JPH0720945B2 - Oxazolidinedione derivative and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel oxazolidinedione derivative and a method for producing the same. More specifically, the present invention has the general formula [Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group or a cycloalkyloxy group, provided that R 1 ¹ , R ² , R ³ and R ⁵ are not hydrogen atoms at the same time; R ⁴ and R ⁵ are independently of each other a hydrogen atom, an alkyl group, an aryl group or R ⁴ and R ⁵ are integrated together to form polymethylene. A chain can be formed; said alkyl group, alkoxy group, alkenyloxy group,
An alkynyloxy group, a cycloalkyloxy group and an aryl group may be substituted] and a method for producing the same.

Conventionally, various derivatives having a substituent at the 5-position of the oxazolidinedione ring have been known. However, it has been reported so far that the oxazolidinedione derivative having a substituted methylidene group at the 5-position is difficult to synthesize. It has not been.

Further, although many heterocyclic compounds having herbicidal activity have been synthesized and put into practical use until now, no oxazolidinediones having practical herbicidal activity have been known so far.

[Problems to be Solved by the Invention] The present invention provides novel compounds having both high selectivity for weeds and strong herbicidal activity, and further provides an industrial production method for these compounds. Is.

[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 object compound 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;
Nitro group; halogen atom such as fluorine, chlorine, bromine or iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group,
A linear or branched alkyl group having 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, such as n-hexyl group, n-heptyl group, and n-octyl group, and this group is one or more halogen atoms. Or the like; methoxy group, ethoxy group, n-propoxy group, isopropoxy group; n-butoxy group, t-butoxy group, etc., having 1 to 18 carbon atoms, preferably 1
~ 8 alkoxy group, which may be substituted with one or more alkoxycarbonyl group (having 2 to 18 carbon atoms), halogen atom, etc .; cyclohexyloxy group, cyclopentyloxy group, cyclopropyloxy group A cycloalkoxy group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, which may be substituted with one or more lower alkyl groups (having 1 to 5 carbon atoms), a halogen atom or the like; allyl Group, methallyl group, propenyl group, butenyl group, pentenyl group, hexenyl group and the like, which is a straight chain or branched chain alkenyl group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and one or more halogen atoms May be substituted; propargyl group, 1-methylpropargyl group,
A linear or branched alkynyl group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as 1,1-dimethylpropargyl, 2-butynyl group, 3-butynyl group, 2-pentynyl group, and 3-pentynyl group; Or may be substituted with two or more halogen atoms or the like; and R ⁴ and R ⁵ are each independently a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, A linear or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms such as isobutyl group, n-hexyl group, and n-octyl group, which may be substituted with one or more halogen atoms. Or a phenyl group, p-chlorophenyl group, p-fluorophenyl group, m, p-dimethoxyphenyl group, p-methylphenyl group, or other aryl group having 6 to 10 carbon atoms, a halogen atom, or 1 to 3 carbon atoms Lower rank R ⁴ and R ⁵ may together form a straight-chain or molecular-chain polymethylene group having 3 to 10 carbon atoms.

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-,
The 2,5-, 3,4-, and 3,5-positions are preferred, and when all three are other than hydrogen, the 2,4,5-, or 2,4,6-position is preferred.

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

When used in a paddy field, the novel oxazolidinedione derivative of the present invention exhibits a strong herbicidal activity against annual weeds such as millet, eel, stiletto, and perennial weeds such as Periwinkle, Firefly, Urikawa and Matsubais. Further, also in the field, it is possible to selectively kill the field weeds such as Aedes peregrinus, Crabgrass, Enocologsa, Shiroza, Polygonum, Aubiyu, Purslane, Psyllium.

Furthermore, the compound of 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. In other words, the compound of the present invention kills grass weeds such as millet, crabgrass, and locust, while it hardly causes phytotoxicity to rice crops such as transplanted rice, wheat, and corn. Almost no phytotoxicity is observed for soybeans, cotton, etc., which are crops other than Poaceae.

The compound of the present invention is mixed with various carriers, extenders, solvents, surfactants, stabilizers, etc., and formulated into a desired form such as wettable powder, emulsion, powder, granules, etc. by a conventional method to prepare a herbicide. used.

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

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

The novel oxazolidinedione derivative represented by the general formula (I) of the present invention has the general formula [Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above,
R ⁶ represents a lower alkyl group (C ₁ ~C _4). ] It can be easily obtained by treating the carbamate represented by the formula with a base. The reaction is preferably carried out in an ordinary organic solvent with heating or reflux.

The first method of the present invention requires treating the carbamate represented by the general formula (II) with a base. Examples of the base used include triethylamine, tripropylamine, tributylamine, N
Of tertiary amines such as 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. Such alkali metal hydrides or basic inorganic compounds such as sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide 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. [In the formula, 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 the formula, R ⁴ , R ⁵ and R ⁶ are as described above. ] It can be easily obtained by reacting with a β, γ-unsaturated-α-hydroxycarboxylic acid ester represented by

