JP2763904B2 - Oxazolidine derivative and method for producing the same - Google Patents

Description

The present invention relates to a novel oxazolidine derivative having herbicidal activity. More specifically, the present invention relates to a novel oxazolidine derivative having a strong weed activity against various kinds of severely damaging weeds and a high selectivity for useful crops, and a method for producing the same.

[Prior Art] Conventionally, derivatives having a substituted phenyl group on the nitrogen atom at the 3-position of the oxazolidine ring and various substituents at the 5-position are known. None of the derivatives have herbicidal activity (see, for example, US Pat. No. 3,2014,010, control compounds 1 and 2).

[Problems to be Solved by the Invention] The present invention provides novel compounds having high selectivity for various harmful weeds and strong herbicidal activity among oxazolidine derivatives. It provides a simple manufacturing method.

[Means for Solving the Problems] As a result of intensive studies on various oxazolidine derivatives, the present inventors have found that a halogen atom is located at the phenyl ring 2 ′ and 4 ′ on the nitrogen atom at the 3-position of the oxazolidine ring, and a halogen atom is located at the 5′-position. Completed the present invention by discovering that 1,3-oxazolidine-2,4-dione derivative having an ether bond introduced therein exhibits strong herbicidal activity against various harmful weeds and high selectivity for useful crops. did.

[Disclosure of the Invention] That is, the present invention relates to a general formula Wherein R ¹ is a hydrogen atom, an alkyl group, a cyanoalkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group,
It represents an alkynyl group or a lower alkyloxylcarbonyl group, and R ² represents an alkyl group or a cycloalkyl group. The alkyl group, cycloalkyl group, aralkyl group, alkenyl group and alkynyl group may be substituted. X ¹ and X ² independently represent a halogen atom. And a substituent such as an ether bond represented by an R ¹ O group at the 5′-position and a halogen atom at the 2′- and 4′-positions of the phenyl ring on the 3-position nitrogen atom. The present invention relates to a novel oxazolidine derivative and a method for producing the same.

When used in a paddy field, the novel oxazolidine derivative of the present invention shows a strong herbicidal effect against annual weeds such as barnyardgrass, oak, scorpion grass, and perennial weeds such as sedge flies, fireflies, urikawa and pine trees. Also in the field, it is possible to selectively kill field weeds such as dog bream, crabgrass, enokorogusa, shiroza, kade, aobille, purslane and plantain.

Furthermore, the compound of the present invention has a strong weedicidal activity, and not only can the initial effect be obtained with a small amount, but also the phytotoxicity to useful cultivated plants is extremely low. In other words, the compound of the present invention kills grasses such as grasses, grasshoppers, and grasshoppers such as grasses, such as grasses and grasshoppers, while causing almost no harm to transplanted rice, wheat, corn, etc. which are grasses of the grass family. Similarly, almost no phytotoxicity was observed on soybeans, cotton, etc., which are crops other than gramineae.

The amount of the herbicide containing the compound of the present invention as an active ingredient varies depending on the method of application, the timing, the type of the target plant, and the like.
10 to 500 g per 10 ares, preferably 30 to
It is about 300g.

According to the present invention, the novel oxazolidine derivative represented by the general formula (I) can be produced, for example, by a method represented by the following reaction formula.

(In the formula, R ¹ , R ² , R ³ , X ¹ and X ² represent the same meaning as described above.) (In the formula, R ¹ ′, R ² , R ⁴ , X ¹ and X ² have the same meaning as described above. Y is a leaving group.) (Wherein, R ¹ , R ² , R ⁵ , R ⁶ , X ¹ and X ² have the same meanings as described above.) A compound represented by the general formula (II), which is a raw material compound for producing the compound of the present invention Is novel and can be produced, for example, by the method shown in the following reaction formula.

(In the formula, R ¹ , R ² , R ³ , X ¹ and X ² have the same meanings as described above. Z represents an isocyanato group or a carbamoyl chloride group.) (Wherein, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , X ¹ and X ² have the same meanings as described above.) Preferred examples and descriptions of the various definitions involved are set forth in detail below.

Preferred "alkyl groups" are linear or branched alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl. Group, pentyl group, 3-pentyl group, hexyl group, 2-hexyl group, octyl group, dodecyl group, 2-dodecyl group, hexadecyl group, octadecyl group, icosyl group, etc., and preferably 1 carbon atom. It has ~ 12.

Preferred "cyanoalkyl groups" are straight-chain or branched-chain cyanoalkyl groups having 1 to 4 carbon atoms in the alkyl moiety, such as cyanomethyl, 1-cyanoethyl, 2
-Cyanoethyl group, 3-cyanopropyl group and the like.
It has two. The cyano group may be substituted at the terminal of the alkyl group or at a position other than the terminal.

Suitable “cycloalkyl group” is a cyclic alkyl group having 1 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and a cyclododecyl group.
６6.

Suitable aralkyl groups are benzyl groups, aralkyl groups such as α-phenethyl group, and the phenyl group is, for example, a halogen atom such as fluorine, chlorine or bromine,
For example, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a lower alkoxy group such as a t-butoxy group, or One or more substituents such as a nitro group may be substituted.

Preferred "alkenyl groups" are straight-chain or branched alkenyl groups having 3 to 10 carbon atoms, such as allyl, methallyl, propenyl, butenyl, pentenyl, hexenyl, prenyl, geranyl, A neryl group and the like can be mentioned.

