Patent Grant
6841519
The present invention relates to a novel isoxazoline derivative and a herbicide containing it as the active ingredient.
The herbicidal activities of isoxazoline derivatives are reported in, for example, JP-A-8-225548, JP-A-9-328477 and JP-A-9-328483. The compounds described in these literatures have a chloromethyl group mainly at the 5-position of the isoxazoline ring, and the isoxazoline derivative of the present invention has been unknown.
Herbicides used for useful crops are desired to be applied to soil or foliage, show a sufficient herbicidal effect at a low amount, and exhibit high selectivity between crop and weeds. The compounds described in the above literatures are not fully satisfactory in these respects.
In view of the above situation, the present inventors made a study on herbicidal effect and selectivity between crop and weeds. As a result, the present inventors found out that a novel isoxazoline derivative is superior in herbicidal effect and selectivity between crop and weeds. The present invention has been completed based on the finding.
The present invention provides:
The definitions of the terms used in the present specification are given below.
“Halogen atom” refers to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
“Alkyl group” refers to a C1 to C10 straight or branched chain alkyl group unless other wise specified; and there can be mentioned, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group, heptyl group and octyl group.
“Cycloalkyl group” refers to a C3 to C8 cycloalkyl group; and there can be mentioned, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
“Alkoxy group” refers to an (alkyl)-O- group wherein the alkyl moiety has the above definition; and there can be mentioned, for example, methoxy group and ethoxy group.
“Alkylthio group”, “alkylsulfinyl group” and “alkylsulfonyl group” refer, respectively, to an (alkyl)-S— group, an (alkyl)-SO— group and an (alkyl)-SO2— group, in each of which the alkyl moiety has the above definition; and there can be mentioned, for example, methylthio group, ethylthio group, methylsulfinyl group, methylsulfonyl group and ethylsulfonyl group.
“Alkenyl group” refers to a C2 to C6 straight or branched chain alkenyl group; and there can be mentioned, for example, ethenyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 2-pentenyl group.
“Alkynyl group” refers to a C2 to C6 straight or branched chain alkynyl group; and there can be mentioned, for example, ethinyl group, 2-propynyl group, 2-butinyl group and 3-butinyl group.
“Alkenyloxy group” and “alkynyloxy group” refer, respectively, to an (alkenyl)-O— group and an (alkynyl)-O— group, in each of which the alkenyl or alkynyl moiety has the above definition; and there can be mentioned, for example, 2-propenyloxy group and 2-propynyloxy group.
“Alkylamino group” and “dialkylamino group” refer, respectively, to an (alkyl)-NH— group and an (alkyl)2—N— group, in each of which the alkyl moiety has the above definition; and there can be mentioned, for example, methylamino group, ethylamino group and dimethylamino group.
“Alkylcarbonyl group”, “(alkylthio)carbonyl group”, “alkoxycarbonyl group”, “alkylaminocarbonyl group” and “dialkylaminocarbonyl group” refer, respectively, to an (alkyl)-CO— group, an (alkylthio)-CO— group, an (alkoxy)-CO— group, an (alkylamino)-CO— group and a (dialkylamino)-CO— group, in each of which the alkyl, alkylthio, alkoxy, alkylamino or dialkylamino moiety has the above definition; and there can be mentioned, for example, acetyl group, methylthiocarbonyl group, ethoxycarbonyl group, methoxycarbonyl group, methylaminocarbonyl group and dimethylaminocarbonyl group.
“Alkylaminocarbonylamino group”, “dialkylaminocarbonylamino group” and “alkoxycarbonylamino group” refer, respectively, to an (alkylaminocarbonyl)-NH— group, a (dialkylaminocarbonyl)-NH— group and an (alkxoycarbonyl)-NH— group, in each of which the alkylaminocarbonyl, dialkylaminocarbonyl or alkoxycarbonyl moiety has the above definition; and there can be mentioned, for example, methylaminocarbonylamino group, dimethylaminocarbonylamino group and methoxycarbonylamino group.
“Optionally substituted phenyl group” includes phenyl groups each having, on the phenyl ring, 1 to 5 substituents such as halogen atom(s), C1 to C6 alkyl group(s), C1 to C6 alkoxy group(s) and the like.
“Optionally substituted phenoxy group” includes phenoxy groups each having, on the phenyl ring, 1 to 5 substituents such as halogen atom (s), C1 to C6 alkyl group(s), C1 to C6 alkoxy group(s) and the like.
