JPH0662370B2 - Herbicide - Google Patents

Description

TECHNICAL FIELD The present invention relates to a herbicide containing a novel oxazolidinedione derivative as an active ingredient. More specifically, the present invention has the general formula [Wherein R ¹ , R ² and R ³ are independently of each other a hydrogen atom, a halogen atom, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cycloalkyloxy group or an alkoxycarbonylalkoxy group; R ⁴ and R ^{4 And 5} each independently represent a hydrogen atom or an alkyl group; the alkenyloxy group may be substituted with a halogen atom], and an oxazolidinedione derivative represented by the formula [5] as an active ingredient.

Heretofore, various derivatives having a substituent at the 5-position of the oxazolidinedione ring have been known, but oxazolidinedione derivatives having a substituted methylidene group at the 5-position are difficult to synthesize and reported so far. 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] The present invention provides an excellent herbicide containing, as an active ingredient, a novel compound having both high selectivity for weeds and strong herbicidal activity.

[Means for Solving Problems] The present inventors have found that among the oxazolidinedione derivatives, 5
It was found that the introduction of a methylidene group having various substituents at the position results in strong herbicidal activity and high selectivity against various weeds.

The oxazolidinedione compound, which is the active ingredient of the present invention, is represented by the general formula (I), wherein R ¹ , R
² and R ³ are each independently a hydrogen atom; a halogen atom such as a fluorine, chlorine, bromine or iodine atom; a methoxy group, an ethoxy group, an n-propoxy group, an isoproxy group; an n-butoxy group, a t-butoxy group. 1 to 1 carbon number
8, preferably 1 to 8 alkoxy groups, which may be one or more alkoxycarbonyl groups (having 2 to 2 carbon atoms).
18) may be substituted; cyclohexyloxy group, cyclopentyloxy group, cyclopropyloxy group and the like, cycloalkoxy group having 3 to 12 carbon atoms, preferably 3 to 8; allyloxy group, methallyloxy group, propenyloxy group A linear or branched alkenyloxy group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as a butenyloxy group, a pentenyloxy group and a hexenyloxy group, which is substituted with one or more halogen atoms or the like. Or propargyloxy group, 1-methylpropargyloxy group, 1,1-dimethylpropargyloxy group, 2-butynyloxy group, 3-butynyloxy group, 2
A linear or branched alkynyloxy group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as a pentynyloxy group or a 3-pentynyloxy group, wherein R ⁴ and R ⁵ are each independently a hydrogen atom; Methyl group,
A linear or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, n-octyl group, etc. is there.

The bonding position of the phenyl group of R ¹ , R ² and R ³ is not particularly limited, but when two of R ^{1 to} R ³ are other than hydrogen, 2,4-, 2,5-, 3,4-, 3,5-position is preferred, and when all three are other than hydrogen, 2,4,5-,
Alternatively, it is preferably at the 2,4,6-position.

Table 1 shows typical compounds represented by the formula (I) of the present invention.

When used in a paddy field, the novel oxazolidinedione derivative which is an active ingredient of the present invention exhibits a strong weed efficacy against annual weeds such as Hyacinthus edulis, Himemisohagi, and perennial weeds such as Cyperus communis, Firefly, Urikawa and Matsubais. Also in the field, it is possible to selectively kill the field weeds such as Aedes peregrinus, Crabgrass, Enocologsa, Silza, Polygonum, Aubiyu, Purslane, Psyllium.

Further, the compound used in the present invention has a strong weed-killing activity, and not only the desired effect can be obtained with a small amount, but the phytotoxicity to useful cultivated plants is extremely low. That is, the compound which is the active ingredient of the present invention kills grass weeds such as millet, crabgrass and green locust, while it gives almost no phytotoxicity to rice plant crops such as transplanted rice, wheat and corn. Absent. Almost no phytotoxicity is observed for soybeans, cotton, etc., which are crops other than Poaceae.

The compound which is the active ingredient of the present invention is mixed with various carriers, fillers, solvents, surfactants, stabilizers and the like, and formulated into a desired form such as a wettable powder, an emulsion, a powder, a powder by a conventional method. Be herbicide.

Further, in the preparation, many active ingredients such as other herbicides, insecticides, fungicides, growth regulators and the like can be mixed.

The amount of the herbicide of the present invention varies depending on the application method, time, type of target plant, etc., but the compound amount is 10 per 10 ares.
It is about 500 g, preferably about 30 to 300 g.

The novel oxazolidinedione derivative represented by the general formula (I), which is the active ingredient of the present invention, has the general formula ^{Wherein, R 1, R 2, R} 3, R 4 and ^{R 5} are as defined above, ^{R 6} represents a lower alkyl group _(C 1 _{~C 4).} ] The carbamic acid ester represented by the above can be easily obtained by treating with a base (first production method). The reaction is preferably carried out in an ordinary organic solvent with heating or reflux.

The first and the first methods are essentially required to treat the carbamate represented by the general formula (II) with a base. The base used is triethylamine, tripropylamine, tributylamine,
Tertiary amines such as N-methylmorpholine and dimethylaniline, aromatic amines such as pyridine, lutidine and pyrimidine, alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, sodium hydride and potassium hydride. Alkali metal hydrides such as, or basic inorganic compounds such as sodium carbonate, potassium carbonate, sodium hydride, potassium hydroxide, and the like can be used. Catalytic amounts of base are generally sufficient.

The compound represented by the general formula (II), which is the starting material for this reaction, can be easily produced according to the following method. [Wherein R ¹ , R ² and R ³ are as described above, and Y
Represents an isocyanato group or a carbamoyl chloride group. ]
The aryl isocyanate or carbamoyl chloride represented by [In formula, R < ⁴ >, R < ⁵ > and R <^6> are as above-mentioned. ]
It can be easily obtained by reacting with a β, γ-unsaturated-α-hydroxycarboxylic acid ester represented by

Aryl isocyanates and carbamoyl chlorides represented by the general formula (III) are compounds that can be easily obtained, for example, from the corresponding aniline derivatives.

The 2-hydroxycarboxylic acid ester represented by the general formula (IV) can be easily produced from an inexpensive commercially available raw material for a lower alkyl ester.

The reaction is carried out by reacting the compound of general formula (III) and the compound of general formula (IV) in an organic solvent, optionally in the presence of a base, at room temperature to reflux temperature.
The compound I) can be produced (Examples 1 to 1 in the table below).
3).

In carrying out the above reaction, the above-mentioned general formula (II
The general formula (I) formed by the reaction of the compounds of I) and (IV)
By treating the carbamic acid ester represented by I) with a base without isolation from the reaction system, the desired oxazolidinedione derivative represented by the above general formula (I) can be produced.

