flask.
-Nitrophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (308 mg, 1.03 mmol) and glycolic acid (81 mg, 1.01 mmol) were added and dissolved in N, N-dimethylformamide (10 ml). did. Triethylamine (0.3 ml) was further added, and the mixture was stirred at 100 ° C. for 7 hours, 1N hydrochloric acid (25 ml) and water (25 ml) were added, and the mixture was extracted with ethyl acetate (25 ml × 4). The organic layer was saturated saline (25m
It was washed with l) and dried over anhydrous magnesium sulfate. The desiccant was removed, and the solvent was evaporated under reduced pressure to give a yellow oil (80 mg). This product was analyzed by ¹ H-NMR, IR spectra, etc. to give 3- (2-fluoro-4-hydroxycarbonylmethyloxy-5-nitrophenyl) -5-
It was confirmed to be isopropylidene-1,3-oxazolidine-2,4-dione.

50 ml equipped with stirrer, dropping funnel and jim funnel
Put reduced iron (1.4g) into a 3-necked flask, and add acetic acid (10m
l) was added and the mixture was heated to reflux until it became a white suspension. Then, a solution of 3- (2-fluoro-4-hydroxycarbonylmethyloxy-5-nitrophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (168 mg) in acetic acid (10 ml) was added dropwise. After completion of dropping, the mixture was stirred at 80 ° C. for 3 hours, and after cooling, the insoluble matter in the system was removed. Water in liquid (50 ml)
Was added and extracted with ethyl acetate (20 ml × 4 times). The organic layer was washed with water (20 ml) and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was removed under reduced pressure to obtain a light brown solid (80 mg). This product was analyzed by analysis of ¹ H-NMR, IR spectrum, etc. to give 3- (7-fluoro-2H
1,4-benzoxazin-3 (4H) -on-6-yl)
-5-isopropylidene-1,3-oxazolidine-2,4-
It was confirmed to be dione (Compound 1).

Production Example 17 3- (2,4-difluoro-5-nitrophenyl) -5
-Isopropylidene-1,3-oxazolidine-2,4-dione (298 mg, 1.0 mmol), methyl 2-hydroxyisovalerate (1.0 g, 7.6 mmol) and triethylamine (0.3 ml)
The mixture was reacted overnight at 2500 atm with a high pressure reactor at room temperature. After the reaction was completed, 0.1N hydrochloric acid (50 ml) was added to the mixture and the mixture was extracted with ethyl acetate (25 ml × 2). Water the organic layer (20
After washing with ml × 5), it was dried over anhydrous magnesium sulfate. The desiccant was removed and the solvent was evaporated under reduced pressure to give a pale yellow oil. This was isolated and purified using silica gel column chromatography to obtain a white solid (319 mg). This product was analyzed by ¹ H-NMR, IR spectra, etc., and was found to be 3- {2-fluoro-4- (1-methoxycarbonyl) isobutyloxy-5-nitrophenyl} -5-
It was confirmed to be isopropylidene-1,3-oxazolidine-2,4-dione. ¹ H-NMR (CDCl ₃ ): δ1.03 (6H, d, J = 6.0Hz), 1.98 (3
H, s), 2.20 (3H, s), 2.30 (1H, m), 3.70 (3H, s), 4.47
(1H, d, J = 5.0Hz), 6.68 (1H, d, J _HF = 11.0Hz), 7.98 (1
H, d, J _HF = 8.0Hz), pmm. IR (neat): 2980,1820,1760,1745cm ^-1 . 50 ml equipped with stirrer, dropping funnel and jim funnel
Reduced iron (1.2 g, 20 mmol) was placed in the three-necked flask, and acetic acid (10 ml) was added, and the mixture was heated under reflux until it became a white suspension.
3- {2-fluoro-4- (1-methoxycarbonyl)
Isobutyloxy-5-nitrophenyl} -5-isopropylidene-1,3-oxazolidine-2,4-dione (253m
A solution of g, 0.62 mmol) in acetic acid (10 ml) was added dropwise under reflux.
After completion of dropping, the mixture was further stirred under reflux for 1 hour, and after cooling, insoluble matter in the system was removed. 1N Hydrochloric acid (25 ml) was added to the obtained solution, and the mixture was extracted with ethyl acetate (25 ml × 3). The organic layer was washed with water (10 ml x 3) and then dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain a light brown solid, which was then reprecipitated from hexane to obtain a light brown solid. This product was analyzed by ¹ H-NMR, IR spectra, etc. to give 3- (7-fluoro-2-isopropyl-2H-1,4-
Benzoxazin-3 (4H) -one-6-yl) -5-
It was confirmed to be isopropylidene-1,3-oxazolidine-2,4-dione (Compound 16).

The thus obtained novel benzoxazinone derivative according to the present invention has excellent performance as a herbicide as described above.

When the novel benzoxazinone derivative is used as a herbicide, it can be used as it is, but generally, one or several auxiliary agents can be mixed and used as a herbicide. Usually, as an auxiliary agent, various carriers, bulking agents,
It is preferred to mix and use a solvent, a surfactant, a stabilizer and the like and formulate into a form such as a wettable powder, an emulsion, a powder and a granule by a conventional method before use.