Preferred "alkynyl groups" are straight or branched chain alkynyl groups having 3 to 8 carbon atoms, such as propargyl, 1-methylpropargyl, 1,1-dimethylpropargyl, 1-ethylpropargyl, 2 -Butynyl group, 3-butynyl group, 2-pentynyl group, 3-pentynyl group and the like.

"Lower" refers to carbon atoms of 1-6 unless otherwise indicated.
Group. Therefore, examples of the “lower alkoxycarbonyl group” include a methoxycarbonyl group, an ethoxycarbonyl group, an isobutyloxycarbonyl group, a hexyloxycarbonyl group and the like.

As the “halogen atom”, a fluorine atom, a chlorine atom,
Although a bromine atom or an iodine atom is mentioned, a fluorine atom, a chlorine atom, or a bromine atom is preferable.

Preferred examples of the "leaving group" for "Y" include, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a halogen atom, a trisulfonyloxy group, a phenylsulfonyloxy group, a methylsulfonyloxy group and the like. And a substituted sulfonyloxy group.

"Z" represents an isocyanato group or a carbamoyl chloride group.

Next, a method for producing the oxazolidine derivative represented by the general formula (I), which is the compound of the present invention, will be described in detail below.

Description of Production Method 1 The compound (I) of the present invention can be produced by a cyclization reaction of a carbamic acid ester represented by the general formula (II).

This reaction is usually performed in the presence of a base. Suitable bases include, for example, tertiary amines such as triethylamine, tripropylamine, tributylamine, N-methylmorpholine, dimethylaniline, pyridine, lutidine,
Aromatic amines such as pyrimidine, sodium methoxide,
Sodium ethoxide, alkali metal alkoxides such as potassium-t-butoxide and sodium hydride, alkali metal hydrides such as potassium hydride or sodium carbonate, potassium carbonate, sodium hydroxide, basic inorganic compounds such as potassium hydroxide, Carboxylic acid metal salts such as sodium acetate, potassium acetate and lithium acetate can be used.

This reaction is performed in an organic solvent. Suitable organic solvents include benzene, toluene, aromatic solvents such as xylene, dioxane, tetrahydrofuran, ether solvents such as dimethoxyethane, methanol, ethanol, alcohol solvents such as isopropanol, or ethyl acetate, dimethylformamide, Organic solvents such as dimethyl sulfoxide and acetonitrile can be mentioned, but the reaction can be carried out in any other solvent that does not adversely affect the reaction.

The reaction temperature is not particularly limited, and is usually room temperature, heating, heating,
Alternatively, the reaction is carried out while heating and refluxing in a solvent used.

After completion of the reaction, the product can be obtained by usual post-treatment. If necessary, the product is purified by column chromatography, recrystallization and the like.

Description of Production Method 2 In this production method, among the compounds of the present invention represented by the general formula (I), an oxazolidine derivative (I ′) having a carbonate ester represented by R ⁴ OC as R ¹ as a hydroxyl-protecting group Is used as a raw material. That is, the carbonate of the compound (I ') is treated under basic conditions to obtain a phenol derivative represented by the general formula (I ") or an alkali metal salt thereof, and then the phenol derivative represented by the general formula (III) A oxazolidine derivative represented by the general formula (I), wherein the starting compound (I ') and the reaction intermediate (I ") in the production method are novel and have the general formula It is included in the compound of the present invention represented by (I).

The hydrolysis reaction of the carbonate ester is carried out in the presence of a base, and is characterized by selectively hydrolyzing only the carbonate ester under basic conditions such that the oxazolidine ring is not hydrolyzed. Suitable bases include sodium carbonate, potassium carbonate, lithium carbonate,
Metal carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and alkali metal alkoxides such as sodium methoxide, sodium ethoxide and lithium methoxide. Can be mentioned. The amount of the base used is preferably 0.5 to 2.0 equivalents to the substrate.

The reaction is performed in a usual organic solvent, but is preferably performed in a protic solvent such as methanol, ethanol, isopropyl alcohol, and t-butanol.
Further, for example, aromatic solvents such as benzene, toluene, xylene, etc., ether solvents such as dioxane, tetrahydrofuran, dimethoxyethane, or aprotic solvents such as dimethylformamide, dimethylsulfoxide, as long as they do not adversely affect the reaction. And a mixed solvent with a protic solvent.

Next, the compound (I) of the present invention can be produced by reacting the oxazolidine derivative (I ″) thus obtained with a compound represented by the general formula (III).

This reaction is carried out in the presence of a base. For example, tertiary amines such as triethylamine, tripropylamine, tributylamine, N-methylmorpholine and dimethylaniline, aromatic amines such as pyridine, lutidine and pyrimidine, sodium methoxide, sodium ethoxide and potassium-t-butoxide. Alkali metal alkoxide, sodium hydride, alkali metal hydride such as potassium hydride or sodium carbonate, potassium carbonate,
Basic inorganic compounds such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide and potassium hydroxide, metal salts of carboxylic acids such as sodium acetate, potassium acetate and lithium acetate; alkyllithium reagents such as methyllithium and n-butyllithium Alternatively, alkali metal amides such as sodium amide and lithium amide can be used.

The reaction is preferably performed in an organic solvent. Suitable organic solvents include aromatic solvents such as benzene, toluene and xylene; ether solvents such as diethyl ether, dioxane, tetrahydrofuran and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and isobutyronitrile. Or an organic solvent such as ethyl acetate, N, N-dimethylformamide, dimethylsulfoxide, and sulfolane, or a mixed solvent thereof.