Examples of the organic solvent used in this reaction include aromatic solvents such as benzene, toluene and kylene, ether solvents such as dioxane, tetrahydrin, dimethoxyethane, alcohol solvents such as methanol, ethanol and isopropyl alcohol, or acetic acid. There are solvents such as ethyl, dimethylformamide, and dimethylsulfoxide.

In the practice of this reaction, after completion of the reaction, the solvent can be removed from the reaction mixture, and the mixture can be separated and purified using a silica gel column or the like, but an insoluble solvent such as an alcoholic solvent may be added, and the mixture may be added if necessary. The pure oxazolidinedione derivative can be easily isolated by separating the crystals that precipitate by cooling.

Among the compounds represented by the above general formula (I) which are the active ingredients of the present invention, the following general formula (I ′) [Wherein R ¹ , R ² , R ⁴ and R ^{5 are as} described above, R ³ ′ is —O—R ⁷ , (R ⁷ is a substituent having the same carbon number as R ^{3 of} formula (I)) Or an unsubstituted alkyl group, an alkenyl group, an alkynyl group, or a cycloalkyl group) is produced by the following second method. That is, the general formula [Wherein R ¹ , R ² , R ⁴ and R ⁵ are as described above and M is a hydrogen atom or an alkali metal] and a phenol derivative represented by the general formula R ⁷ -Y (VI) R ⁷ is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group or cycloalkyl group,
Y is a leaving group] [reaction in the presence of a base when M is a hydrogen atom in the general formula (V)] (second production method) The reaction is preferably carried out in an organic solvent. As the organic solvent, hexane, heptane, aliphatic hydrocarbons such as ligroin, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, diisopropyl ether,
Ethers such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and isobutyronitrile, amides such as N, N-dimethylformamide, sulfur compounds such as dimethyl sulfoxide and sulfolane. It is possible to use types and the like or a mixture thereof.

In the general formula (V), when M is a hydrogen atom, the general formula (V
As the base used in the reaction with the compound of I),
Organic bases such as pyridine, triethylamine, N, N-dimethylaniline, sodium hydroxide, potassium hydroxide,
Inorganic bases such as sodium carbonate and potassium carbonate, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, and carboxylic acid alkali metal salts such as sodium acetate and potassium acetate can be used.

When chloride, bromide or sulfonate is used as the compound represented by the general formula (VI) in this reaction, depending on the compound, iodide such as potassium iodide or sodium iodide, tetraethylammonium bromide or benzyltriethylammonium may be used. By adding a quaternary ammonium salt such as bromide or iodide, the progress of the reaction can be accelerated and the compound which is the active ingredient of the present invention can be obtained in good yield.

After completion of the reaction, the product can be obtained by a usual post-treatment, but if necessary, it is purified by column chromatography, recrystallization or the like.

The compound represented by the general formula (VI), which is the starting material for this reaction, can be easily prepared from commercially available starting materials, such as methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, isopropyl bromide, Alkyl halogen compounds such as isopropyl iodide, butyl bromide, butyl iodide, sec-butyl bromide, cyclohexyl iodide, cyclohexyl bromide, cyclopentyl bromide, cyclopentyl iodide, cyclopropyl bromide, propargyl chloride, propargyl bromide, propargyl iodide, 1 -Bromo-2-butyne, 1-chloro-2-butyne, 2-chloro-1-butyne, 2-bromo-1-butyne, 3-bromo-3-methyl-1-butyne, 3-chloro-3-methyl -1-butyne Acetylene such as 1-bromo-2-pentyne, 6-chloro-1-hexyne, 1-bromo-3-pentyne, 3-bromo-1-butyne, 3-chloro-1-butyne, 4-bromo-1-butyne Compound, allyl bromide, allyl chloride, methallyl bromide, crotyl chloride, crotyl bromide, 1,3-dichloro-1-propene, 2,3-dichloro-1-propene, 4
-Bromo-3-methyl-1-butene, prenyl bromide, 3-bromo-3-methyl-1-butene, 2,3-dibromo-1-butene and other olefin compounds, ethyl 2-bromoacetate, 2-chloroacetic acid Substituted alkyl halogen compounds such as ethyl, methyl 2-bromopropionate, ethyl 2-bromoacetate, isopropyl 2-bromoacetate, (2'-ethyl) hexyl 2-bromopropionate, or propargyl alcohol, 1-butyne-3. Alcohols such as -ol, 3-methyl-1-butyn-3-ol, 1-butyn-4-ol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, methyl glycolate and methyl lactate. Sulfonates of common lower aliphatic alcohols, p-toluene sulfonates, benzes Sulfonic acid ester or the like can be used.

The phenol derivative represented by the general formula (V), which is a raw material for producing the compound which is the active ingredient of the present invention, has the general formula [In the formula, R ¹ , R ² , R ⁴ and R ⁵ have the same meanings as described above, and R ⁸ represents a lower alkyl group having 1 to 4 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ] The carbonic acid ester derivative represented by the above can be easily produced by treating it in an ordinary organic solvent in the presence of a base. (See Reference Examples 4 to 12 below) Further, in carrying out the reaction in the second production method,
A metal salt of a phenol derivative obtained by treating the compound of the general formula (VII) with a base [M in the general formula (V)
Is an alkali metal) and is reacted with the compound represented by the general formula (VI) without isolation from the reaction system to give 1,3-oxazolidine-2, represented by the general formula (I ′). 4-dione derivatives can be prepared. Further, the oxazolidinedione derivative represented by the general formula (VII) can be produced by the following method.

That is, the nitrobenzene derivative (VIII) (in the formula, R ¹
And R ² have the same meaning as described above. R ⁸ represents a lower alkyl group or an aralkyl group. ) Is reduced in the presence of a catalyst such as platinum oxide, platinum-carbon, palladium-carbon or the like to give an aniline derivative (IX) (in the formula, R ¹ , R ² and R ^2
8 has the same meaning as described above. ) And then easily converted to the isocyanate derivative (X) (wherein R ¹ , R ² and R ⁸ have the same meanings as described above) by treating with phosgene gas or trichloromethyl chloroformate. You can Next, this isocyanate derivative (X) and β, γ-unsaturated glycolic acid ester (XI) (in the formula, R ⁴ and R ⁵ have the same meanings as described above, and R ⁹ is a lower alkyl having 1 to 4 carbon atoms). And a carbamate derivative (XII) (in the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹ are the same as those described above). Have the same meaning.) And cyclizing the carbamic acid ester derivative using a tertiary amine such as triethylamine or tributylamine, an inorganic base such as potassium carbonate or sodium methoxide, or a carboxylic acid salt such as sodium acetate as a base. Can produce an oxazolidinedione derivative (VII).