The aryl isocyanates and carbamoyl chlorides represented by the general formula (III) are compounds that can be easily obtained from corresponding aniline derivatives, and examples of aryl isocyanates include phenyl isocyanate and o, m
Or p-fluorophenyl isocyanate, o, m or p
-Chlorophenyl isocyanate o, m or p-bromophenyl isocyanate, o, m or p-iodophenyl isocyanate, 2,3-dichlorophenyl isocyanate, 2,4-dichlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate , 3,5-dichlorophenyl isocyanate, 2,3-difluorophenyl isocyanate, 2,4-difluorophenyl isocyanate, 2,5-difluorophenyl isocyanate, 3,4-difluorophenyl isocyanate, 3,5-difluorophenyl isocyanate, 2, 4-dibromophenyl isocyanate, 2,4,6-trichlorophenyl isocyanate, 2,4,5-trichlorophenyl isocyanate, 3,4,5-trichlorophenyl isocyanate, 2,4,6-trifluorophenyl isocyanate , 2-chloro-4-fluorophenyl isocyanate, 2-fluoro-4-chlorophenyl isocyanate, 2-chloro-4-bromophenyl isocyanate, 2-fluoro-4-bromophenyl isocyanate, 2-chloro-4-iodophenyl isocyanate ,
2,4-dichloro-6-fluorophenyl isocyanate, 3,5-dichloro-4-fluorophenyl isocyanate, 3,5-dichloro-4-bromophenyl isocyanate, 3,4-dichloro-5-fluorophenyl isocyanate, 2, 4-dichloro-6-bromophenyl isocyanate, 2,4-dichloro-5-fluorophenyl isocyanate, 2,4-difluoro-6-chlorophenyl isocyanate, o, m or p-methylphenyl isocyanate, o, m or p-ethyl Phenyl isocyanate, o, m or p-isopropylphenyl isocyanate, o, m or p-t-butylphenyl isocyanate, 2-chloro-
5-methylphenyl isocyanate, 2-fluoro-5
-Methylphenyl isocyanate, 4-chloro-5-methylphenyl isocyanate, 2-chloro-4-isopropylphenyl isocyanate, 2,4-dichloro-5-
Methylphenyl isocyanate, 2,4-difluoro-5
-Methylphenyl isocyanate, 2-fluoro-4-
Chloro-5-methylphenyl isocyanate, o, m or p-methoxyphenyl isocyanate, o, m or p-isopropoxyphenyl isocyanate, o, m or p-t
-Butoxyphenyl isocyanate, 2-chloro-5-
Methoxyphenyl isocyanate, 2-fluoro-5-
Methoxyphenyl isocyanate, 4-chloro-5-methoxyphenyl isocyanate, 2,4-dichloro-5-
Isopropoxyphenyl isocyanate, 2,4-difluoro-5-isopropoxyphenyl isocyanate, 2
-Fluoro-4-chloro-5-isopropoxyphenyl isocyanate, 2,4-dichloro-5-methoxyphenyl isocyanate, 2,4-dichloro-5-ethoxyphenyl isocyanate, 2-fluoro-4-chloro-5-
Methoxyphenyl isocyanate, 2-fluoro-4-
Chloro-5-ethoxyphenyl isocyanate, 2-fluoro-4-bromo-5-isopropoxyphenyl isocyanate, 2,4-dichloro-5-t-butoxyphenyl isocyanate, o, m or p-nitrophenyl isocyanate, 2-chloro -4-nitrophenyl isocyanate, 2-fluoro-4-nitrophenyl isocyanate, 2-nitro-4-chlorophenyl isocyanate,
2-nitro-4-fluorophenyl isocyanate, o,
m or p-trifluoromethylphenyl isocyanate, o, m or p- (fluoromethyl) phenyl isocyanate, o, m or p- (chloromethyl) phenyl isocyanate, o, m or p- (bromomethyl) phenyl isocyanate, 2- Chloro-5-trifluoromethylphenyl isocyanate, 2-fluoro-5-trifluoromethylphenyl isocyanate, 4-chloro-5-trifluoromethylphenyl isocyanate, 2-nitro-
4-trifluoromethylphenyl isocyanate, 2-
Trifluoromethyl-4-nitrophenyl isocyanate, 3,5-dichloro-4-nitrophenyl isocyanate, 2-nitro-5-methylphenyl isocyanate,
3-nitro-4-methylphenyl isocyanate, 2-
Substituted phenyl isocyanate such as trifluoromethyl-4-bromophenyl isocyanate and 3,5-bis (trifluoromethyl) phenyl isocyanate can be used in the reaction. Further, as the carbamoyl chloride derivative, phenylcarbamoyl chloride, o, m or p-
Fluorophenylcarbamoyl chloride, o, m or p-
Bromophenylcarbamoyl chloride, o, m or p-chlorophenylcarbamoyl chloride, o, m or p-iodophenylcarbamoyl chloride, 2,3-dichlorophenylcarbamoyl chloride, 2,4-dichlorophenylcarbamoyl chloride, 2,5-dichlorophenylcarbamoyl chloride, 3,4-dichlorophenylcarbamoyl chloride, 3,5-dichlorophenylcarbamoyl chloride, 2,3-difluorophenylcarbamoyl chloride,
2,4-difluorophenylcarbamoyl chloride, 3,5-
Difluorophenylcarbamoyl chloride, 2,4-dibromophenylcarbamoyl chloride, 2,4,6-trichlorophenylcarbamoyl chloride, 2,4,5-trichlorophenylcarbamoyl chloride, 2-chloro-4-fluorophenylcarbamoyl chloride, 2-fluoro -4
-Chlorophenylcarbamoyl chloride, 2-chloro-
4-bromophenylcarbamoyl chloride, 2-chloro-4-iodophenylcarbamoyl chloride, 3,5-dichloro-4-fluorophenylcarbamoyl chloride,