When chloride, bromide or sulfonic acid ester is used as the compound represented by the general formula (III) in this reaction, depending on the compound, iodide such as potassium iodide or sodium iodide, tetraethylammonium bromide, benzyltriethyl may be used. The progress of the reaction can be accelerated by adding a quaternary ammonium salt such as ammonium bromide or iodide.

The reaction temperature varies depending on the base or solvent used, but is not particularly limited, and the reaction is carried out under cooling, at room temperature, under heating or under heating.

After completion of the reaction, the product can be obtained by usual post-treatment. If necessary, the product is purified by column chromatography, recrystallization and the like.

In carrying out the present reaction, a metal salt of phenol of compound (I ″) can be used. This metal salt can be obtained by treating compound (I ′) or compound (I ″) with a base. Can be used for the next reaction with or without isolation from the reaction system.

Description of Production Method 3 Compound (I) of the present invention can be produced by hydrogenating a double bond under hydrogenation conditions of a derivative having a substituted methylidene group at the 5-position of the oxazolidine ring represented by the general formula (IV). it can.

For this reduction reaction, a normal olefin reduction reaction can be used, but palladium carbon, palladium black, palladium asbestos, palladium silica, palladium alumina, rhodium carbon, rhodium asbestos, rhodium silica, rhodium alumina, platinum carbon, platinum oxide And a homogeneous hydrogenation catalyst comprising a transition metal complex such as palladium, rhodium, iridium and ruthenium.

This reaction is preferably performed in an organic solvent. Suitable organic solvents vary depending on the catalyst used, but include methanol, ethanol, isopropanol, alcohol solvents such as ethylene glycol, benzene, toluene,
Organic solvents such as aromatic solvents such as xylene, ether solvents such as diethyl ether, dioxane, tetrahydrofuran, and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitonyl and isobutyronitrile; and mixed solvents thereof. Can be used. In particular, when a heterogeneous catalytic hydrogenation catalyst is used, it is preferable to use an alcohol solvent in terms of yield and selectivity.

The reaction proceeds sufficiently even at a hydrogen pressure of normal pressure, but the reaction time can be shortened if the reaction is carried out under a hydrogen pressure of about several atmospheres.

After completion of the reaction, the hydrogenation catalyst can be recovered by filtration and the product can be obtained by ordinary post-treatment. If necessary, the product is purified by column chromatography, recrystallization, or the like.

 Next, a method for producing a starting compound will be described in detail below.

Description of Production Method 1 of Starting Compound The carbamic acid ester derivative represented by the general formula (II) is obtained by converting an aryl isocyanate represented by the general formula (V) or carbamoyl chloride to an α-hydroxycarboxylic acid ester represented by the general formula (VI) Can be produced by reacting

This reaction is usually performed in the presence of a base. Suitable bases include, for example, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc .; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, lithium methoxide, potassium-t-butoxide; Tertiary amines such as triethylamine, tripropylamine, tributylamine, N-methylmorpholine, dimethylaniline, pyridine;
Aromatic amines such as lutidine and pyrimidine can be used.

This reaction is performed in an organic solvent. Suitable organic solvents include aromatic solvents such as benzene, toluene, and xylene; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, and dimethoxyethane; and organic solvents such as ethyl acetate, dimethylformamide, dimethylsulfoxide, and acetonitrile. The reaction can be carried out in any other solvent that does not adversely affect the reaction.

The reaction temperature is not particularly limited, and is usually room temperature, heating, heating,
Alternatively, the reaction is carried out while heating and refluxing in a solvent used.

After completion of the reaction, the product can be obtained by usual post-treatment. If necessary, the product is purified by column chromatography, recrystallization and the like.

Description of Production Method 2 for Starting Compound The carbamic acid ester derivative represented by the general formula (II) is a compound represented by the general formula (VII) which is a known compound described in JP-A-62-174065. Can be produced by hydrogenating a double bond under hydrogenation conditions.

For this reduction reaction, a normal olefin reduction reaction can be used, but palladium carbon, palladium black, palladium asbestos, palladium silica, palladium alumina, rhodium carbon, rhodium asbestos, rhodium silica, rhodium alumina, platinum carbon, platinum oxide And a homogeneous hydrogenation catalyst comprising a transition metal complex such as palladium, rhodium, iridium and ruthenium.

This reaction is preferably performed in an organic solvent. Suitable organic solvents vary depending on the catalyst used, but include methanol, ethanol, isopropanol, alcohol solvents such as ethylene glycol, benzene, toluene,
Organic solvents such as aromatic solvents such as xylene, ether solvents such as diethyl ether, dioxane, tetrahydrofuran, and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and isobutyronitrile; and mixed solvents thereof. Can be used. In particular, when a heterogeneous catalytic hydrogenation catalyst is used, it is preferable to use an alcohol solvent in terms of yield and selectivity.

The reaction proceeds sufficiently even at a hydrogen pressure of normal pressure, but the reaction time can be shortened if the reaction is carried out under a hydrogen pressure of about several atmospheres.

After completion of the reaction, the hydrogenation catalyst can be recovered by filtration and the product can be obtained by ordinary post-treatment. If necessary, the product is purified by column chromatography, recrystallization, or the like.

Table 1 shows typical oxazolidine derivatives represented by the general formula (I) of the present invention which can be synthesized in this manner.