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Synthesis Reference Examples, Formulation Examples, and Experimental Examples. The physical properties and spectrum measurement values of the compounds synthesized in Synthesis Examples 1 to 38 are shown in Tables 2 and 3.

Synthesis example 1. 2- {N-4'-chlorophenyl) carbamoyloxy}
Methyl-3-methyl-3-butenoate (2.71 g, 10 mmol
) In benzene (50 ml) solution with triethylamine (1.0 ml)
Was added and the mixture was heated under reflux for 5 hours. The solvent was completely removed under reduced pressure, and then methanol was added to precipitate white crystals (1.87
g) was isolated by filtration. This is NMR and I
From R, it was confirmed to be 3- (4'-chlorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Synthesis example 2. 2- {N- (2 ', 4'-dichloro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-
Methyl butenoate (1.82 g, 5.0 mmol) Benzene (50 m
l) Sodium methoxide (0.1 g) was added to the solution and heated under reflux for 1 hour, and then the solvent was distilled off. Methanol (20m
l) was added and after cooling, white crystals (1.10 g) precipitated were separated. This is 3- (2 ', 4'-dichloro-5'-isopropoxyphenyl) -5-isopropylidene-1,
NM that it is 3-oxazolidine-2,4-dione
It was confirmed by R and IR.

Synthesis example 3. Sodium was added to a solution of methyl 2- {N- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate (1.79 g, 5 mmol) in toluene (50 ml). Methoxide (0.1 g) was added and the mixture was heated under reflux for 2 hours. Then, the solvent was completely distilled off, methanol (20 ml) was added, the mixture was cooled, and white crystals (0.98
g) was separated. This one is from NMR and IR,
It was confirmed to be 3- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Synthesis example 4. Methyl 2- {N- (2 ', 4'-difluorophenyl) carbamoyloxy} -3-methyl-3-butenoate (1.43
g, 5 mmol) in toluene (30 ml) was added with sodium methoxide (50 mg), and the mixture was heated under reflux for 3 hours. The solvent was completely removed under reduced pressure, and then methanol was added to precipitate white crystals (0.76 g) which were isolated by filtration. This was confirmed to be 3- (2 ', 4'-difluorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione by NMR and IR.

Synthesis example 5. Methyl 2- {N- (4'-fluorophenyl) carbamoyloxy} -3-ethyl-3-butenoate and 2- {N-
(2 ', 4'-Dichlorophenyl) carbamoyloxy}
A mixture of methyl-methyl-3-pentenoate (1.40 g, 5
N-methylmorpholine (0.5 ml) was added to a benzene (30 ml) solution of (mmol) and reacted for 3 hours while heating under reflux. The solvent was distilled off completely, and then methanol was added to isolate precipitated white crystals (1.05 g). This is NMR and I
From R, 3- (2 ', 4'-dichlorophenyl) -5-
(2 'Butylidene) -1,3-oxazolidine-2,4
-Confirmed to be Zion.

Synthesis examples 6-10. In the same manner as in Synthesis Example 1, the corresponding oxazolidinedione derivative was synthesized from the following carbamate ester.

Synthesis Example 6: 2- {N- (4'-bromophenyl)
Methyl carbamoyloxy} -3-ethyl-3-butenoate and methyl 2- {N- (4′-bromophenyl) carbamoyloxy} -3-methyl-3-pentenoate Synthesis Example 7: 2- {N- (2 ′, Methyl 4′-dichlorophenyl) carbamoyloxy} -3-methyl-3-butenoate Synthesis Example 8: Methyl 2- {N- (4′-fluorophenyl)) carbamoyloxy} -3-methyl-3-butenoate Synthesis Example 9: 2- {N- (4'-chlorophenyl)
Ethyl carbamoyloxy} -3-ethyl-3-butenoate and methyl 2- {N- (4'-chlorophenyl) carbamoyloxy} -3-methyl-3-pentenoate Synthesis Example 10: 2- {N- (2'-nitro -4'-trifluoromethylphenyl) carbamoyloxy} -3-
Methyl methyl-3-butenoate Synthesis Examples 11 to 14 In the same manner as in Synthesis Example 2, the corresponding oxazolidinedione derivative was synthesized from the following carbamate ester.

Synthesis Example 11: Methyl 2- {N- (2 ′, 4′-dichlorophenyl) carbamoyloxy} -3-methyl-3-butenoate Synthesis Example 12: 2- {N- (2 ′, 4 ′, 6′-tri Chlorophenyl) carbamoyloxy} -3-methyl-3
-Methyl butenoate Synthesis example 13: 2- {N- (2 ', 4'-dichlorophenyl) carbamoyloxy} -3-ethyl-3-pentenoate methyl Synthesis example 14: 2- {N- (4'-chlorophenyl)
Carbamoyloxy} -2- (1'-cyclohexenyl)
Methyl acetate Synthetic example 15. 2,4-dichlorophenyl isocyanate (4.16 g, 2
A solution of 2.2 mmol) and methyl 2-hydroxy-3-methyl-3-butenoate (5.72 g, 44 mmol) in benzene (60 ml) was reacted under heating under reflux for 2.5 hours. N of reaction mixture
From the MR and IR spectra, the raw material isocyanate completely disappeared, and the carbamic acid ester [2- {N- (2 ', 4'-dichlorophenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl ester] as an adduct was obtained. Has been generated. Then, sodium methoxide (100 mg) was added and the mixture was heated under reflux for 5 hours. Then, the solvent was distilled off, methanol (20 ml) was added, and after cooling, white crystals (3.32 g) precipitated were separated. It was confirmed from NMR, IR, etc. that this was 3- (2 ', 4'-dichlorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Synthesis example 16. 2-Fluoro-4-chloro-5-isopropoxyphenylisocyanate (2.30 g, 10 mmol) and methyl 2-hydroxy-3-methyl-3-budenate (3.0 g, 23 mmol).
A solution of () in toluene (50 ml) was reacted at 80 ° C for 3 hours. From the IR and ¹ H-NMR spectra of the reaction mixture, the isocyanate completely disappeared and the carbamic acid ester [2- {N-2′-fluoro-4′-chloro-5′-isopropoxyphenyl) carbamoyloxy} which was an adduct was obtained. It was confirmed that [-3-methyl-3-methyl-3-butenoate] was produced. Then sodium methoxide (0.1
g) was added, and the mixture was reacted for 5 hours under heating and ring distillation. Methanol (10 ml) was added to the reaction mixture obtained by completely distilling off the solvent, and white crystals (1.49 g) precipitated after cooling were separated.
This product has a 3-
It was confirmed to be (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Synthesis example 17. Reaction was carried out in the same manner as in Synthesis Example 15, except that 3,5-dichlorophenyl isocyanate was used as the isocyanate.
3- (3 ', 5'-Dichlorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione was obtained.