3,5-dichloro-4-bromophenylcarbamoyl chloride, 2,4-dichloro-6-fluorophenylcarbamoyl chloride, o, m or p-methylphenylcarbamoyl chloride, o, m or p-isopropyl phenylcarbamoyl chloride, 2 -Chloro-5-methylphenylcarbamoyl chloride, 2-fluoro-5-methylphenylcarbamoyl chloride, 4-chloro-5-methylphenylcarbamoyl chloride, 2-fluoro-4-isopropylphenylcarbamoyl chloride, 2,4-dichloro-
5-methylphenylcarbamoyl chloride, o, m or p
-Methoxyphenylcarbamoyl chloride, o, m or p
-Ethoxyphenylcarbamoyl chloride, o, m or p
-T-butoxyphenylcarbamoyl chloride, 2-chloro-5-methoxyphenylcarbamoyl chloride, 2
-Fluoro-5-methoxyphenylcarbamoyl chloride, 4-chloro-5-methoxyphenylcarbamoyl chloride, 2,4-dichloro-5-isopropoxyphenylcarbamoyl chloride, 2,4-dichloro-5-methoxyphenylcarbamoyl chloride, 2, 4-dichloro-5-
Ethoxyphenylcarbamoyl chloride, 2,4-difluoro-5-methoxyphenylcarbamoyl chloride, 2,
4-difluoro-5-ethoxyphenylcarbamoyl chloride, 2,4-difluoro-5-isopropoxyphenylcarbamoyl chloride, 2-fluoro-4-chloro-
5-methoxyphenylcarbamoyl chloride, 2-fluoro-4-chloro-5-ethoxyphenylcarbamoyl chloride, 2-fluoro-4-chloro-5-isopropoxyphenylcarbamoyl chloride, 2-fluoro-4
-Chloro-5-t-butoxyphenylcarbamoyl chloride, 2-chloro-4-fluoro-5-methoxyphenylcarbamoyl chloride, 2-fluoro-4-bromo-
5-isopropoxyphenylcarbamoyl chloride, o,
m or p-nitrophenylcarbamoyl chloride, 2-
Chloro-4-nitrophenylcarbamoyl chloride, 2
-Fluoro-4-nitrophenylcarbamoyl chloride, 2-nitro-4-fluorophenylcarbamoyl chloride, 2-bromo-4-nitrophenylcarbamoyl chloride, o, m or p-trifluoromethylphenylcarbamoyl chloride, o, m or p -(Fluoromethyl)
Phenylcarbamoyl chloride, o, m or p- (chloromethyl) phenylcarbamoyl chloride, o, m or p-
(Bromomethyl) phenylcarbamoyl chloride, 2-
Chloro-5-trifluoromethylphenylcarbamoyl chloride, 2-fluoro-5-trifluoromethylphenylcarbamoyl chloride, 4-chloro-5-trifluoromethylphenylcarbamoyl chloride, 2-nitro-4-trifluoromethylphenylcarbamoyl chloride, 2-trifluoromethyl-4-nitrophenylcarbamoyl chloride, 2-nitro-4-trifluoromethyl-5-methoxyphenylcarbamoyl chloride, 3,5
-Dichloro-4-nitrophenylcarbamoyl chloride, 2-nitro-5-methylphenylcarbamoyl chloride, 2-trifluoromethyl-4-bromophenylcarbamoyl chloride, substitution of 3,5-bis (trifluoromethyl) phenylcarbamoyl chloride, etc. Phenylcarbamoyl chloride can be used. The 2-hydroxycarboxylic acid ester represented by the general formula (IV) can be easily produced from inexpensive commercially available raw materials, and for example, methyl 2-hydroxy-3-methyl-3-butenoate and 2-hydroxy-3-methyl- Methyl 3-pentenoate, Methyl 2-hydroxy-3-ethyl-3-butenoate, Methyl 2-hydroxy-3-ethyl-3-pentenoate, Methyl 2-hydroxy-3-butyl-3-butenoate, 2- Methyl hydroxy-3-methyl-3-heptenoate, methyl 2-hydroxy-3-methyl-3-nonenate, methyl 2-hydroxy-3-hexyl-3-butenoate, 2-hydroxy-3- (1′- Cyclopentenyl) methyl acetate, 2-hydroxy-3- (1'-cyclohexenyl) methyl acetate, 2-hydroxy-3- (1'-cycloheptenyl)
Methyl acetate, 2-hydroxy-3- (1'-cyclododecenyl) acetic acid, methyl 2-hydroxy-3-butyl-3-pentenoate, methyl 2-hydroxy-3-ethyl-3-heptenoate, 2-hydroxy-3 -Methyl pentyl-3-octenoate, 2-hydroxy-3-phenyl-3-
Methyl butenoate, 2-hydroxy-3-phenyl-3-
Methyl pentenoate, 2-hydroxy-3-phenyl-3
-Methyl hexenoate, methyl 2-hydroxy-3- (4'-chlorophenyl) -3-butenoate, methyl 2-hydroxy-3- (4'-fluorophenyl) -3-butenoate, 2-hydroxy-3- (4'-bromophenyl)-
Methyl 3-butenoate, 2-hydroxy-3- (3 ', 4'
-Dimethoxyphenyl) -3-butenoic acid methyl, 2-hydroxy-3- (3 ', 4'-dichlorophenyl) -3-
Methyl butenoate, 2-hydroxy-3- (4'-methylphenyl) -3-butenoic acid methyl, 2-hydroxy-3
Methyl-(4'-chlorophenyl) -3-pentenoate,
2-hydroxy-3- (4'-fluorophenyl) -3
-Methyl pentenoate, 2-hydroxy-3- (3 ', 5'
Methyl -dichlorophenyl) -3-butenoate and lower alkyl esters thereof such as ethyl ester, isopropyl ester, isobutyl ester, t-butyl ester and the like can be used. The reaction has the general formula (II
The compound of general formula (II) can be produced by carrying out the compound of general formula (IV) and the compound of general formula (IV) in an organic solvent, optionally in the presence of a base, at room temperature to reflux temperature (see below). See Reference Examples 1 to 3).