“Optionally substituted benzyloxy group” includes benzyloxy groups each having, on the phenyl ring and at the benzylic position, 1 to 7 substituents such as halogen atom(s), C1 to C6 alkyl group(s), C1 to C6 alkoxy group(s) and the like.
“Optionally substituted phenoxycarbonyl group” includes phenoxycarbonyl groups each having, on the phenyl ring, 1 to 5 substituents such as halogen atom(s), C1 to C6 alkyl group(s), C1 to C6 alkoxy group(s) and the like.
“Salt” refers to a salt between the carboxyl group, sulfonyl group, hydroxyl group, amino group or other group present in the compound of the general formula [1] and a metal, an organic base, an organic acid or an inorganic acid. As the metal, there can be mentioned alkali metals such as sodium, potassium and the like, and alkaline earth metals such as magnesium, calcium and the like. As the organic base, there can be mentioned triethylamine, diisopropylamine, etc. As the organic acid, there can be mentioned acetic acid, oxalic acid, maleic acid, p-toluenesulfonic acid, etc. As the inorganic acid, there can be mentioned hydrochloric acid, sulfuric acid, nitric acid, etc.
Preferable examples of the compound of the general formula [I] are those compounds wherein R1 and R2 are a C1 to C3 alkyl group or a C1 to C3 alkoxyalkyl group, R3 and R4 are a hydrogen atom or a C1 to C3 alkyl group, Q is a group represented by —S(O)n-(CR5R6)m-, R5 and R6 are a hydrogen atom or a C1 to C3 alkyl group, n is 2, m is 1, and Y is an optionally substituted phenyl group or a C2 to C10 alkyl group.
Next, representative examples of the present compound of the general formula [I] are shown in Tables 1 to 24. However, the present compound is not restricted to these. Incidentally, the No. of each compound is used also in the later description.
The following abbreviations used in the following tables indicate the following groups.
The present compound represented by the general formula [I] can be produced according to the processes shown below. However, the production process is not restricted to these.
<Production Process 1>Steps 1 to 4
[wherein L is a leaving group such as halogen atom, phenylsulfonyl group which may be substituted with C1 to C4 alkyl group (e.g. p-toluenesulfonyl group), C1 to C4 alkylsulfonyl group (e.g. methylsulfonyl group) or the like (chlorine atom is preferred); and R1, R2, R3, R4, R5, R6, Y and m have the same definitions as given above].
The above production process is explained in detail on each step.
(Step 1)
A compound represented by the general formula [II] is reacted with a mercaptan derivative represented by the general formula [III] in the presence of a base in an appropriate solvent or without using any solvent (preferably in an appropriate solvent), or with a salt (which is a sodium salt or a potassium salt) of a mercaptan derivative represented by the general formula [III] in an appropriate solvent, whereby an intended sulfide derivative represented by the general formula [IV] can be obtained.
The solvent can be exemplified by ethers such as diethyl ether, diethoxyethane, dioxane, tetrahydrofuran (THF) and the like; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene and the like; amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone and the like; sulfur compounds such as dimethyl sulfoxide (DMSO), sulfolane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol and the like; ketones such as acetone, 2-butanone and the like; nitriles such as acetonitrile and the like; water; and mixtures thereof.
The base can be exemplified by metal hydrides such as sodium hydride and the like; alkali metal amides such as sodium amide, lithium diisopropylamide and the like; organic bases such as pyridine, triethylamine, 1,8-diazabicyclo[5.4.0]-7-undecene and the like; inorganic bases such as alkali metal hydroxide (e.g. sodium hydroxide or potassium hydroxide), alkaline earth metal hydroxide (e.g. calcium hydroxide or magnesium hydroxide), alkali metal carbonate (e.g. sodium carbonate or potassium carbonate), alkali metal bicarbonate (e.g. sodium hydrogencarbonate or potassium hydrogencarbonate) and the like; and alcohol metal salts such as sodium methoxide, potassium tert-butoxide and the like.
The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 100° C. The reaction time differs depending upon the compounds used but is 0.5 to 24 hours.
(Step 2)
In the oxidation reaction of the sulfide derivative represented by the general formula [IV], the sulfide derivative of the general formula [IV] is reacted with an oxidizing agent (for example, an organic peroxide such as m-chloroperbenzoic acid, performic acid or peracetic acid, or an inorganic peroxide such as hydrogen peroxide, potassium permanganate or sodium periodate) in an appropriate solvent, whereby an intended sulfoxide derivative represented by the general formula [V] can be obtained.