Synthesis example 18. The reaction was performed in the same manner as in Synthesis Example 15 except that methyl 2-hydroxy-3-ethyl-3-pentenoate was used as the 2-hydroxycarboxylic acid ester, and 3- (2 ', 4'-dichlorophenyl) -5- ( 3'-Pentylidene) -1,3
-Oxazolidine-2,4-dione was obtained.

Synthesis example 19. Phenylisocyanate (1.19 g, 10 mmol) and methyl 2-hydroxy-3-methyl-3-butenoate (2.0 g, 15
A solution of mmol) in benzene (50 ml) was reacted for 2 hours at room temperature. From the NMR and IR spectra of the reaction mixture, the starting isocyanate disappeared, and the adduct of albamic acid ester [2- (N-phenylcarbamoyloxy)-
It was confirmed that 3-methyl-3-methylbutenoate] was produced. Then, triethylamine was added and the reaction was carried out under benzene reflux for 3 hours. Then, the solvent was distilled off and methanol (10 ml) was added to obtain white crystals (1.51 g) which were precipitated.
It was confirmed from NMR, IR, etc. that this was 3-phenyl-5-isopropylidene-1,3-ocisazolidine-2,4-dione.

Synthesis examples 20 to 26. In the same manner as in Synthesis Example 15, a corresponding carbamic acid ester was synthesized from the following aryl isocyanate and 2-hydroxycarboxylic acid ester, and then treated with a base to synthesize a desired oxazolidinedione derivative.

Synthesis Example 20: 2-Fluorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-butenoate Synthesis Example 20 ′: 4-Chlorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-heptenoate and 2-hydroxy Methyl -3-butyl-3-butenoate Synthesis Example 21: 4-Chlorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-nonenate and methyl 2-hydroxy-3-hexyl-3-butenoate Synthesis Example 22: 3,4-Dichlorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-butenoate Synthesis Example 23: Phenylisocyanate and methyl 2-hydroxy-2-ethyl-3-pentenoate Synthesis Example 24: 3,4-Dichlorophenylisocyanate And 2-hydroxy-3-phenyl-3-butenoic acid methyl ester Synthesis Example 25: 3,4-dichlorophenyl isocyanate and 2-hydroxy-3- (4′-chlorophenyl)
Methyl-3-butenoate Synthesis Example 26: Phenyl isocyanate and methyl 2-hydroxy-3- (4′-chlorophenyl) -3-butenoate Synthesis Examples 27 to 31. In the same manner as in Synthesis Example 19, the target oxazolidinedione derivative was synthesized by synthesizing the corresponding carbamate from the following aryl isocyanate and 2-hydroxycarboxylic acid ester and treating with a base.

Synthetic Example 27: 4-chlorophenylisocyanate and methyl 2-hydroxy-3-ethyl-pentenoate Synthetic Example 28: 4-fluorophenyl isocyanate and methyl 2-hydroxy-3methyl-3-butenoate Synthetic Example 29: 3,5 -Dichlorophenyl isocyanate and 2-hydroxy-3- (4'-chlorophenyl)
Methyl-3-butenoate Synthesis example 30: 4-Chlorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-butenoate Synthesis example 31: 4-Fluorophenylisocyanate and 2-hydroxy-3-ethyl-3-pentenoic acid Methyl and methyl 2-hydroxy-3-ethyl-3-butenoate Synthesis example 32. N- (3,5-dichlorophenyl) carbamoyl chloride prepared from 3,5-dichloroaniline (3.24 g, 20 mmol) and trichloromethyl chloroformate and methyl 2-hydroxy-3-methyl-3-butenoate (1.30 g, 10 mmo
l) in benzene (50ml) solution, triethylamine (2m
l) was added and reacted at room temperature for 3 hours. The precipitated triethylamine hydrochloride was separated and the solvent and excess triethylamine were removed. From the NMR and IR spectra of the mixture, it was confirmed that methyl 2- {N- (3 ', 5'-dichlorophenyl) carbamoyloxy} -3-methyl-3-butenoate was produced. Then, sodium methoxide (50 mg) was added and the mixture was reacted under heating under reflux for 3 hours. After completion of the reaction, the solvent was completely distilled off, and the resulting reaction mixture was added.
0.1N hydrochloric acid was added and the mixture was extracted with ether. After drying, the solvent was completely removed, and then methanol was added to precipitate white crystals.
(1.80 g) was obtained. It was confirmed that this was 3- (3 ', 5'-dichlorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Synthesis example 33. 2-Fluoroaniline (2.22 g, 20 mmol) and N- (4-fluorophenyl) carbamoyl chloride prepared from trichloromethyl chloroformate and 2-hydroxy-3-
Triethylamine (2 ml) was added to a benzene (50 ml) solution of methyl-3-butenoate (1.30 g, 10 mmol), and the mixture was reacted at room temperature for 3 hours. Then, the reaction mixture was reacted under heating under reflux for 3 hours, after completion of the reaction, the solvent and the like were completely distilled off, and 0.1N hydrochloric acid was added to the obtained reaction mixture, followed by extraction with ether. After drying, the solvent was completely removed, methanol was added, and the mixture was cooled to give white crystals (1.17 g) which were precipitated. This is the target 3- (4'-fluorophenyl)-
5-isopropylidene-1,3-oxazolidine-2,
It was confirmed to be 4-dione from the spectrum and the like.

Synthesis example 34. The reaction was performed in the same manner as in Synthesis Example 27 except that a mixture of methyl 2-hydroxy-3-ethyl-3-butenoate and methyl 2-hydroxy-3-methyl-3-pentenoate was used as the 2-hydroxycarboxylic acid ester. Done, 3-
(4'-Fluorophenyl) -5-isobutylidene-
1,3-oxazolidine-2,4-dione (0.41 g) was obtained.

Synthesis example 35. Ethyl 2-hydroxy-3-methyl-3-butenoate (3,6 g, 25 mmol) was added to 4-ethylphenylisocyanate prepared from 4-ethylaniline (3.63 g, 30 mmol) and trichloromethyl chloroformate and benzene was added. (50 ml)
The mixture was heated to reflux in the presence of pyridine (1.0 ml) in the solvent. After 2 hours, the solvent and the like were completely distilled off, and methanol was added to the resulting mixture to precipitate white crystals (3.3 g) which were isolated by filtration. From NMR, IR, etc., it was confirmed that this was 3- (4'-ethylphenyl) -5-isopropylpyridene-1,3-oxazolidine-2,4-dione.