Examples of the carbamic acid represented by the general formula (II) and the ester include 2- (N-phenylcarbamoyloxy)-
Methyl 3-methyl-3-butenoate, ethyl 2- (N-phenylcarbamoyloxy) -3-methyl-3-butenoate, 2- (N-phenylcarbamoyloxy) -3-methyl-3-butenoic acid Isobutyl, methyl 2- {N- (2'-chlorophenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- {N- (2'-fluorophenyl)
Methyl carbamoyloxy} -3-methyl-3-butenoate, 2- {N- (3′-fluorophenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl, 2- {N
-(2'-Bromophenyl) carbamoyloxy} -3-
Methyl methyl-3-butenoate, 2- {N- (4'-chlorophenyl) carbamoyloxy} -3-methyl-3-butenoate methyl, 2- {N- (4'-fluorophenyl)
Methyl carbamoyloxy} -3-methyl-3-butenoate, methyl 2- {N- (4′-bromophenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- {N-
(2 ', 4'-Dichlorophenyl) carbamoyloxy}-
Methyl 3-methyl-3-butenoate, 2- {N- (2 ',
Methyl 5'-dichlorophenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- {N- (3 ', 4'-dichlorophenyl) carbamoyloxy} -3-methyl-3
-Methyl butenoate, 2- {N- (3 ', 5'-dichlorophenyl) carbamoyloxy} -3-methyl-3-butenoate methyl, 2- {N- (2', 4'-difluorophenyl) carbamoyloxy}- Methyl 3-methyl-3-butenoate, 2- {N- (2 ', 4'-dibromophenyl) carbamoyloxy} -3-methyl-3-butenoate methyl, 2
-{N- (2'-chloro-4'-fluorophenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl ester,
2- {N- (2'-bromo-4'-fluorophenyl)
Methyl carbamoyloxy} -3-methyl-3-butenoate, 2- {N- (2'-bromo-4'-chlorophenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl 2- {N- (2 ' , 4 ', 6'-Trichlorophenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl, 2- {N- (2', 4 ', 6'-trifluorophenyl) carbamoyloxy} -3-methyl-3 -Methyl butenoate, 2- {N- (2 ', 4', 6'-tribromophenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl ester, 2- {N- (3 ', 5'-dichloro) -4'-fluorophenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl ester, 2- {N- (3'-chloro-4'-methylphenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl ester, 2- {N- (3 - fluoro-4'-methylphenyl) Karubamoirokishi} -3-methyl-3-
Methyl butenoate, 2- {N- (4'-methylphenyl)
Methyl carbamoyloxy} -3-methyl-3-butenoate, methyl 2- {N- (4'-ethylphenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- {N-
Methyl (2'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- {N-
Methyl (3'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- {N-
Methyl (4'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- [N-
Methyl {3 ', 5'-bis (trifluoromethyl) phenyl} carbamoyloxy] -3-methyl-3-butenoate,
Methyl 2- {N- (2'-chloromethylphenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- {N
-(4'-Bromomethylphenyl) carbamoyloxy}
Methyl-3-methyl-3-butenoate, 2- {N- (2 '
-Nitrophenyl) carbamoyloxy} -3-methyl-
Methyl 3-butenoate, 2- {N- (3'-nitrophenyl) carbamoyloxy} -3-methyl-3-butenoate methyl, 2- {N- (4'-nitrophenyl) carbamoyloxy} -3-methyl- 3-methyl butenoate, 2- {N
-(2 ', 4'-dinitrophenyl) carbamoyloxy}
Methyl-3-methyl-3-butenoate, 2- {N-
(3 ', 5'-Dinitrophenyl) carbamoyloxy}-
Methyl 3-methyl-3-butenoate, 2- {N- (2'methoxyphenyl) carbamoyloxy} -3-methyl-3
-Methyl butenoate, 2- {N- (4'-methoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate methyl, 2- {N- (2'-chloro-5'-trifluoromethylphenyl) carbamoyloxy } -3-Methyl-3
-Methyl butenoate, 2- {N- (2'-trifluoromethyl-4'-bromophenyl) carbamoyloxy} -3
Methyl-3-methyl-3-butenoate, 2- {N- (3'-trifluoromethyl-4'-fluorophenyl) carbamoyloxy} -3-methyl-3-butenoate methyl, 2-
Methyl {N- (2'-chloro-4'-nitrophenyl) carbamoyloxy} -3-methyl-3-butenoate, 2-
Methyl {N- (2'-chloro-5'-methoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate, 2
-{N- (3'-nitro-4'-methylphenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl ester, 2
-{N- (4'-nitro-2'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-butenoate methyl, 2- {N- (2'-nitro-4'-trifluorophenyl) carbamoyloxy } -3-Methyl-3-
Methyl butenoate, 2- {N- (4'-nitro-3'-trifluoromethylphenyl) carbamoyloxy} -3-