Hereinafter, the present invention will be described in more detail with reference to Examples and Production Examples.

Example 1 Ethyl 2- {N- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) carbamoyloxy} isovalerate synthesized by the method of Production Example 1 (500 mg, 1.33 mmol)
To a toluene (30 ml) solution was added a catalytic amount of sodium acetate, and the mixture was stirred under reflux for 5 hours. After completion of the reaction, the solution was washed with 1N hydrochloric acid, the organic layer was dried, and the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to give pure 3- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl). ) -5-Isopropyl-1,3-oxazolidine-2,4-dione [Compound 1]
(240 mg, 55% yield).

Example 2 To a solution of 3- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (400 mg, 1.22 mmol) in ethanol (30 ml) A catalytic amount of 10% Pd / C (80 mg) was added, and the mixture was reacted at room temperature under a hydrogen atmosphere at normal pressure until absorption of hydrogen gas ceased. After completion of the reaction, the catalyst was separated and the liquid was concentrated under reduced pressure to obtain a colorless and transparent oil. Then, the product was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to give pure 3- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl). White crystals (310 mg, yield 77%) of -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 1] were obtained.

Example 3 A toluene (50 ml) solution of 2,4-dichloro-5-isopropoxyphenyl isocyanate (1.0 g, 4.06 mmol) and ethyl 2-hydroxyisovalerate (890 mg, 6.09 mmol) was prepared.
Stirred at 80 ° C. for 3 hours. IR and ¹ H-NMR of the reaction mixture
From the spectrum, it was confirmed that the isocyanate had completely disappeared and the adduct, carbamic acid ester 2- {N- (2,4'-dichloro-5'-isopropoxyphenyl) carbamoyloxy} isovalerate ethyl was formed. did.
Then, a catalytic amount of sodium acetate was added, and the mixture was
Stirred for hours. After completion of the reaction, the solution was washed with 1N hydrochloric acid, the organic layer was dried, and then concentrated under reduced pressure. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate /
Hexane = 1/10) to give pure 3-
(2 ', 4'-dichloro-5'-isopropoxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-
Dione [compound 2] (470 mg, yield 33%) was obtained.

Example 4 Ethyl 2- {N- (2'-fluoro-4'-chloro-5'-cyclopentyloxyphenyl) carbamoyloxy} -3-methyl-3-butenoate (800 mg, 2.0 mmol) synthesized by the method of Production Example 2 A catalytic amount of sodium acetate was added to a toluene (30 ml) solution, and the mixture was stirred under reflux for 3 hours.
After completion of the reaction, the solution was washed with 1N hydrochloric acid, the organic layer was dried, and the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/5) to give pure 3- (2'-).
There was obtained a white solid (540 mg, yield 76%) of fluoro-4'-chloro-5'-cyclopentyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione. ¹ H-NMR (CDCl ₃ , TMS, δ ppm): 1.58 to 1.91 (8H, m),
2.00 (3H, s), 2.26 (3H, s), 4.73 (1H, m), 6.77 (1H,
d), 7.27 (1H, d); IR (K Brdisk, cm ^-1 ): 1820,1743,169
3; MP: 98-99.5 ° C. Next, the thus obtained 3-
(2'-Fluoro-4'-chloro-5'-cyclopentyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (500 mg, 1.41 mmol) in ethanol (30 ml) solution Of 10% Pd / C (100 mg) was added, and the mixture was reacted at room temperature under a hydrogen atmosphere at normal pressure until absorption of hydrogen gas ceased. After completion of the reaction, the catalyst was separated and the liquid was concentrated under reduced pressure to obtain a colorless and transparent oil. Then, a small amount of methanol was added, and white crystals (360 mg, yield: 72%) precipitated after cooling were obtained. This is the objective 3-
It was confirmed by spectrum and the like that it was (2'-fluoro-4'-chloro-5'-cyclopentyloxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 3].

Example 5 Potassium carbonate was added to a solution of 3- (2'-fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione (700 mg, 2.43 mmol) in acetonitrile (30 ml). (340 mg) was added and the mixture was stirred under reflux for 1 hour. Then propargyl bromide (2m
l) was added and the mixture was further stirred under reflux for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 1N hydrochloric acid was added, and the mixture was extracted with ether. After drying the organic layer, the solvent was distilled off under reduced pressure to obtain a pale yellow oil. This was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 1 /
Purified by 10) to give pure 3- (2'-fluoro-4'-chloro-5'-propargyloxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-
Dione [compound 4] (480 mg, yield 61%) was obtained.

Example 6 3- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) -5- (2 "-butylidene) -1,3
To a solution of oxazolidine-2,4-dione (300 mg, 0.88 mmol) in ethanol (30 ml) was added a catalytic amount of 10% Pd / C (60 mg), and the mixture was heated to room temperature under a hydrogen atmosphere at normal pressure until the absorption of hydrogen gas ceased. Was reacted. After completion of the reaction, the catalyst was separated and the liquid was concentrated under reduced pressure to obtain a colorless and transparent oil.
Then, the product was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to give pure 3- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl). -5- (2 "-butyl) -1,3-oxazolidine-2,4-dione [compound 5] (240 mg, yield 80%) was obtained.