Synthesis example 36. 3,5-dichlorophenyl isocyanate (1.88 g, 10
2-Hydroxy-2-cyclopentenylacetate (1.95 g, 15 mmol) was added to (mmol) and reacted in a benzene (30 ml) solvent, and it was confirmed by spectrum that the isocyanate disappeared and a carbamate was formed. After that, triethylamine (0.5 ml) was added, and the mixture was reacted under reflux of benzene for 3 hours. The solvent and the like were completely distilled off, and methanol was added to separate precipitated white crystals (1.24 g). This is 3- (3 ', 5'-dichlorophenyl) -5-
Cyclopentylden-1,3-oxazolidine-2,4
-It was confirmed to be dione from NMR and IR spectra.

Synthesis example 37. 2-hydroxycarboxylic acid ester is 2-hydroxy-
Synthetic example except that it is methyl 3-ethyl-3-pentenoate
Reaction was carried out in the same manner as in 36, and 3- (3 ', 5'-dichlorophenyl) -5- (3'-pentylidene) -1,3-
Oxazolidine-2,4-dione was obtained.

Synthesis example 38. Methyl 2 {N- (2'-chloro-5'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-heptenoate and methyl 3-butyl-3-butenoate (1.9
To a solution of 7 g, 5 mmol) in toluene (30 ml), potassium-
t-Butoxide (50 mg) was added and the mixture was reacted with heating under reflux for 2 hours. After completion of the reaction, the solvent was distilled off, methanol was added to the obtained mixture and the mixture was cooled. Precipitated white crystals (0.85 g)
Separated. This was confirmed to be 3- (2'-chloro-5'-trifluoromethylphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione by NMR and IR spectra.

The starting compounds of the above Synthetic Examples 1-38 were prepared by the following Reference Examples 1-4.

Reference example 1. 2,4-Dichloro-5-isopropoxyphenylisocyanate (1.72 g, 7 mmol) and 2-hydroxy-3-
A solution of methyl-3-butenoate methyl (1.04 g, 8 mmol) in benzene (20 ml) was heated under reflux for 2 hours. The obtained reaction mixture was separated and purified by a silica gel column to give methyl 2- {N- (2 ', 4'-dichloro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate (0.67). g) was obtained as a colorless transparent oil. ¹ H-NMR (CDCl ₃ -TMS, ppm): δ 1.37
(d, 6H, J = 6Hz), 1.82 (d, 3H, J = 1.5Hz)
, 3.72 (s, 3H), 4.53 (sept, 1H, J = 6Hz)
, 5.07 (q, 1H, J = 1.5Hz), 5.17 (br, s,
1H), 5.30 (s, 1H), 7.13 (br, s, 1H),
7.25 (s, 1H), 7.87 (s, 1H).

IR (neat, cm ^-1 ): 3350, 1740, 1410, 1210, 860.

Reference example 2. To a solution of N- (2,4-difluorophenyl) carbamoyl chloride (2.58 g, 20 mmol) in benzene (30 ml), 2
Methyl -hydroxy-3-methyl-3-butenoate (3.0
g, 23 mmol), and then N-methylmorpholine
(2.5 ml) was added and reacted at room temperature for 3 hours. After completion of the reaction, water was added to separate the organic layer, and the organic layer was dried and the solvent was distilled off to separate and purify the reaction mixture, which was purified by a silica gel column to give 2- {N- (2 ', 4'-difluorophenyl). ) Carbamoyloxy} -3-methyl-3
-Methyl butenoate (3.99 g) was obtained. ¹ H-NMR (CDCl ₃ -TMS, ppm): δ 1.80
(d, 3H), 3.71 (s, 3H), 5.03 (q, 1H), 5.1
5 (s, 1H), 5.30 (d, 1H), 6.78 (m, 2
H), 7.07 (br, s, 1H), 8.03 (m, 1H).

IR (neat, cm ^-1 ): 3350, 1740, 1430, 1220, 850.

Reference example 3. 2,4-dichlorophenyl isocyanate (3.80 g, 2
0.2 mmol) and methyl 2-hydroxy-3-methyl-3-butenoate (3.05 g, 23.5 mmol) in toluene (80 ml) were reacted under heating under reflux for 5 hours, and the resulting reaction mixture was separated and purified by a silica gel column. By doing 2-
Methyl {N- (2 ', 4'-dichlorophenyl) carbamoyloxy} -3-methyl-3-butenoate (4.02 g) was obtained as a colorless transparent oil. ¹ H-NMR (CDCl ₃ -TMS, ppm): δ 1.85
(D, 3H), 3.78 (s, 3H), 5.23 (q, 1H),
5.23 (br, s, 1H), 5.48 (s, 1H), 7.12 (m, 1
H) 7.35 (m, 2H), 8.13 (d, 1H).

IR (neat, cm ^-1 ): 3350, 1738, 1420, 1215, 855.

The second manufacturing method will be described below in Synthesis Examples 39 to 46.

Synthesis Example 39 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (0.72 g, 2.5 mmol) in acetonitrile (30 ml) solution Sodium carbonate (0.16 g) was added and the mixture was reacted under reflux for 1 hour. Then propargyl bromide (0.36 g, 3.0 mmol) was added and the mixture was refluxed for another 1
Reacted for hours. After completion of the reaction, 0.1N-hydrochloric acid was added to make the mixture weakly acidic, the mixture was extracted with chloroform, dried and the solvent was distilled off to obtain a pale yellow oil. This was purified by silica gel column chromatography to give pure 3- (2'-
Fluoro-4'-chloro-5'-propargyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione was obtained. (Yield 0.53 g, yield 65
%) Synthetic example 40 3- (2'-Fluoro-4'-bromo-5-hydroxyphenyl) -5- (sec-butylidene) -1,3-oxazolidine-2,4-dione (0.26 g, 0.82 mmol) in acetonitrile (25 ml) Potassium carbonate (0.11 g) was added to the solution, and the mixture was reacted under reflux for 1 hour. Then, propargyl bromide (0.1 g, 0.83 mmol) was added, and the mixture was further reacted for 1 hour. By the same operation as in Synthesis Example 1, 3- (2'-fluoro-4'-bromo-5-propargyloxy) -5- (s
ec-Butylidene) -1,3-oxazolidine-2,4-
Dione (0.24 g, 77%) was obtained.

Synthesis example 41 3- (2'-fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (0.57 g, 2.0 mmol) and potassium carbonate (0.27 g) 1-butyn-3-ol p-toluenesulfonic acid ester (0.5 g, 2.2 mmol) and a catalytic amount of benzyltriethylammonium bromide (about 20 mg) were added to the acetone nitrile (30 ml) solution of (1) and heated under reflux for 15 hours. After completion of the reaction, ether was added and the solution was washed with 1N-hydrochloric acid, dried and the solvent was distilled off to obtain a light brown oily substance. This product was separated and purified by silica gel column chromatography to give 3- {2'-fluoro-
4'-chloro-5 '-(1 "-methylpropargyl) oxyphenyl} -5-isopropylidene-1,3-oxazolidine-2,4-dione (0.34 g, yield 50%) was obtained.