The solvent can be exemplified by halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like; ethers such as dioxane, tetrahydrofuran (THF), dimethoxyethane, diethyl ether and the like; amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone and the like; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol and the like; ketones such as acetone, 2-butanone and the like; nitrites such as acetonitrile and the like; acetic acid; water; and mixtures thereof.
The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 60° C. The reaction time differs depending upon the compounds used but is 1 to 72 hours.
(Step 3)
The sulfoxide derivative represented by the general formula [V] is reacted with an oxidizing agent (the same as described in the step 2) in an appropriate solvent (the same as described in the step 2), whereby an intended sulfone derivative represented by the general formula [VI] can be obtained.
The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 60° C. The reaction time differs depending upon the compounds used but is 1 to 72 hours.
(Step 4)
When, in the oxidation reaction of the sulfide derivative represented by the general formula [IV], the oxidizing agent is used by an appropriate amount, the sulfone derivative represented by the general formula [VI] can be obtained without isolating the sulfoxide derivative represented by the general formula [V].
That is, the sulfide derivative represented by the general formula [IV] is reacted with an oxidizing agent (the same as described in the step 2) in an appropriate solvent (the same as described in the step 2), whereby an intended sulfoxide derivative represented by the general formula [V] can be obtained.
The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 60° C. The reaction time differs depending upon the compounds used but is 1 to 72 hours.
A compound represented by the genera, formula [II] wherein L is a halogen atom, can be synthesized by the following step 5.
(Step 5)
[wherein X1 is a halogen atom (a chlorine atom is preferred), and R1, R2, R3 and R4 have the same definitions as given above].
That is, a compound represented by the general formula [VIII] is reacted with an olefin derivative represented by the general formula [VII] in the presence of a base in an appropriate solvent or without using any solvent (preferably in an appropriate solvent), whereby isoxazoline compounds represented by the general formulas [IX] and [X] can be obtained. When both R3 and R4 are a hydrogen atom, an isoxazoline compound represented by the general formula [IX] is obtained preferentially.
The solvent can be exemplified by ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethyl ether, dioxane, tetrahydrofuran and the like; halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; acetic acid esters such as ethyl acetate, butyl acetate and the like; water; and mixtures thereof.
The base can be exemplified by alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like; alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide and the like; alkali metal carbonates such as sodium carbonate, potassium carbonate and the like; alkali metal bicarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and the like; alkali metal acetates such as sodium acetate, potassium acetate and the like; alkali metal fluorides such as sodium fluoride, potassium fluoride and the like; and organic bases such as pyridine, triethylamine, 1,8-diazabicyclo[5.4.0]-7-undecene and the like.
The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 80° C. The reaction time differs depending upon the compounds used but is 0.5 hour to 2 weeks.
Incidentally, the compound represented by the general formula [VII] used in the above step 5 as an intermidiate can be a commercial product or synthesized by a known reaction such as Wittig reaction or the like. The compound represented by the general formula [VIII] can be synthesized by, for example, a method described in Liebigs Annalen der Chemie, p. 985 (1989).
(wherein X1, R1, R2, R3, R4, R5, R6, Y and m have the same definitions as given above; R0 is a C1 to C4 alkyl group or a benzyl group, preferably a lower alkyl group such as methyl group, ethyl group or the like; and base is the same as described in the step 1).
The sulfide derivative represented by the general formula [IV], described in the Production Process 1 can be obtained also by the following process.
That is, a compound represented by the general formula [XI] is reacted with sodium hydrogensulfide hydrate represented by the general formula [XII] in the presence of a base (the same as described in the step 1) in an appropriate solvent or without using any solvent (preferably in an appropriate solvent) (Rongalit may be added in some cases), whereby a mercaptan salt represented by the general formula [XIII] can be obtained in the reaction system. The reaction mixture is reacted with a halogen derivative represented by the general formula [XIV] without isolating the mercaptan salt represented by the general formula [XIII], whereby a sulfide derivative represented by the general formula [IV] can be obtained.
The solvent can be exemplified by ethers such as dioxane, tetrahydrofuran (THF) and the like; halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like; amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone and the like; sulfur compounds such as dimethyl sulfoxide (DMSO), sulfolane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol and the like; ketones such as acetone, 2-butanone and the like; nitrites such as acetonitrile and the like; water; and mixtures thereof.
The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 100° C. The reaction time differs depending upon the compounds used but is 0.5 to 24 hours.