Example 7 According to the method of Preparation Example, 2-fluoro-4-chloro-
2- {N- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) carbamoyloxy} -2-cyclopentylacetic acid synthesized from 5-isopropoxyphenylisocyanate and ethyl 2-hydroxy-2-cyclopentylacetate To a solution of methyl (400 mg, 1.0 mmol) in N, N-dimethylformamide (30 ml) was added a catalytic amount of sodium acetate, and the mixture was stirred at 50 ° C. for 8 hours. After completion of the reaction, 1N hydrochloric acid was added to the solution, and the mixture was extracted with ether. Wash the ether layer with 1N hydrochloric acid
It was washed twice, dried and concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) and recrystallized from methanol to give pure 3- (2'-fluoro-4'-).
A white solid (170 mg, 48% yield) of chloro-5'-isopropoxyphenyl) -5-cyclopentyl-1,3-oxazolidine-2,4-dione [compound 6] was obtained.

Example 8 Oily (about 60%) sodium hydride (170 mg, 25 mmol)
After washing with hexane, tetrahydrofuran (30 ml)
And then add 3- (2'-fluoro-4'-chloro-
5'-hydroxyphenyl) -5-isopropyl-1,3
-Oxazolidine-2,4-dione (1.0 g, 3.48 mmol) was added, and the mixture was stirred at room temperature until hydrogen generation stopped. By removing the solvent, a white solid of 3- (2'-fluoro-4'-chloro-5'-sodiumoxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione was obtained. Ethyl iodide (2 ml) was added to an acetonitrile solution (30 ml) of the mixture, and the mixture was stirred under reflux for 3 hours. After completion of the reaction, 1N hydrochloric acid was added, and the mixture was extracted with chloroform. After drying the organic layer, the solvent was distilled off under reduced pressure to obtain a pale yellow oil. This was recrystallized from methanol to give 3- (2'-fluoro-4'-chloro-5'-ethoxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 7] ( 700 mg, yield 64%).

Example 9 To a solution of 3- (2'-fluoro-4'-chloro-5'-hexyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (500 mg, 1.35 mmol) in ethanol (30 ml) A catalytic amount of 10% Pd / C (100 mg) was added, and the mixture was allowed to react at room temperature under a hydrogen atmosphere at normal pressure until the absorption of hydrogen gas ceased. After completion of the reaction, the catalyst was separated and the liquid was concentrated under reduced pressure to obtain a colorless and transparent oil. Then, the target 3 is obtained by recrystallization from methanol.
-(2'-Fluoro-4'-chloro-5'-hexyloxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 8] (330 mg, yield 66%) was obtained. .

Example 10 3- (2'-fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) -5-isopropyl-1,
To a solution of 3 poxazolidine-2,4-dione (15.2 g, 44.0 mmol) in dry methanol (150 ml) was added potassium carbonate (3.04 g, 22.
0 mmol) and stirred at room temperature for 3 hours. After the reaction,
A saturated aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with ether. After drying the ether layer, the solvent was distilled off under reduced pressure to obtain a pale yellow oil. This was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to give 3- (2'-
Fluoro-4'-chloro-5'-hydroxycyphenyl) -5-isopropyl-1,3-oxazolidine-2,4 dione [compound 14] (10.5 g, 83% yield) was obtained. Next, allyl bromide (2 ml) and potassium carbonate (340 mg) were added to a solution of this phenol derivative (700 mg, 2.43 mmol) in acetonitrile (30 ml), and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 1N hydrochloric acid was added, and the mixture was extracted with ether. After drying the organic layer, the solvent was distilled off under reduced pressure to obtain a pale yellow oil. This was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane =
Purified by 1/10) to give pure 3- (2'-fluoro-4'-chloro-5'-allyloxyphenyl)
-5-Isopropyl-1,3-oxazolidine-2,4-dione [compound 9] (540 mg, yield 68%) was obtained.

Example 11 3- (2'-fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) -5-isopropyl-1,
To a solution of 3-oxazolidine-2,4-dione (800 mg, 2.31 mmol) in dry methanol (30 ml) was added potassium carbonate (160 mg, 1.
16 mmol) and stirred at room temperature for 2 hours. Then, the solvent was distilled off under reduced pressure, fresh acetonitrile (30 ml) and allyl bromide (2 ml) were added, and the mixture was stirred under reflux for 3 hours.
After completion of the reaction, the solvent was distilled off under reduced pressure, 1N hydrochloric acid was added, and the mixture was extracted with ether. After drying the ether layer, the solvent was distilled off under reduced pressure to obtain a pale yellow oil. This was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to give 3-
(2'-fluoro-4'-chloro-5'-allyloxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 9] (240 mg, yield 32%) was obtained.

Example 12 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione (700 mg, 2.43 mmol) in N, N-dimethylformamide (30 ml) ) To the solution was added potassium carbonate (340 mg), and the mixture was stirred at 70 ° C for 40 minutes. Then, methallyl chloride (2.0 ml) was added, and the mixture was further stirred at 70 ° C. for 12 hours. After completion of the reaction, 1N hydrochloric acid was added to the solution, and the mixture was extracted with ether. The ether layer was washed three times with 1N hydrochloric acid, the organic layer was dried, and the solvent was distilled off under reduced pressure to obtain a pale yellow oil. This was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to give pure 3- (2'-fluoro-4'-chloro-5'-methacryloxyphenyl) -5. A colorless transparent oil (480 mg, yield 58%) of -isopropyl-1,3-oxazolidine-2,4-dione [compound 10] was obtained.