Synthesis Example 42 A solution of 3- (2 ', 4'-dichloro-5'-hydroxyphenyl) -5- (sec-butylidene) -1,3-oxazolidine-2,4-dione (1.58 g.5.0 mmol) in acetonitrile (30 ml). Potassium carbonate (0.69 g) was added to and heated under reflux for 2 hours. Then, ethyl 2-bromopropionate (0.93 g, 5.1 mmol) was added and the mixture was further refluxed for 1 hour. After completion of the reaction, ether was added to the solution, the mixed solution was washed with 1N-hydrochloric acid, dried and the solvent was distilled off. By separating and purifying the obtained oil using a silica gel column,
3- {2 ', 4'-dichloro-5'-(1 "-ethoxycarbonylethyl) oxyphenyl} -5- (sec-butylidene) -1,3-oxazolidine-2,4-dione (1.51 g, yield Rate 73%).

Synthesis Example 43 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (2.85 g, 10 mmol) and isopropyl iodide (3 ml) And potassium carbonate (3.5g)
An acetonitrile (50 ml) solution of was heated 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, ether was distilled off under reduced pressure, and methanol was added to the resulting oil and cooled. The precipitated crystals were isolated by filtration. This is 3- {2'-fluoro-4'-chloro-5'-isopropoxyphenyl)
-5-isopropylidene-1,3-oxazolidine-
It was confirmed to be 2,4-dione (Compound 27) (3.10 g, yield 95%) (Compound 27).

Synthesis Example 44 DM of 3- (2'-fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (175 mg, 0.61 mmol)
Potassium carbonate (42 mg) was added to the F (10 ml) solution at room temperature for 3
Stir for hours. Then 2,3-dichloro-1-propene
(0.5 ml) was added, and the mixture was further stirred at room temperature for 1 hour. After completion of the reaction, the solvent and the like were removed under reduced pressure, 0.1N-hydrochloric acid was added, and the mixture was extracted with ether. After drying, ether was removed from the solution under reduced pressure, and methanol was added to cool the solution. Precipitated white crystals (80
mg, yield 36%) is the target 3- {2'-fluoro-
It was 4'-chloro-5- (2 "-chloroallyl) oxyphenyl} -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Synthesis Example 45 3- (2'-fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) -5-isopropylidene-
1,3-oxazolidine-2,4-dione (3.43 g, 10
mmol) in methanol (50 ml) and K ₂ CO ₃ (1.38
g, 10 mmol) was added and the mixture was heated to reflux for 1 hour. Then, the solvent was completely removed under reduced pressure, and fresh acetonitrile (50
ml) was added. Further, propargyl bromide (5 ml) was added and the reaction was carried out at room temperature for 2 hours. The reaction mixture was treated as in Synthesis Example 39 and purified by silica gel column chromatography to give 3- (2′-fluoro-4 ′).
-Chloro-5'-propargyloxyphenyl) -5-
Isopropylidene-1,3-oxazolidine-2,4-
Dione (0.89 g, yield 28%) was obtained.

Synthesis Example 46 Oily (about 60%) sodium hydride (5.0 mmol) was washed with hexane to remove the solvent, dry tetrahydrofuran (10 ml) was added, and then 3- (2'-fluoro-4'-).
Chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (1.
43 g, 5.0 mmol) was added, and the mixture was stirred at room temperature until the generation of hydrogen stopped. By removing the solvent, 3- (2 '
A white solid of -fluoro-4'-chloro-5'-sodium oxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione was obtained. Then, add acetonitrile (10 ml) and methyl iodide (1 m
l) was added and the mixture was heated with stirring for 3 hours. After the reaction was completed, 0.1N-hydrochloric acid was added to weakly acidify, the mixture was extracted with chloroform, dried and the solvent was distilled off to obtain a pale yellow oil. By adding a small amount of methanol to this product and cooling it, 3-
White crystals (1.42 g, yield 95%) of (2'-fluoro-4'-chloro-5'-methoxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione were obtained.

Compounds 30 to 30 shown in Table 1 were prepared according to the methods of Synthesis Examples 39 to 46.
56 was synthesized. Physical properties and spectrum measurement values of the obtained compound are shown in Tables 4 and 5.

Hereinafter, the production of the starting compounds used in Synthesis Examples 39 to 46 will be described in Dry Examples 4 to 11.

Reference example 4 3- (2'- synthesized by the method shown in Reference Example 12 below
Fluoro-4′-chloro-5′-methoxycarbonyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (3.44 g, 10 mmol) in dry methanol (100 ml) was added to potassium carbonate. (1.38g,
10 mmol) was added and the mixture was refluxed for 2 hours. Aqueous ammonium chloride solution was added to the mixture, and the mixture was extracted with ether. After drying, the solvent was distilled off and the resulting crude oil was purified by column chromatography to give pure 3- (2'-fluoro-4'-chloro-5'-hydroxyphenyl) -5-.
Isopropylidene-1,3-oxazolidine-2,4-
Dione (1.60 g) was obtained. ¹ H-NMR (CDCl ₃ , TMS, ppm): δ 2.06 (3
H, s), 2.29 (3H, s), 5.78 (1H, br s), 6.9
8 (1H, d), 7.25 (d, 1H).

IR (KBrdisk, cm ^-1 ): 3425, 1820, 1738, 1685.

M. P. : 133-135 ° C.

Reference example 5 3- (2′-4 ′) synthesized using 2,4-dichloro-5-methoxycarbonyloxynitrobenzene as a starting material and in the same manner as in Reference Examples 6, 9, 10 and 4.
-Dichloro-5'-methoxycarbanyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (3.60 g, 10 mmol) in dry methanol (100 ml) was added potassium carbonate (0.69 g). 5 mmol)
Was refluxed for 2 hours. By treating in the same manner as in Reference Example 1, 3- (2'-4'-dichloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (1.72 g) was obtained. It was ¹ H-NMR (CDCl ₃ , TMS, ppm): δ 2.03
(3H, s), 2.27 (3H, s), 6.90 (1H, s),
7.48 (1H, s).

IR (KBrdisk, cm ^-1 ): 3400, 1820, 1739, 1690.