Methyl methyl-3-butenoate, 2- {N- (3'-methoxy-5'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-butenoate methyl, 2- {N
Methyl-(2'-methoxy-5'-nitrophenyl) carbamoyloxy} -3-methyl-3-butenoate, 2-
{N- (2 ', 4'-dichloro-5-methoxyphenyl)
Methyl carbamoyloxy} -3-methyl-3-butenoate, 2- {N- (4'-chloro-2'-fluoro-5-
Methoxyphenyl) carbamoyloxy} -3-methyl-
Methyl 3-butenoate, 2- {N- (4'-bromo-2 '
-Fluoro-5-ethoxyphenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl ester, 2- {N-
Methyl (2 ', 4'-dichloro-5'-methoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate, 2
-{N- (2 ', 4'-dichloro-5'-ethoxyphenyl) carbamoyloxy} -3-methyl-3-butenoic acid ethyl ester, 2- {N- (2', 4'-dichloro-5-isopropoxy (Phenyl) carbamoyloxy} -3-methyl-3
-Isobutyl butenoate, 2- {N- (2 ', 4'-dichloro-5'-t-butoxyphenyl) carbamoyloxy}
Methyl-3-methyl-3-butenoate, 2- {N-
Isobutyl (2 ', 4'-dichloro-5'-hexyloxyphenyl) carbamoyloxy} -3-methyl-3-butenoate, 2- {N- (4'-chloro-2'-fluoro-5'-methoxyphenyl) ) Carbamoyloxy} -3-
Methyl methyl-3-butenoate, 2- {N- (4'-chloro-2'-fluoro-5'-ethoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate ethyl, 2-
{N- (4'-chloro-2'-fluoro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-
Methyl 3-butenoate, 2- {N- (4'-chloro-2 '
-Fluoro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate isobutyl, 2
-{N- (4'-chloro-2'-fluoro-5'-t-
Butoxyphenyl) carbamoyloxy} -3-methyl-
Methyl 3-butenoate, 2- {N- (4'-chloro-2 '
-Fluoro-5'-isobutoxyphenyl) carbamoyloxy} -3-methyl-3-pentenoate methyl, 2-
{N- (4'-chloro-2'-fluoro-5'-methosylphenyl) carbamoyloxy} -3-methyl-3-pentenoate isobutyl, 2- {N- (4'-chloro-2 '
-Fluoro-5'-ethoxyphenyl) carbamoyloxy} -3-methyl-3-pentenoate methyl, 2- {N-
Methyl (4'-chloro-2'-fluoro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-pentenoate, 2- {N- (4'-chloro-2'-fluoro-5'- Isopropoxyphenyl) carbamoyloxy} -3-octyl-3-pentenoate isobutyl,
2- {N- (4'-chloro-2'-fluoro-5'-t
-Butoxyphenyl) carbamoyloxy} -3-methyl-3-pentenoate methyl, 2- {N- (4'-chloro-
Methyl 2'-fluoro-5'-methoxyphenyl) carbamoyloxy} -3-ethyl-3-butenoate, 2- {N
-(4'-chloro-2'-fluoro-5'-isopropoxyphenyl) carbamoyloxy} -3-ethyl-3-
Isobutyl butenoate, 2- {N- (4'-chloro-2 '
-Fluoro-5'-ethoxyphenyl) carbamoyloxy} -3-ethyl-3-butenoic acid methyl ester, 2- {N-
Methyl (4'-chloro-2'-fluoro-5'-isopropoxyphenyl) carbamoyloxy} -3-octyl-3-ethyl-3-fudenate, 2- {N- (4'-chloro-2'-fluoro- 5'-isopropoxyphenyl) carbamoyloxy} -3-butenoic acid isobutyl, 2- {N
Methyl-(4'-chloro-2'-fluoro-5'-t-butoxyphenyl) carbamoyloxy} -3-ethyl-3-butenoate, 2- {N- (4'-chloro-3'-methoxyphenyl) Carbamoyloxy} -3-methyl-3-
Methyl butenoate, 2- {N- (4'-chloro-3'-methoxyphenyl) carbamoyloxy} -3-methyl-3
-Isobutyl butenoate, 2- {N- (4'-chloro-
3'-Ethoxyphenyl) carbamoyloxy} -3-methyl-3-butenoic acid ethyl ester, 2- {N- (4'-chloro-3'-isopropoxyphenyl) carbamoyloxy}
Methyl-3-methyl-3-butenoate, 2- {N- (4 '
-Chloro-3'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-butenoic acid isobutyl, 2-
{N- (4'-chloro-3'-pentyloxyphenyl) carbamoyloxy} -3-methyl-3-butenoic acid isobutyl, 2- {N- (4'-chloro-3'-hexyloxyphenyl) carbamoyloxy}- 3-methyl-3
-Isobutyl butenoate, 2- {N- (4'-chloro-
3'-heptyloxyphenyl) carbamoyloxy}-
Isobutyl 3-methyl-3-butenoate, 2- {N-
(4'-Chloro-3'-octyloxyphenyl) carbamoyloxy} -3-methyl-3-butenoate isobutyl, 2- {N- (4'-chloro-3'-nonyloxyphenyl) carbamoyloxy} -3-methyl Isobutyl-3-butenoate, 2- {N- (4'-fluoro-3'-methoxyphenyl) carbamoyloxy} -3-methyl-3
-Methyl butenoate, 2- {N- (4'-fluoro-3 '
-Isopropoxyphenyl) carbamoyloxy} -3-
Isobutyl methyl-3-butenoate, 2- {N- (4'-
Fluoro-3′-octyloxyphenyl) carbamoyloxy} -3-methyl-3-butenoic acid ethyl ester, 2- {N
Methyl-(4'-chloro-3'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-pentenoate, 2- {N- (4'-chloro-3'-isopropoxyphenyl) carbamoyloxy} -3- Methyl methyl-3-hexenoate, 2- {N- (4'-fluoro-3'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-heptenoate, 2- {N- (4'-chloro- 3'-isopropoxyphenyl) carbamoyloxy}