Example 13 By the same operation as the method shown in Example 5, 3-
(2'-fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-
2,4-dione (700 mg, 2.43 mmol) and 1-iodododecane and 3- (2'-fluoro-4'-chloro-5'-dodecyloxyphenyl) -5-isopropyl-1,3-oxazolidin-2 , 4-dione [compound 11] (760 mg, yield 6
9%).

Example 14 To a solution of 3- (2'-fluoro-4'-chloro-5'-dodecyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (500 mg, 1.10 mmol) in ethanol (30 ml) A catalytic amount of 10% Pd / C (100 mg) was added, and the mixture was allowed to react at room temperature under a hydrogen atmosphere at normal pressure until the absorption of hydrogen gas ceased. After completion of the reaction, the catalyst was separated and the liquid was concentrated under reduced pressure to obtain a colorless and transparent oil. Then, this was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to give pure 3- (2'-fluoro-4'-chloro-5'-dodecyloxyphenyl)-. A colorless transparent oil (420 mg, 84% yield) of 5-isopropyl-1,3-oxazolidine-2,4-dione [compound 11] was obtained.

Example 15 By the same operation as the method shown in Example 5, 3-
(2'-fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-
2,4-Dione (800 mg, 2.78 mmol) and (1-bromoethyl) benzene and 3- {2′-fluoro-4′-chloro-5 ′-(1 ″ -phenylethyl) oxyphenyl}
-5-Isopropyl-1,3-oxazolidine-2,4-dione [compound 12] (490 mg, yield 45%) was obtained.

Example 16 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione (700 mg, 2.43 mmol) in N, N-dimethylformamide (30 ml) ) Potassium carbonate (340 mg) was added to the solution, and the mixture was heated with stirring at 70 ° C for 40 minutes. Then, 2-iodododecane (0.7 ml) was added, and the mixture was further stirred at 70 ° C for 12 hours. After completion of the reaction, 1N hydrochloric acid was added to the solution, and the mixture was extracted with ether. The ether layer was washed three times with 1N hydrochloric acid, the organic layer was dried, and the solvent was distilled off under reduced pressure to obtain a pale yellow oil. This is subjected to silica gel column chromatography (eluent:
Purification by ethyl acetate / hexane = 1/10) gives pure 3- {2'-fluoro-4'-chloro-5'-
A colorless transparent oil (490 mg, yield 44%) of (2 "-dodecyl) oxyphenyl} -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 13] was obtained.

Example 17 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (200 mg, 0.70 mmol) in ethanol (20 ml) solution An amount of 10% Pd / C (40 mg) was added, and the mixture was reacted at room temperature under a hydrogen atmosphere at normal pressure until absorption of hydrogen gas ceased. After completion of the reaction, the catalyst was separated and the liquid was concentrated under reduced pressure to obtain a colorless and transparent oil. Then, this was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to give pure 3- (2'-fluoro-4'-chloro-).
5'-hydroxyphenyl) -5-isopropyl-1,3
-Oxazolidine-2,4-dione [compound 14] (180 mg,
Yield 89%).

Example 18 Ethyl 2- {N- (2'-fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) carbamoyloxy} isovalerate synthesized by the method of Production Example 3 (24.5 g,
To a solution of 62.5 mmol) in toluene (200 ml) was added a catalytic amount of sodium acetate, and the mixture was stirred under reflux for 3 hours. After completion of the reaction, 1N hydrochloric acid was added to the solution, and the mixture was extracted with ether. The organic layer was washed three times with 1N hydrochloric acid, dried and concentrated under reduced pressure. The obtained oil is subjected to silica gel column chromatography (eluent:
Purification by ethyl acetate / hexane = 1/3), 3-
(2'-fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 15] (15.2 g, yield 7
0%).

Example 19 3- (2'-Fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (370 mg, 1.08 mmol)
l) in ethanol (30 ml) solution with a catalytic amount of 10% Pd / C (80m
g) was added, and the mixture was reacted at room temperature under a hydrogen atmosphere at normal pressure until the absorption of hydrogen gas ceased. After completion of the reaction, the catalyst was separated and the liquid was concentrated under reduced pressure to obtain a colorless and transparent oil. Then, this was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to give pure 3- (2'-fluoro-4 ').
-Chloro-5'-methoxycarbonyloxyphenyl)
-5-Isopropyl-1,3-oxazolidine-2,4-dione [compound 15] (350 mg, yield 94%) was obtained.

Example 20 By the same operation as the method shown in Example 5, 3-
(2'-chloro-4'-chloro-5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4
-Dione (300 mg, 0.99 mmol) and propargyl bromide to give 3- (2'-chloro-4'-chloro-5'-propargyloxyphenyl) -5-isopropyl-1,3-
Oxazolidine-2,4-dione [compound 16] (264 mg, yield 81%) was obtained.

Example 21 By the same operation as in the method shown in Example 5, 3-
(2 ', 4'-dichloro-5'-hydroxyphenyl)-
5- (2 "-hexyl) -1,3-oxazolidine-2,4-
From dione (350 mg, 1.0 mmol) and propargyl bromide, 3- (2 ', 4'-dichloro-5'-propargyloxyphenyl) -5- (2 "-hexyl) -1,3-oxazolidine-2,4 -Dione [compound 17] (315 mg, yield 82
%).

Example 22 By the same operation as the method shown in Example 5, 3-
(2'-Fluoro-4'-fluoro-5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione (878 mg, 3.25 mmol) and propargyl bromide gave 3- (2 '-Fluoro-4'-fluoro-
5'-propargyloxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 18]
(503 mg, yield 52%) was obtained.