The sulfone derivative represented by the general formula [XI] can be produced by the method shown in the Step 1 of the Production Process 1. In this case, the group —(CR5R6)n—Y in the general formula [III] is an alkyl group or a benzyl group.
Next, the method for producing the present compound, the method for formulation with the present compound, and the application are specifically described by way of Examples. The method for producing the intermediate for the present compound is also described.
To a solution of 2.8 g (22.5 mmoles) of benzylmercaptan dissolved in 50 ml of dimethylformamide were added, in a nitrogen current, 3.2 g (23.2 mmoles) of anhydrous potassium carbonate and 3.0 g (22.5 mmoles) of 3-chloro-5,5-dimethyl-2-isoxazoline. The mixture was stirred at 100° C. for 2 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with ethyl acetate. The resulting organic layer was washed with water and an aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein, and the residue was purified by silica gel column chromatography to obtain 3.1 g (yield: 62.0%) of 3-benzylthio-5,5-dimethyl-2-isoxazoline as a yellow oily substance (refractive index nD20=1.5521).
1H-NMR [CDCl3/TMSδ(ppm)]: 7.24-7.39 (5H,m), 4.26 (2H,s), 2.77 (2H,s), 1.40 (6H,s)
To a solution of 4.1 g (15.0 mmoles) of 5-ethyl-3-(2,6-difluorobenzylthio)-5-methyl-2-isoxazoline dissolved in 50 ml of chloroform was added, with ice-cooling, 4.6 g (18.8 mmoles) of m-chloroperbenzoic acid (70%). The mixture was stirred for 1 hour and then at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with chloroform. The resulting organic phase was washed with an aqueous sodium hydrogensulfite solution, an aqueous potassium carbonate solution, water and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was purified by silica gel column chromatography (solvent system: hexane-ethyl acetate) to obtain 1.5 g (yield: 34.8%) of 5-ethyl-3-(2,6-difluorobenzylsulfinyl)-5-methyl-2-isoxazloline as a white powder (melting point: 30° C. or less).
1H-NMR [CDCl3/TMSδ(ppm)]: 7.39-7.28 (1H, m), 7.03-6.94 (2H, m), 4.38 (2H, s), 3.04 (1H, ABq, J=17.2, Δυ=85.7 Hz)+3.12 (1H, s) 1.75 (2H, m), 1.44 (3H, s)+1.41 (3H, 3), 0.97 (3H, m)
To a solution of 0.8 g (2.8 mmoles) of 5-ethyl-3-(2,6-difluorobenzylsulfinyl)-5-methyl-2-isoxazoline dissolved in 50 ml of chloroform was added, with ice-cooling, 1.0 g (4.1 mmoles) of m-chloroperbenzoic acid. The mixture was stirred for 1 hour and then at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with chloroform. The resulting organic phase was washed with an aqueous sodium hydrogensulfite solution, an aqueous potassium carbonate solution, water and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was purified by silica gel column chromatography (solvent system: hexane-ethyl acetate) to obtain 0.6 g (yield: 75.0%) of 5-ethyl-3-(2,6-difluorobenzylsulfonyl)-5-methyl-2-isoxazloline as a white powder (melting point: 64 to 65° C.).
1H-NMR [CDCl3/TMSδ(ppm)] 7.36-7.46 (1H,m), 6.98-7.04 (2H,m), 4.73 (2H,s), 3.04 (2H, ABq, J=17.2, Δυ-51.1 Hz), 1.77 (2H,q), 1.46 (3H,s), 0.97 (3H,t)
To a solution of 3.9 g (15.2 mmoles) of 3-(2,6-difluorobenzylthio)-5,5-dimethyl-2-isoxazoline dissolved in 50 ml of chloroform was added, with ice-cooling, 8.5 g (34.5 mmoles) of m-chloroperbenzoic acid. The mixture was stirred for 1 hour and then at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with chloroform. The resulting organic phase was washed with an aqueous sodium hydrogensulfite solution, an aqueous potassium carbonate solution, water and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was washed with diisopropyl ether to obtain 3.4 g (yield: 77.3%) of 3-(2,6-difluorobenzylsulfonyl)-5,5-dimethyl-2-isoxazbline as a white powder (melting point: 110 to 111° C.).