M. P. : 166 to 168 ° C.

Reference example 6 Add platinum dioxide (1.5 g) to a solution of 2-fluoro-4-chloro-5-methoxycarbonyloxynitrobenzene (52.1 g, 0.24 mol) in ethanol (600 ml) and stop absorbing hydrogen gas under a hydrogen atmosphere at normal pressure. To room temperature. After completion of the reaction, the catalyst was separated, and the solvent was distilled off from the obtained pale yellow transparent solution under reduced pressure to obtain a pale reddish brown oily substance. This product is almost pure from the NMR spectrum.
It was confirmed to be sulfolo-4-chloro-5-methoxycarbonyloxyaniline. This product can be purified by silica gel column chromatography, but can be used as it is in the next reaction. ¹ H-NMR (CDCl ₃ , TMS, ppm): δ 3.86
(3H, s), 4.13 (2H, br s), 6.48 (1H, d,
J _HF = 8 Hz), 6.92 (1 H, d, J _HF = 10 Hz).

Reference example 7 Platinum dioxide (1.0 g) was added to a solution of 2-fluoro-4-bromo-5-methoxycarbonyloxynitrobenzene (30.4 g, 0.1 mol) in ethanol (300 ml), and the mixture was stirred under a hydrogen atmosphere until hydrogen absorption stopped. . After completion of the reaction, the catalyst was separated, and the solvent was distilled off from the solution under reduced pressure to obtain a brown solid (28.0 g) of 2-fluoro-4-bromo-5-methoxycarbonyloxyaniline. ¹ H-NMR (OCl ₄ −, TMS, ppm): δ 3.83
(3H, s), 5.01 (2H, br s), 6.63 (1H, d,
J _HF = 7.6 Hz), 7.06 (1H, d, J _HF = 9.8 Hz).

Reference example 8 Trichloromethyl chloroformate (15 ml, 155 mmol) in a 500 ml three-necked flask equipped with a dropping funnel and a distillation device.
Was added to a solution of ethyl acetate (150 ml) in 2-fluoro-4-bromo-5-synthesized by the method shown in Reference Example 4.
Methoxycarbonyloxyaniline (28.0g, 113mmol
The ethyl acetate solution of) was added dropwise in 20 minutes. 80 after dropping
The mixture was heated to ° C and ethyl acetate was distilled off. After allowing to cool, carbon tetrachloride (150 ml) was added to remove insoluble materials, and the solvent was distilled off from the solution under reduced pressure to give 2-fluoro-4-bromo-5.
A brown solid of -methoxycarbonyloxyphenylisocyanate (29.1 g, 94% yield) was obtained. ¹ H-NMR (CCl ₄ , TMS, ppm): δ 3.87 (3
H, s), 6.89 (1 H, d, J _HF = 6.8 Hz), 7.31 (1
H, d, J _HF = 8.6 Hz).

IR (KBrdisk, cm ^-1 ): 2260, 1770.

Reference example 9 2-fluoro-4-chloro-5-methoxycarbonyloxyaniline (21.9 g, 10 mmol) and trichloromethyl chloroformate (19 ml) were synthesized by the same procedure as in Reference Example 7 by the method shown in Reference Example 3- Fluoro-4
-Chloro-5-methoxycarbonyloxyphenylisocyanate (20.6 g, yield 84%) was obtained. ¹ H-NMR (CDCl ₃ , TMS, ppm): δ 3.88
(3H, s), 6.97 (1H, d), 7.37 (1H, d).

IR (KBrdisk, cm ^-1 ): 2260, 1770.

Reference example 10 2-Fluoro-4-chloro-5'-methoxycarbonyloxyphenylisocyanate (2.45 g, 10 mmol) synthesized by the method shown in Reference Examples 6 and 9 and ethyl 2-hydroxy-3-methyl-3-butenoate ( 1.44 g, 10 mmo
A catalytic amount of triethylamine was added to a solution of l) in benzene (50 ml) and the mixture was stirred at room temperature for 0.5 hour. After the reaction is complete, add 1
The organic layer was washed with N-hydrochloric acid, dried and then concentrated under reduced pressure. The obtained pale yellow oily substance was separated and purified by a silica gel column to give N- (2-fluoro-4-chloro-5-methoxycarbonyloxyphenyl) carbamic acid (1'-ethoxycarbonyl) methallyl ester (yield 85%. ) Got. ¹ H-NMR (CDCl ₃ , TMS, ppm): δ1.29
(3H, t), 1.84 (3H, br s), 3.93 (3H,
s), 4.24 (2H, q), 5.14 (1H, m), 5.23 (1
H, m), 5.45 (1H, s), 7.20 (1H, d), 7.0
~ 7.35 (1H, brs), 8.10 (1H, d).

Reference example 11 2-Fluoro-4-bromo-5-methoxycarbonyloxyphenylisocyanate (2.74 g, 9.5 mmol) synthesized by the method shown in Reference Examples 7 and 8 and a small excess of 2
The mixture was heated to reflux for 1 hour in a solvent of methyl-hydroxy-3-methyl-3-pentenoate and benzene (50 ml). The reaction mixture was washed with 1N-hydrochloric acid, dried and the solvent was evaporated. The obtained oily substance is separated and purified using a silica gel column, and N-
(2'-Fluoro-4-bromo-5-methoxycarbonyloxyphenyl) carbamic acid (1'-methoxycarbonyl-2'-methyl-2'-butenyl ester (2.47
g, yield 57%) was obtained. ¹ H-NMR (CCl ₄ , TMS, ppm): δ 1.67 (3
H, s), 1.70 (3H, d), 3.70 (3H, s), 3.87
(3H, s), 5.27 (1H, s), 5.68 (1H, m),
7.0 (1H, br s), 7.27 (1H, d), 8.03 (1H,
d).

Reference example 12 N- synthesized by the method shown in Reference Examples 6, 9 and 10
A catalytic amount of sodium acetate was added to a benzene solution (20 ml) of (2-fluoro-4-chloro-5-methoxycarbonyloxyphenyl) carbamic acid (1'-ethoxycarbonyl) methallyl ester (1.95 g, 5.0 mmol) for 12 hours. Refluxed. After completion of the reaction, the solution was washed with 1N-hydrochloric acid, dried and the solvent was distilled off. The obtained oily substance was purified using a silica gel column to give 3- (2'-fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2. , 4-dione (1.27 g, yield 74%) was obtained. ¹ H-NMR (CDCl ₃ , TMS, ppm): δ 2.05 (3H, s), 2.28 (3H, s), 3.95 (3H,
s), 7.32 (d, 1H), 7.42 (1H, d).

The compound which is the active ingredient of the present invention obtained as shown in the synthesis example has excellent performance as a herbicide as described above.