Methyl-3-methyl-3-octenoate, 2- {N-
Methyl (4'-chloro-3'-isopropoxyphenyl) carbamoyloxy} -3-octyl-3-butenoate,
2- {N- (4'-chloro-3'-isopropoxyphenyl) carbamoyloxy} -3-octyl-3-isobutyl octenoate, 2- {N- (4'-fluoro-3'-
Methyl isopropoxyphenyl) carbamoyloxy} -3-methyl-3-pentenoate, 2- {N- (4′-fluoro-3′-isopropoxyphenyl) carbamoyloxy} -3-dodecyl-3-pentenoate isobutyl, 2-
{N- (4'-fluorophenyl) carbamoyloxy}
Methyl-3-methyl-3-pentenoate, 2- {N-
(4'-Fluorophenyl) carbamoyloxy} -3-
Methyl ethyl-3-butenoate, 2- {N- (4'-chlorophenyl) carbamoyloxy} -3-ethyl-3-butenoate isobutyl, 2- {N- (4'-chlorophenyl) carbamoyloxy} -3-methyl- Methyl 3-pentenoate, 2- {N- (4'-bromophenyl) carbamoyloxy} -3-ethyl-3-butenoic acid methyl, 2-
{N- (4'-bromophenyl) carbamoyloxy}-
Methyl 3-methyl-3-pentenoate, 2- {N-
(2 ', 4'-Dichlorophenyl) carbamoyloxy}-
Methyl 3-ethyl-3-pentenoate, 2- {N- (4 '
-Chlorophenyl) carbamoyloxy} -2- (1 "-
Cyclohexenyl) methyl acetate, 2- {N- (4'-chlorophenyl) carbamoyloxy} -3-methyl-3-
Methyl heptenoate, 2- {N- (4'-chlorophenyl) carbamoyloxy} -3-butyl-3-butenoic acid methyl, 2- {N- (4'-chlorophenyl) carbamoyloxy} -3-methyl-3-nonenoic acid Methyl, 2- {N
-(4'-chlorophenyl) carbamoyloxy} -3-
Methyl hexyl-3-butenoate, 2- (N-phenylcarbamoyloxy) -3-ethyl-3-pentenoate, 2- {N- (3 ', 4'-dichlorophenyl) carbamoyloxy} -3-phenyl- Methyl 3-butenoate, 2
Methyl-{N- (3 ', 4'-dichlorophenyl) carbamoyloxy} -3- (4 "-chloro-phenyl) -3-butenoate, 2- {N- (3', 5'-dichlorophenyl)
Carbamoyloxy} -3- (4 ″ -fluorophenyl)
Methyl-3-butenoate, 2- {N- (3 ', 5'-dichlorophenyl) carbamoyloxy} -3- (4 "-fluorophenyl) -3-methyl butenoate, 2- {N- (2'
Methyl -fluoro-4'-chloro-5'-isopropoxyphenyl) carbamoyloxy} -3- (4 "-fluorophenyl) -3-butenoate, 2- (N-phenylcarbamoyloxy) -3- (4 ' -Chlorophenyl) -3-
Methyl butenoate, 2- {N- (4'-chlorophenyl)
Methyl carbamoyloxy} -3-ethyl-3-pentenoate, 2- {N- (4′-fluorophenyl) lumamoyloxy} -3-methyl-3-pentenoate, 2- {N
-(4'-Fluorophenyl) carbamoyloxy} -3
-Methyl ethyl-3-butenoate, 2- {N- (3 ', 5'
-Dichlorophenyl) carbamoyloxy} -2- (1 "
-Cyclopentenyl) methyl acetate, 2- {N- (2'-
Fluoro-4'-chloro-5'-isopropoxyphenyl) carbamoyloxy} -2- (1 "-cyclohexenyl) methyl acetate, 2- {N- (2 ', 4'-dichloro-
5'-isopropoxyphenyl) carbamoyloxy}-
2- (1 ″ -cyclododecenyl) methyl acetate, 2- {N
Methyl-(2'-chloro-5'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-pentenoate, 2- {N- (2'-chloro-5'-trifluoromethylphenyl) carbamoyloxy}- 3-butyl-
Methyl 3-butenoate, 2- {N- (2'-chloro-5 '
-Trifluoromethylphenyl) carbamoyloxy}-
Ethyl 3-methyl-3-pentenoate, 2- {N- (2 '
-Chloro-5'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-pentenoate isobutyl, 2- {N- (2'-chloro-5'-trifluoromethylphenyl) carbamoyloxy} -3-butyl- 3-
Isobutyl butenoate, 2- {N- (2'-fluoro-
Methyl 4'-chloro-5'-isopropoxyphenyl) carbamoyloxy} -3-butyl-3-butenoate, 2-
{N- (2'-Fluoro-4'-isopropoxyphenyl) carbamoyloxy} -3-butyl-3-butenoate isobutyl, 2- {N- (2'-fluoro-4'-chloro-5'-isopropoxy Phenyl) carbamoyloxy}
Methyl-3-methyl-3-pentenoate, 2- {N-
(2'-Fluoro-4'-chloro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-pentenoate isobutyl, 2- {N- (3 ', 5'-dichlorophenyl) carbamoyloxy} -3- Methyl (4'-chlorobenzyl) -3-butenoate, 2- {N- (3 ', 5'
-Dichlorophenyl) carbamoyloxy} -3- (4 "
-Fluorobenzyl) -3-butenoic acid ethyl, 2- {N
-(3 ', 5'-dichlorophenyl) carbamoyloxy}
-3- (3 ", 5" -dichlorobenzyl) -3-isobutyl butenoate, 2- {N- (3 ', 5'-dichlorophenyl) carbamoyloxy} -3-methyl-4- (4 "-dichlorophenyl)- 3-Methyl 3-butenoate, 2- {N-
(3 ', 5'-Dichlorophenyl) carbamoyloxy}-
Ethyl 3-methyl-4- (4 "-fluorophenyl) -3-butenoate, 2- {N- (3 ', 5'-dichlorophenyl) carbamoyloxy} -3-methyl-4- (3", 5 "
-Dichlorophenyl) -3-butenoic acid isobutyl and the like can be mentioned, which can be used as a raw material for the reaction of the present invention.