1H-NMR [CDCl3/TMSδ(ppm)]: 7.35-7.45 (1H,m), 6.98-7.03 (2H,m), 4.72 (2H,s), 3.06 (2H,s), 1.51 (6H,s)
To a solution of 5.0 g (28.2 mmoles) of 3-methylsulfonyl-5,5-dimethyl-2-isoxazoline (present compound No. 2-1) dissolved in 50 ml of DMF were added, with ice-cooling, 4.5 g (purity: 70%, 56.1 mmoles) of sodium hydrogensulfide hydrate, 7.8 g (56.4 mmoles) of potassium carbonate and 8.7 g (56.5 mmoles) of Rongalit. The mixture was stirred for 2 hours. Thereto was added 5.8 g (28.0 mmoles) of 2,6-difluorobenzylbenzyl bromide. The mixture was stirred at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with ethyl acetate. The resulting organic phase was washed with an aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was purified by silica gel column chromatography (solvent system=hexane-ethyl acetate) to obtain 5.8 g (yield: 80.0%) of 3-(2,6-difluorobenzylthio)-5,5-dimethyl-2-isoxazoline as a white powder (melting point: 77 to 80° C.).
1H-NMR [CDCl3/TMSδ(ppm)]: 7.20-7.28 (1H,m), 6.86-6.93 (2H,m), 4.35 (2H,s), 2.81 (2H,s), 1.43 (6H,s)<
To a solution of 193.0 g (1.07 M) of 3-chloro-5,5-dimethyl-2-isoxazoline dissolved in 500 ml of DMF was dropwise added, with ice-cooling, 1.0 kg (content=15%, 2.14 M) of an aqueous sodium methanethiolate solution. The mixture was stirred at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with ethyl acetate. The resulting organic phase was washed with an aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein, to obtain 115.0 g (yield: 74.1%) of 3-methylthio-5,5-dimethyl-2-isoxazoline. This residue (141.2 mmoles) was dissolved in 1 liter of chloroform. Thereto was added, with ice-cooling, 392.0 g (1.59 M) of m-chloroperbenzoic acid (purity: 70%), followed by stirring at that temperature for 1 hour and at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the precipitated m-chloroperbenzoic acid was removed by filtration. The filtrate was washed with an aqueous sodium hydrogensulfite solution, water, an aqueous sodium hydrogencarbonate solution and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was washed with diisopropyl ether to obtain 77.6 g (yield: 59.1%) of 3-methylsulfonyl-5,5-dimethyl-2-isoxazoline as a white powder (melting point: 82 to 84° C.).
1H-NMR [CDCl3/TMSδ(ppm)]: 3.26 (3H,s), 3.12 (2H,s), 1.51 (6H,s)
534.0 g (4.0 moles) of N-chlorosuccinimide was slowly added, at 65 to 70° C., to a solution of 182.7 g (2.05 moles) of glyoxylic aldoxime dissolved in 2 liters of dimethoxyethane, followed by refluxing for 1 hour with heating. Thereto were added, with ice-cooling, 1,440.0 g (14.4 moles) of potassium hydrogencarbonate and 10 ml of water. To the mixture was added 360.0 g (6.4 moles) of 2-methylpropene, followed by stirring at room temperature for 24 hours to give rise to a reaction. The reaction mixture was poured into water, followed by extraction with isopropyl ether. The resulting organic phase was washed with water and an aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein, to obtain 107.7 g (yield: 40.0%) of 3-chloro-5,5-dimethyl-2-isoxazoline as a yellow viscous liquid.
1H-NMR [CDCl3/TMSδ(ppm)]: 2.93 (2H,s), 1.47 (6H,s)
61.9 g (463.4 mmoles) of N-chlorosuccinimide was slowly added, at 60° C., to a solution of 20.6 g (231.7 mmoles) of glyoxylic acid aldoxime dissolved in 500 ml of dimethoxyethane. Then, the mixture was refluxed for 10 minutes with heating. Thereto were added, with ice-cooling, 50 ml (463.4 mmoles) of 2-methyl-1-butene, 98.9 g (1,622 mmoles) of potassium hydrogencarbonate and 10 ml of water, followed by stirring for 12 hours to give rise to a reaction. The reaction mixture was poured into water, followed by extraction with n-hexane. The resulting organic layer was washed with water and an aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein, to obtain 13.9 g (yield: 40.6%) of 3-chloro-5-ethyl-5-methyl-2-isoxazoline as a light yellow viscous liquid.
1H-NMR [CDCl3/TMSδ(ppm)]: 2.91 (2H, Abq, J=17.0, Δυ=46.1 Hz), 1.73 (2H,q), 1.42 (3H,s), 0.96 (3H,t)
Below are shown the properties (1H-NMR [CDCl3/TMSδ(ppm)]) of the present compounds produced according to the Production Process 1 or the Production Process 2.