Examples of the solvent which is one of the auxiliary agents in the herbicide of the present invention containing a novel benzoxazinone derivative as an active ingredient include, for example, water, alcohols, ketones, ethers, aliphatic and aromatic hydrocarbons, and halogenated carbon. Hydrogen, acid amides, esters, nitriles and the like are suitable, and one kind or a mixture of two or more kinds thereof is used.

As the extender, clay such as kaolin and bentonite, talc such as talc and pyrophyllite, diatomaceous earth, mineral powder such as oxide such as white carbon and soybean powder, CM
Vegetable powder such as C is used. Further, a surfactant may be used as a spreading agent, a dispersant, an emulsifier, and a penetrant. Examples of the surfactant include nonionic surfactants, cationic surfactants and amphoteric surfactants. These surfactants are utilized as one kind or a mixture of two or more kinds depending on the application.

Preferable use of the herbicide of the present invention having a novel benzoxazinone derivative as an active ingredient includes soil treatment, water surface treatment, foliage treatment, etc. Can be effective.

In addition, the herbicide of the present invention containing a novel benzoxazinone derivative as an active ingredient is another active ingredient which does not inhibit the herbicidal activity of the present active ingredient, such as other herbicides, insecticides, fungicides, plant growth. It is also possible to use a mixture of regulators or the like or to use together.

Next, the present invention will be described in more detail with reference to Examples of the herbicide of the present invention containing a novel benzoxazinone derivative as an active ingredient and test examples in which the herbicidal effect of the present herbicide was examined. The parts are parts by weight.

Example 1 (Emulsion) 20 parts of compound 1, 35 parts of xylene, 40 parts of cyclohexanone
And 5 parts of Solbol 900A (manufactured by Toho Chemical Co., Ltd.) were uniformly mixed to obtain an emulsion. Other compounds were processed in the same manner as above to obtain emulsions.

Example 2 (wettable powder) 50 parts of the compound 1 of the present invention, 25 parts of diatomaceous earth, 22 parts of clay,
A mixture of 3 parts of Lunox R100C (manufactured by Toho Kagaku Co., Ltd.) was uniformly mixed and pulverized, and then a predetermined amount of water was added to obtain a wettable powder. Other compounds were treated in the same manner as above to obtain a wettable powder.

Example 3 (Granule) A mixture of 5 parts of compound 1, 35 parts of bentonite, 55 parts of talc, and 5 parts of sodium lignin sulfonate was uniformly mixed and pulverized, and then water was added and kneaded, and granulated by an extrusion granulator. After being made into a granule, it was dried and granulated to obtain a granule. Other compounds were treated in the same manner as above to obtain granules.

Test Example 1 (Effect on paddy field weeds) Wagner pots of 1 / 5,000 are were filled with paddy soil, and seeds of millet, eel and lythrum and 2
Rice seedlings (variety: Nipponbare) at the 3rd leaf stage were sowed or transplanted and kept in a moist state. After 5 days, the water entered to a depth of 4 cm. Thereafter, the novel benzoxazinone derivative according to the present invention, which was made into a wettable powder or an emulsion according to the examples, was used for 20, 10,
A predetermined amount of the diluted solution was surface-treated on the water so that the amount became 5 g.

On the 20th day after the treatment, the herbicidal effect on the test plant and the phytotoxicity against rice were investigated by the following criteria,
The results in Table 4 were obtained.

Test Example 2 (Effects on field weeds) Field soil was packed in a vat having an area of 16 × 11 cm ² and a depth of 7 cm, and seeds of crabgrass, chrysalis, Inubiyu, and soybean were sowed on the vat, and 1 cm of soil was covered thereon. . The next day, a predetermined amount of the diluting solution was evenly sprayed on the soil cover so that the benzoxazinone derivative according to the present invention, which was made into a wettable powder or an emulsion according to the example, was 20,10,5 g per are. Twenty days after the treatment, the herbicidal effect on the test weeds and the phytotoxicity on soybeans were examined in the same manner as in Test Example 1. Table 5 shows the results.

Test Example 3 (Effect of foliage treatment) A bat having an area of 16 × 11 cm ² and a depth of 7 cm was filled with field soil, and sowing seeds of sorghum, chrysalis, indica, and corn were sown on the foliage of a plant grown 15 days later. The portion was spray-treated with a predetermined concentration of a wettable powder according to the example or a dilute solution of the benzoxazinone derivative according to the present invention, which was made into an emulsion, with a water amount of 10 liters per are. On the 20th day after the treatment, the herbicidal effect against the test weeds and the phytotoxicity against corn were examined in the same manner as in Test Example 1. Table 6 shows the results.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Sato 1963-4, Yawata Kaigan-dori, Ichihara-shi, Chiba (72) Inventor Hiroaki Hirose 2-17 Tatsumidai-higashi, Ichihara-shi, Chiba A-208 (72) Inventor Yokota Masahiro 2-17 Tatsumidaito, Ichihara-shi, Chiba A-204 (72) Inventor Shoin Nagato 3-13-13-106 (56) Kahama, Adachi-ku, Tokyo (56) Reference JP-A-1-308278 (JP, A)

Claims (1)

(57) [Claims] 1. An agriculturally acceptable carrier or diluent and a general formula [In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² represents a hydrogen atom, an alkyl group, a cyanoalkyl group, an alkenyl group, an alkynyl group or an aralkyl group. ] The herbicide consisting of the benzoxazinone derivative shown by these.