In carrying out the reaction of the present invention, the carbamate represented by the general formula (II) produced by the reaction of the compounds of the general formulas (III) and (IV) is isolated from the reaction system. However, the desired oxazolidinedione derivative represented by the general formula (I) can be produced by treating with a base.

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

Further, in carrying out the reaction of the present invention, 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. The pure oxazolidinedione derivative can be easily isolated by separating the precipitated crystals by cooling accordingly.

Among the compounds represented by the above general formula (I) 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 Which represents 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, and Y
Is a leaving group] and [reacted in the presence of a base when M in the general formula (V) is a hydrogen atom].

The reaction is preferably carried out in an organic solvent. As the organic solvent, hexane, heptane, aliphatic hydrocarbons such as ligroin, aromatic hydrocarbons such as benzene, toluene, xylene, diethyl ether, diisopropyl ether,
Dioxane, tetrahydrofuran, ethers such as ethylene glycol dimethyl ether, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and isodetylonitrile, 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, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, sodium acetate, acetic acid A carboxylic acid alkali metal salt such as potassium can be used.

When chloride, bromide or sulfonic acid ester is used as the compound represented by the general formula (VI) in this reaction, iodide such as potassium iodide or sodium iodide, tetraethylammonium bromide or benzyltriethylammonium may be used depending on the compound. By adding a quaternary ammonium salt such as bromide or iodide, the reaction can be accelerated and the compound 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. -Buchin 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-
Olefin compounds such as 1-butene, ethyl 2-bromoacetate, ethyl 2-chloroacetate, methyl 2-bromopropionate, ethyl 2-bromoacetate, isopropyl 2-bromoacetate, 2-bromopropionate (2'-ethyl) Substituted alkyl halogen compounds such as hexyl, or propargyl alcohol, 1-butyn-3-ol, 3-methyl-1-butyn-3-ol, 1-butyn-4-ol, allyl alcohol, methallyl alcohol, 3- Alcohols such as methyl-3-buten-1-ol, methyl glycolate and methyl lactate, and sulfonic acid esters of ordinary lower aliphatic alcohols, p-toluenesulfonic acid ester, benzenesulfonic acid ester and the like can be used. .

The above-mentioned general formula (V) which is a raw material for producing the compound of the present invention
The phenol derivative represented by [In the formula, R ¹ , R ² , R ⁴ and R ⁵ have the same meanings as described above, and R ⁸ is a lower alkyl group having 1 to 4 carbon atoms or 7 carbon atoms.
Represents -10 aralkyl groups. ] 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) In carrying out the reaction of the present invention, a metal salt of a phenol derivative obtained by treating the compound of the general formula (VII) with a base [general formula (V)] In the case where M is an alkali metal) is reacted with the compound represented by the general formula (VI) without isolation from the reaction system to give the 1,3-oxazolidine-formula represented by the general formula (I ′). 2,4-
Dione derivatives can be prepared.

Further, the oxazolidinedione derivative represented by the general formula (VII) can be produced by the following method.

That is, nitrobenzene derivative (VIII) (in the formula, R ¹ and R ² have the same meanings as described above, R ⁸ represents a lower alkyl group or an aralkyl group.) Reduction in the presence of a catalyst to give an aniline derivative (IX) (wherein R ¹ , R ² and R ⁸ have the same meanings as described above), and then treating this with phosgene gas or trichloromethyl chloroformate. Easily reacts with the isocyanate derivative (X) (wherein R ¹ ,
R ² and R ⁸ have the same meanings as described above. ) Can be converted to. Next, with this isocyanate derivative (X),
β, γ-unsaturated glycolic acid ester (XI) (in the formula, R ⁴
And R ⁵ have the same meaning as described above, and R ⁹ has 1 to 4 carbon atoms.
Represents a lower alkyl group. ) And optionally in the presence of a base to give a carbamate derivative (XII) (wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ and R ⁹
Represents the same meaning as described above. ) Can be led to. And cyclizing this carbamate 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 Examples, Reference Examples and Experimental Examples. The physical properties and spectrum measurement values of the compounds synthesized in Examples 1 to 38 are shown in Tables 2 and 3.