Present compound 1-602: 6.71-7.23 (3H,m), 4.84 (2H,s), 4.04 (2H,q), 2.81 (2H,s), 2.47 (3H,s), 1.42 (6H,s)
Present compound 1-603: 6.72-7.23 (3H,m), 4.85 (2H,s), 3.93 (2H,t), 2.82 (2H,s), 2.47 (3H,s), 1.83 (2H,m), 1.42 (6H,s), 1.04 (3H,t)
Present compound 1-605: 6.72-7.29 (3H,m), 4.85 (2H,s), 3.98 (2H,t), 2.81 (2H,s), 2.47 (3H,s), 1.80 (2H,m), 1.38 (6H,s), 0.97 (3H,t)
Present compound 1-606: 6.72-7.27 (3H,m), 6.05 (1H,m), 5.43 (1H,d), 5.29 (1H,d), 4.87 (2H,s), 4.57 (2H,d), 2.88 (2H,s), 2.48 (3H,s), 1.44 (6H,s)
Present compound 1-607: 6.92-7.30 (3H,m), 4.84 (2H,s), 4.71 (2H,d), 2.96 (2H,s) 2.52 (1H,s), 2.48 (3H,s), 1.46 (6H,s)
Present compound 1-228: 7.44-7.34 (2H,min), 7.02-6.92 (2H,m), 4.71 (2H,s), 3.86 (3H,s), 2.81 (2H, ABq, J=117.4, Δυ=54.2 Hz), 1.68 (2H,q), 1.36 (3H,s), 0.90 (3H,t)
Present cornpound 1-590: 7.28 (1H,dd), 7.08 (1H,d), 6.86 (1H,d), 6.05 (1H,m), 5.45 (1H,d), 5.32 (1H,d), 4.90 (2H,s), 4.63 (2H,d), 3.00 (2H,s), 1.47 (6H,s)
Present compound 1-599: 8.07 (1H,d), 7.47-7.56 (3H,m), 6.05 (1H,m), 5.42 (1H,d), 5.31 (1H,d), 5.31 (2H,s), 4.83 (2H,d), 2.94 (2H,s) 1.43 (6H,s)
The herbicide of the present invention contains, as the active ingredient, an isoxazoline derivative represented by the genera formula [I] or a salt thereof.
In using the compound of the present invention as a herbicide, the present compound may be used by itself. It can also be used in the form of a powder, a wettable powder, an emulsifiable concentrate, fine granules, granules, etc. by blending with a carrier, a surfactant, a dispersant, an adjuvant, etc. all generally used in formulation.
As the carrier used in formulation, there can be mentioned, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, calcium carbonate, slaked lime, siliceous sand, ammonium sulfate, urea and the like; and liquid carriers such as isopropyl alcohol, xylene, cyclohexane, methylnaphthalene and the like.
As the surfactant and the dispersant, there can be mentioned, for example, metal salts of alkylbenzenesulfonic acids, metal salts of dinaphthylmethanedisulfonic acid, salts of alcohol sulfates, alkylarylsulfonic acid salts, ligninsulfonic acid salts, polyoxyethylene glycol ether, polyoxyethylene alkyl aryl ethers, monoalkylates of polyoxyethylene sorbitan and the like. As the adjuvant, there can be mentioned, for example, carboxymethyl cellulose, polyethylene glycol and gum arabic. The present herbicide, when used, is diluted to an appropriate concentration and sprayed or applied directly.
The herbicide of the present invention can be used by spraying on plant foliage, application to soil, application on water surface, etc. The amount of the active ingredient used is determined appropriately so as to meet the application purpose. When the present compound is made into a powder or granules, the amount is appropriately determined in a range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight. When the present compound is made into an emulsifiable concentrate or a wettable powder, the amount is appropriately determined in a range of 1 to 90% by weight, 5 to 50% by weight.
The amount of the present herbicide used varies depending upon the kind of the compound used, the target weed, the tendency of weed emergence, the environmental conditions, the type of the herbicide used, etc. When the present herbicide is used per se as in the case of a powder or granules, the amount is appropriately selected in a range of 0.1 g to 5 kg, preferably 1 g to 1 kg per 10 ares in terms of the active ingredient. When the present herbicide is used in a liquid form as in the case of an emulsifiable concentrate or a wettable powder, the amount is appropriately selected in a range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm in terms of the active ingredient.
The compound of the present invention may be mixed as necessary with an insecticide, a fungicide, other herbicide, a plant growth-regulating agent, a fertilizer, etc.