Example 23 In a manner similar to that described in Production Example 1, 2- {N- (2 ', 4'-difluoro-)-synthesized from 2,4-difluoro-5-propoxyphenylisocyanate and methyl lactate.
5'-Propoxyphenyl) carbamoyloxydimethyl lactate (635 mg, 2.0 mmol) in acetonitrile (30 ml)
To the mixture was added potassium carbonate (150 mg), and the mixture was stirred at room temperature for 6 hours. After the reaction was completed, 1N hydrochloric acid was added to the solution, and ether (50 ml ×
Extracted in 3). After drying the organic layer and removing the solvent, the resulting oil was purified by silica gel column chromatography (eluent: chloroform / hexane = 1/3) to give pure 3- (2 ', 4'-). Difluoro-
5'-propoxyphenyl) -5-methyl-1,3-oxazolidine-2,4-dione [compound 19] (320 mg, yield 56
%).

Example 24 In the same manner as in the method described in Production Example 1, 2-fluoro-
2-Synthesized from 4-chloro-5-propoxyphenylisocyanate and methyl 2-hydroxyisovalerate
Potassium carbonate (50 mg) was added to an acetonitrile solution (30 ml) of {N- (2'-fluoro-4'-chloro-5'-propoxyphenyl) carbamoyloxy} isovalerate (362 mg, 1.0 mmol), and the mixture was added at room temperature for 6 hours. Stirred. Post-treatment was carried out in the same manner as in Example 23 to give 3- (2'-fluoro-4'-chloro-5'-propoxyphenyl)-
5-isopropyl 1,3-oxazolidine-2,4-dione (205 mg, 62% yield) was obtained.

Example 25 By the same operation as the method shown in Example 5, 3-
(2'-Fluoro-4'-fluoro) -5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-2,4-dione (650 mg, 2.41 mmol) and (±) -2-chloropropio From nitrile, 3-{(2'-fluoro-4'-fluoro) -5 '-(2-cyanoethyl) oxyphenyl} -5-isopropyl-1,3-oxazolidine-2,4-dione [compound 21] ( 380 mg, yield 49%).

Example 26 By the same operation as the method shown in Example 5, 3-
(2'-chloro-4'-chloro) -5'-hydroxyphenyl) -5-isopropyl-1,3-oxazolidine-
From 2,4-dione (202 mg, 0.67 mmol) and (±) -2-chloropropionitrile, 3-{(2'-chloro-4 '
-Chloro) -5 '-(2-cyanoethyl) oxyphenyl} -5-isopropyl-1,3-oxazolidine-2,4-
Dione [compound 22] (114 mg, yield 48%) was obtained.

Production Example 1 Ether (30 mg, 2.26 mmol) of 2-fluoro-4-chloro-5-isopropoxyphenyl isocyanate (500 mg, 2.18 mmol) and ethyl 2-hydroxyisovalerate (476 mg, 3.26 mmol)
A small amount of propylene oxide and triethylamine (0.2 ml) were added to the solution, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the solution was washed three times with 1N hydrochloric acid, and the organic layer was dried and then concentrated under reduced pressure. The obtained light brown oily substance is subjected to silica gel column chromatography (eluent: ethyl acetate / hexane =
Purification by 1/10) yields pure 2- {N-
Ethyl (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) carbamoyloxy {isovalerate
0 mg, 67% yield).

Production Example 2 2-fluoro-4-chloro-5-cyclopentyloxyphenyl isocyanate (800 mg, 3.13 mmol) and ethyl 2-hydroxy-3-methyl-3-butenoate (679 mg, 4.
A small amount of propylene oxide and triethylamine (0.2 ml) were added to a solution of (71 mmol) in ether (30), and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the solution was washed three times with 1N hydrochloric acid, and the organic layer was dried and then concentrated under reduced pressure. The obtained light brown oily substance is subjected to silica gel column chromatography (eluent:
The product was purified by ethyl acetate / hexane = 1/10) and recrystallized from a mixed solvent of ether-hexane to give pure 2- {N- (2'-fluoro-4'-chloro-5'-).
Cyclopentyloxyphenyl) carbamoyloxy｝-
Ethyl 3-methyl-3-butenoate (1.01 g, yield 81%) was obtained. Next, a catalytic amount of 10% Pd / C (100 mg) was added to a solution of this in ethanol (30 ml) and reacted at room temperature under a hydrogen atmosphere at normal pressure until the absorption of hydrogen gas ceased. After completion of the reaction, the catalyst was separated and the liquid was concentrated under reduced pressure to obtain a colorless and transparent oil. Then, the desired 2- {N- (2'-fluoro-
4'-chloro-5'-cyclopentyloxyphenyl)
Ethyl carbamoyloxydiisovalerate (730 mg, yield 72
%).

Production Example 3 2-fluoro-4-chloro-5-methoxycarbonyloxyphenyl isocyanate (25 g, 102 mmol) and 2-
Propylene oxide (3 ml) and triethylamine (2.0 ml) were added to a solution of ethyl hydroxyisovalerate (22.4 g, 153 mmol) in ether (300 ml), and the mixture was stirred at room temperature for 3 hours.
After completion of the reaction, the solution was washed three times with 1N hydrochloric acid, and the organic layer was dried and then concentrated under reduced pressure. The resulting oily portion was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to give 2- {N- (2 ′).
Thus, ethyl -fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) carbamoyloxydiisovalerate (24.5 g, yield 61%) was obtained. MP: 79-81 ° C The compound of the present invention thus obtained has excellent performance as an active ingredient of a herbicide as described above.