In using this active ingredient compound as a herbicide, it can be used as it is, but generally, it can be used as a herbicide of the present invention by mixing one or several kinds of auxiliary agents. Usually, as an auxiliary agent, various carriers, bulking agents,
It is preferable that a solvent, a surfactant, a stabilizer and the like are mixed and formulated into a form such as a wettable powder, an emulsion, a powder or a powder by a conventional method before use.

Examples of the solvent which is one of the auxiliary agents in the herbicides using the compound of the present invention include water, alcohols, ketones, ethers, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons and 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, clays such as kaolin and bentonite, talcs such as talc and pyrophyllite, diatomaceous earth, mineral powders such as oxides of white carbon and soybean powder, C
Vegetable powder such as MC is preferable, and one kind or a mixture of two or more kinds thereof is used.

Moreover, you may use surfactant as a spreading agent, a dispersing agent, an emulsifier, and a penetrating agent. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.
These surfactants are utilized as one kind or a mixture of two or more kinds depending on the application.

Preferable uses of the herbicide using the compound of the present invention include soil treatment, water surface treatment, foliage treatment, and the like, and the application of the weed control agent from before germination to at the time of larvae gives particularly excellent effects.

Further, the herbicide using the compound of the present invention, other active ingredients which do not inhibit the herbicidal activity of the present active ingredient, for example, other herbicides, insecticides, fungicides, plant growth regulators or the like are mixed or used. It is also possible to use together.

Next, the present invention will be described in more detail with reference to formulation examples of herbicides using the compound of the present invention, and test examples of herbicidal effects of the herbicides, but the present invention is limited to those exemplified in these specific examples. It is not something that will be done. The parts are parts by weight.

Formulation Example 1 (Emulsion) 20 parts of the compound which is the active ingredient of the present invention, 75 parts of xylene and 5 parts of Solpol 900A (manufactured by Toho Kagaku Co., Ltd.) are uniformly mixed to obtain an emulsion.

Formulation Example 2 (Wettable powder) A mixture of 50 parts of the compound of the present invention, 25 parts of diatomaceous earth, 22 parts of clay and 3 parts of Lunox R100 C (manufactured by Toho Kagaku Co., Ltd.) is uniformly mixed and pulverized to obtain a wettable powder. To do.

Formulation Example 3 (Granule) 5 parts of the compound which is the active ingredient of the present invention, bentonite 35
Parts, 55 parts of talc and 5 parts of sodium lignin sulfonate are uniformly mixed and pulverized, then water is added and kneaded, granulated by an extrusion granulator, dried and sized to obtain granules. .

Test Example 1 (Effects on paddy field weeds) Wagner pots of 1 / 5,000 are were filled with paddy field soil, and seeds of spiny flesh, eels, lythrum and 3
Rice seedlings (cultivar: Nihonbare) at ˜4 leaf stage were sown or transplanted and kept in a flooded state. After 5 days, the active ingredient of the herbicide using the compound of the present invention made into granules according to Formulation Example 3 is
A predetermined amount of water was surface-treated so that the weight was 50, 25, 20, 10, 12, 5 and 5 g. Thirty days after the treatment with granules, the herbicidal effect on the test plants and the phytotoxicity against rice were investigated according to the following criteria, and the results shown in Table 6 were obtained.

Judgment Criteria Killing rate: Residual grass content ratio (%) 0: 81-100 1: 61-80 2: 41-60 3: 21-40 4: 6-20 5: 0-5 Drug damage: Growth rate- : None +: Slight harm ++: Small harm +++: Medium harm ++++: Severe harm ×: Withered Test Example 2 (Effect of Field Soil Treatment) Field soil was filled in a Wagner pot of 1 / 5,000 are, and seeds of corngrass, cotton, soybeans as crops were sown as weeds.
1 cm of soil was covered on it. The next day, the diluting solution of the wettable powder shown in Formulation Example 2 was added in an amount of 50, 25, 2
It was evenly sprayed on the soil cover so as to be 0, 10, 12, 5 and 5 g, and 20 days after the treatment, the herbicidal effect and the chemical damage were examined in the same manner as in Test Example 1. The results are shown in Table 7.

Test Example 3 (Effects of foliage treatment) Wagner pots of 1 / 5,000 are were filled with upland soil, and weeds such as barnyardgrass, crabgrass, sardines, Amaranthus serrata, and Shiroza were sown, and foliage of weeds grown after 20 days. Part of each of the test compounds prepared from the emulsion shown in Formulation Example 1 was diluted with water, and the test solution was uniformly sprayed to the test plants at a spray water amount of 100 / 10a. On the 20th day after the treatment, the herbicidal effect and the phytotoxicity (on wheat, soybean and corn) were evaluated in the same manner as in Test Example 1. The results are shown in Table 8.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsuko Murata 15-19 Toyomachi, Sagamihara City, Kanagawa Prefecture (72) Inventor Hiroaki Hirose 2-17 Tatsumidai Higashi, Ichihara City, Chiba Prefecture A-208 (72) Inventor Masahiro Yokota 2-17 Tatsumidai-higashi, Ichihara-shi, Chiba A-204 (72) Inventor Shoin Nagato 3-13-13-106, Kahama, Adachi-ku, Tokyo

Claims (5)

[Claims] 1. An agriculturally acceptable carrier or diluent and a general formula: [Wherein R ¹ , R ² and R ³ are independently of each other a hydrogen atom, a halogen atom, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cycloalkyloxy group or an alkoxycarbonylalkoxy group; R ⁴ and R ^{4 And 5} each independently represent a hydrogen atom or an alkyl group; provided that the alkenyloxy group may be substituted with a halogen atom]. 2. R ¹ , R ² and R ³ are independently of each other a hydrogen atom; a halogen atom; or an oxazolidinedione derivative which is a linear or branched alkoxy group having 1 to 8 carbon atoms. The herbicide according to claim 1. 3. An oxazolidinedione derivative in which R ⁴ and R ⁵ are each independently a hydrogen atom; or a linear or branched alkyl group having 1 to 8 carbon atoms is used. The herbicide according to Item 2 or Item 2. 4. R ¹ , R ² and R ³ independently of one another are a hydrogen atom; a halogen atom; an alkoxyl group having 1 to 8 carbon atoms which may be substituted with an alkyloxycarbonyl group having 2 to 18 carbon atoms; A cycloalkyl group having 3 to 8 carbon atoms; a linear or branched alkenyloxy group having 2 to 8 carbon atoms which may be substituted with one or more halogen atoms; an alkynyl group having 2 to 8 carbon atoms The herbicide according to claim 1, wherein an oxazolidinedione derivative having an oxy group is used. 5. An oxazolidinedione derivative in which R ⁴ and R ⁵ are each independently a hydrogen atom or a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms is used. The herbicide described.