Next, formulation from the present compound is described specifically by showing typical examples of formulation. The kinds of compounds and additives and their compounding ratios are not restricted to those shown below and can be varied widely. In the following description, “parts” refer to parts by weight.
<Formulation 1>Wettable Powder
10 parts of a compound (1-5) are mixed with 0.5 part of polyoxyethylene octylphenyl ether, 0.5 part of a sodium salt of a β-naphthalenesulfonic acid-formalin condensate, 20 parts of diatomaceous earth and 69 parts of clay. The mixture is mixed and pulverlized to obtain a wettable powder.
<Formulation 2>Wettable Powder
10 parts of a compound (1-5) are mixed with 0.5 part of polyoxyethylene octylphenyl ether, 0.5 part of a sodium salt of a β-naphthalenesulfonic acid-formalin condensate, 20 parts of diatomaceous earth, 5 parts of white carbon and 64 parts of clay. The mixture is mixed and pulverlized to obtain a wettable powder.
<Formulation 3>Wettable Powder
10 parts of a compound (1-5) are mixed with 0.5 part of polyoxyethylene octylphenyl ether, 0.5 part of a sodium salt of a β-naphthalenesulfonic acid-formalin condensate, 20 parts of diatomaceous earth, 5 parts of white carbon and 64 parts of calcium carbonate. The mixture is mixed and pulverlized to obtain a wettable powder.
<Formulation 4>Emulsifiable Concentrate
To 30 parts of a compound (1-5) are added 60 parts of an equal volume mixture of xylene and isophorone and 10 parts of a surfactant mixture of a polyoxyethylene sorbitan alkylate, a polyoxyethylene alkylaryl polymer and an alkylarylsulfonate. The resulting mixture is stirred sufficiently to obtain an emulsifiable concentrate.
<Formulation 5>Granules
There are mixed 10 parts of a compound (1-5), 80 parts of an extender which is a 1:3 mixture of talc and bentonite, 5 parts of white carbon, 5 parts of a surfactant mixture of a polyoxyethylene sorbitan alkylate, a polyoxyethylene alkylaryl polymer and an alkylarylsulfonate. The resulting mixture is kneaded sufficiently to form a paste. The paste is extruded through the eyes (diameter: 0.7 mm) of a sieve. The extrudate is dried and cut into a length of 0.5 to 1 mm to obtain granules.
Next, Test Examples of the present compound are described to show the effect of the present compound.
A paddy field soil was filled in a plastic pot of 100 cm2 and subjected to puddling. Then, seeds of Echinochloa oryzicola Vasing. (Eo) were sowed and water was filled in a depth of 3 cm. Next day, wettable powders produced in accordance with the Formulation 1 were diluted with water and dropped on the water surface. The application amount of each wettable powder was 100 g per 10 ares in terms of the active ingredient. Then, breeding was made in a greenhouse, and the herbicidal effect of each wettable powder was examined at the 21st day from the treatment in accordance with the standard shown in Table 40. The results are shown in Tables 41 to 43.
An upland field soil was filed in a plastic pot of 80 cm2. Seeds of Echinochloa crus-galli (L.) Beauv. var. crusgall (Ec) and Setaria viridis (L.) Beauv. (Se) were sowed, followed by covering with the same soil. Wettable powders produced in accordance with the Formulation 1 were diluted with water and sprayed uniformly: on the soil surface using a small sprayer, in an amount of 100 liters per 10 ares so that the amount of each active ingredient became 100 g per 10 ares. Then, breeding was made in a greenhouse, and the herbicidal effect of each wettable powder was examined at the 21st day from the treatment in accordance with the standard shown in Table 40. The results are shown in Tables 44 to 46.
An upland field soil was filed in a plastic pot of 80 cm2. Seeds of Echinochloa crus-galli (L.) Beauv. var. crusgalli (Ec) were sowed. Breeding was made in a greenhouse for 2 weeks. Wettable powders produced in accordance with the Formulation 1 were diluted with water and sprayed on the whole foliage of plants from above the plants using a small sprayer in an amount of 100 liters per 10 ares so that the amount of each active ingredient became 100 g per 10 ares. Then, breeding was made in the greenhouse, and the herbicidal effect of each wettable powder was examined at the 14th day from the treatment in accordance with the standard shown in Table 40. The results are shown in Tables 47 and 48.