In using the compound of the present invention as a herbicide,
Although it can be used as it is, generally, one or several adjuvants can be mixed and used as a herbicide. Usually, as an auxiliary agent, various simple substances, extenders, solvents, surfactants, stabilizers, etc. are blended and formulated into a form such as a wettable powder, an emulsion, a powder, a granule, and the like by a conventional method, and used. preferable.

As a solvent which is one of the auxiliary agents in the herbicide containing the compound of the present invention as an active ingredient, for example, water, alcohols,
Ketones, ethers, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, acid amides, esters,
Nitriles are suitable, and one or a mixture of two or more of them is used. Clays such as kaolin and bentonite; talc such as talc and pyrophyllite; mineral powders such as diatomaceous earth and oxides such as white carbon; and vegetable powders such as soybean powder and CMC are used as fillers. Is done. Further, a surfactant may be used as a spreading agent, a dispersant, an emulsifier, and a penetrant. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. These surfactants are utilized as one kind or a mixture of two or more kinds depending on the use.

Preferable methods of using the herbicide containing the compound of the present invention as an active ingredient include soil treatment, water surface treatment, foliage treatment, and the like. Can be.

Further, a herbicide containing the compound of the present invention as an active ingredient, other active ingredients that do not inhibit the herbicidal activity of the present active ingredient,
For example, other herbicides, insecticides, fungicides, plant growth regulators and the like can be used in combination or in combination.

Next, a formulation example of a herbicide containing the compound of the present invention as an active ingredient,
The present invention will be described in more detail with reference to Test Examples and the herbicidal effect of the present herbicide. The parts are by weight.

Formulation 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. Emulsions were obtained in the same manner for each of Compounds 2-13 and 16-20.

Formulation Example 2 (Wettable powder) A mixture of 50 parts of compound 1, 25 parts of diatomaceous earth, 22 parts of clay, and 3 parts of Lunox R100C (manufactured by Toho Chemical) is evenly mixed and pulverized, and a predetermined amount of water is added thereto to add a wettable powder. I got Compound 2-1
For each of 3, 16-20, a wettable powder was obtained in the same manner.

Formulation Example 3 (granules) A mixture of 5 parts of compound 1, 35 parts of pentonite, 55 parts of talc, and 5 parts of sodium ligninsulfonate is uniformly mixed and pulverized, and then kneaded by adding water, followed by extrusion granulator. After granulation, drying and sizing were performed to obtain granules. Compound 2-13, 16-20
In each case, granules were obtained in the same manner.

Test Example 1 (Effect on paddy field weeds) Paddy field soil was filled in a 1 / 5,000 arel Wagner pot, and the seeds of barnyardgrass, konagi, himemisohagi, and 2
Rice seedlings (variety: Nipponbare) at the 3rd leaf stage were sowed or transplanted and kept in a moist state. Five days later, water was introduced to a depth of 4 cm. Thereafter, a predetermined amount of a diluent was treated with water so that the compound of the present invention in the form of a wettable powder or an emulsion according to the formulation example became 20, 10, 5 g per are. Twenty days after the treatment, the herbicidal effect on the test plant and the phytotoxicity on the rice were investigated according to the following criteria, and the results shown in Table 4 were obtained.

Tables also show the results of investigations performed on the herbicidal activity of the comparative control compound using the same criteria.

Test Example 2 (Effects on Field Weeds) A field vat having an area of 16 × 11 cm ² and a depth of 7 cm was filled with field soil, and seeds of Meishishiba, Shiroza, Inubeyu, and soybeans were sown and covered with 1 cm of soil thereon. . The next day, the compound of the present invention made into a wettable powder or an emulsion according to the formulation example was added per are.
A predetermined amount of the diluting solution was evenly spread on the covering soil so that the weight became 20, 10, and 5 grams. Twenty days after the treatment, the weed 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 (Effects of Foliage Treatment) A 1 / 5,000-are Wagner pot was filled with field soil, and corn, weeds such as Shiroza, Inutade and Inubiyu were sown in the field soil, and the foliage of a plant grown 20 days later was grown. Each test compound formulated in the emulsion shown in Formulation Example 1 was diluted with water to a predetermined concentration, and a chemical solution having a predetermined concentration was sprayed uniformly on the test plant at a spray rate of 100 / 10a. Twenty days after the treatment, the herbicidal effect and the phytotoxicity were evaluated in the same manner as in Test Example 1. The results are shown in Table 6.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroaki Hirose 2-17 A-208, Tatsumidaihigashi, Ichihara City, Chiba Prefecture (72) Inventor Shoin Nagato 3-13-13-106, Kahama, Adachi-ku, Tokyo (56) References JP-A-62-167713 (JP, A) JP-A-62-174065 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (1) General formula Wherein R ¹ is a hydrogen atom, an alkyl group, a cyanoalkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group,
It represents an alkynyl group or a lower alkyloxycarbonyl group, and R ² represents an alkyl group or a cycloalkyl group. The alkyl group, cycloalkyl group, aralkyl group, alkenyl group and alkynyl group may be substituted. X ¹ and X ² independently represent a halogen atom. The oxazolidine derivative represented by these.