A paddy field soil was filled in a plastic pot of 100 cm2 and subjected to puddling. Seeds of Echinochloa oryzicola Vasing. (Eo) were sowed; two-leaf stage seedlings of rice (Or) were transplanted in a depth of 2 cm; and water was filled in a depth of 3 cm. Next day, wettable powders produced in accordance with the Formulation 1 were diluted with water and dropped on the water surface. The application amount of each wettable powder was 100 g per 10 ares in terms of the active ingredient. Then, breeding was made in a greenhouse. At the 21st day from the treatment, the phytotoxicity and herbicidal effect of each wettable powder were examined in accordance with the standard shown in Table 40. The results are shown in Table 49.
A paddy field soil was filled in a plastic pot of 100 cm2 and subjected to puddling. Seeds of Monochoria vaginalis Presl (Mo) and Scirpus juncoides Roxb. subsp. juncoides Roxb. (Sc) were sowed; water was filled in a depth of 3 cm; and breeding was made. When Mo reached a 1-leaf stage and Sc reached a 2-leaf stage, wettable powders produced in accordance with the Formulation 1 were diluted with water and dropped on the water surface. The application amount of each wettable powder was 100 g per 10 ares in terms of the active ingredient. Then, breeding was made in a greenhouse. At the 30th day from the treatment, the herbicidal effect of each wettable powder was examined in accordance with the standard shown in Table 40. The results are shown in Table 51. Incidentally, the details of comparative compounds 1 and 2 are shown in Table 50.
Test for herbicidal effect to broadleaf weeds by upland field soil treatment
An upland field soil was filled in a plastic pot of 80 cm2. Seeds of Polygonum lapathifolium L. subsp. nodosum (Pers.) Kitam. (Po) and Chenopodium album L. (Ch) were sowed, followed by covering with the same soil. Wettable powders produced in accordance with the Formulation 1 were diluted with water and sprayed uniformly on the soil surface using a small sprayer, in an amount of 100 liters per 10 ares so that the amount of each active ingredient became 100 g per 10 ares. Then, breeding was made in a greenhouse. At the 30th day from the treatment, the herbicidal effect of each wettable powder was examined in accordance with the standard shown in Table 40. The results are shown in Table 52. Incidentally, the details of comparative compounds 1 and 3 are shown in Table 50.
The compound represented by the general formula [I] according to the present invention shows an excellent herbicidal effect, at a low application amount over a wide period, from before germination to growth, to various weeds causing problems in upland fields, for example, Gramineae weeds [e.g. Echinochloa crus-galli (L.) Beauv. var. crus-galli, Digitaria ciliaris (Retz.) Koeler, Setaria viridis (L.) Beauv., Poa annua L., Sorghum halepense (L.) Pers., Alopecurus aequalis Sobol. var. amurensis (Komar.) Ohwi, and wild oats], broadleaf weeds [Polygonum lapathifolium L. nodosum (Pers.) Kitam., Amaranthus viridis L., Chenopodium album L., Stellaria media (L.) Villars, Abutilon avicennae, Sida spinosa, cassia obtusifolia, Ambrosia artemisiifolia L. var. elatior (L.) Desc., and morning glory], and perennial or annual cyperaceous weeds [e.g. Cyperus rotundus L., cyperus esculentus, Kyllinga brevifolia Rottb. subsp. leiolepis (Fraxch. et Savat.) T. Koyama, Cyperus microiria Steud., and Cyperus iria L.].
Further, the present compound shows a herbicidal effect, at a low application amount over a wide period from before germination to growth, also to weeds emerging in paddy fields, i.e. annual weeds [e.g. Echinochloa oryzicola Vasing., Cyperus difformis L., Monochoria vaginalis (Burm. f.) Presl. var. plantaginea (Roxb.) Solms-Laub., and Lindernia pyxidara L.] and perennial weeds [e.g. Cyperus serotinus Rottb., Eleocharis kuroguwai Ohwi, and Scirpus juncoides Roxb. subsp. hotarui (Ohwi) T. Koyama].
The herbicide of the present invention has high safety to crops, particularly to rice, wheat, barley, corn, grain sorghum, soybean, cotton, sugar beat, lawn, fruit trees, etc.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11-225878 | Aug 1999 | JP | national |
This application is a 371 of PCT/JP00/05325 filed Aug. 9, 2000.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCTJP00/05325 | 8/9/2000 | WO | 00 | 2/8/2002 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO0112613 | 2/22/2001 | WO | A |
| Number | Date | Country |
|---|---|---|
| 8-225548 | Sep 1996 | JP |
| 8-225548 | Sep 1996 | JP |
| 0050410 | Aug 2000 | WO |