Example 1. 2- {N-4'-chlorophenyl) carbamoyloxy}
Triethylamine (1.0 ml) was added to a benzene (50 ml) solution of methyl-3-methyl-3-butenoate (2.71 g, 10 mmol), 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) which were isolated by filtration. This is from 3-NMR and IR
(4 ', chlorophenyl) -5-isopropylidene-1,
It was confirmed to be 3-oxazolidine-2,4-dione.

Example 2. Sodium methoxide was added to a solution of methyl 2- {N- (2 ', 4'-dichloro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate (1.82g, 5.0mmol) in benzene (50ml). (0.1 g) was added and the mixture was heated under reflux for 1 hr, and then the solvent was distilled off. Methanol (20 ml) was added and the mixture was cooled, and white crystals (1.10 g) precipitated were separated. It was confirmed from NMR and IR that this was 3- (2 ', 4'-dichloro-5'-isopropoxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Example 3. Methyl 2- {N- (2'-fluoro-4'-chloro-5'-isopropoxyphenyl) carbamoyloxy} -3-methyl-3-butenoate (1.79g, 5mmol) in toluene (5
Sodium methoxide (0.1 g) was added to the solution (0 ml) and the mixture was heated under reflux for 2 hours. Then, the solvent was distilled off completely, methanol (20 ml) was added, and the mixture was cooled and the white crystals (0.98 g) precipitated were separated. This product was confirmed to be 3- (2 '
-Fluoro-4'-chloro-5'-isopropoxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione was confirmed.

Example 4. Methyl 2- {N- (2 ', 4'-difluorophenyl) carbamoyloxy} -3-methyl-3-butenoate (1.43 g,
Sodium methoxide (50 mg) was added to a toluene (30 ml) solution of 5 mmol) 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 compound was analyzed by NMR and IR to be 3- (2 ', 4'-difluorophenyl) -5-
It was confirmed to be isopropylidene-1,3-oxazolidine-2,4-dione.

Example 5. Methyl 2- {N- (4'-fluorophenyl) carbamoyloxy} -3-ethyl-3-butenoate and 2- {N-
(2 ', 4'-Dichlorophenyl) carbamoyloxy}-
Mixture of methyl-3-pentenoate (1.40g, 5mmo
N-Methylmorpholine (0.5 ml) was added to a solution of l) in benzene (30 ml) and the mixture was reacted under heating under reflux for 3 hours. The solvent was distilled off completely, and then methanol was added to isolate precipitated white crystals (1.05 g). From NMR and IR, it was confirmed that this was 3- (2 ', 4'-dichlorophenyl) -5- (2'butylidene) -1,3-oxazolidine-2,4-dione.

Examples 6 to 10 In the same manner as in Example 1, the corresponding oxazolidinedione derivative was synthesized from the following carbamate.

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

Example 11: Methyl 2- {N- (2 ', 4'-dichlorophenyl) carbamoyloxy} -3-methyl-3-butenoate Example 12: 2- {N- (2', 4 ', 6'-Tri Methyl (chlorophenyl) carbamoyloxy} -3-methyl-3-butenoate Example 13: 2- {N- (2 ′, 4′-dichlorophenyl) carbamoyloxy} -3-ethyl-3-pentenoate methyl Example 14: 2- Methyl {N- (4'-chlorophenyl) carbamoyloxy} -2- (1'-cyclohexenyl) acetate Example 15. 2,4-Dichlorophenyl isocyanate (4.16g, 22.2mmo
A solution of l) 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. From the NMR and IR spectra of the reaction mixture, the starting isocyanate disappeared completely,
Carbamic acid ester [2- {N-
(2 ', 4'-Dichlorophenyl) carbamoyloxy}-
It was confirmed that 3-methyl-3-methylbutenoate] was produced. Then, sodium methoxide (100 mg) was added and the mixture was heated under reflux for 5 hours. Next, the solvent was distilled off, methanol (20 ml) was added, and the mixture was cooled, and white crystals precipitated (3.32 g).
Separated. This is a 3- (2 ', 4'- from NMR, IR, etc.
It was confirmed to be dichlorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Example 16. 2-fluoro-4-chloro-5-isopropoxyphenyl isocyanate (2.30 g, 10 mmol) and 2-hydroxy-
A solution of methyl 3-methyl-3-butenoate (3.0 g, 23 mmol) in toluene (50 ml) was reacted for 3 hours at 80 ° C. From the IR and ¹ H-NMR spectra of the reaction mixture, the isocyanate disappeared completely and the carbamic acid ester [2- {N- (2'-fluoro-4'-chloro-5'-
It was confirmed that isopropoxyphenyl) carbamoyloxy} -3-methyl-3-butenoic acid methyl] was produced. Then, sodium methoxide (0.1 g) was added, and the mixture was reacted for 5 hours while heating under reflux. 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 shows 3- (2'-fluoro-4'-) from NMR and IR spectra.
It was confirmed to be chloro-5'-isopropoxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

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

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

Example 19. Phenylisocyanate (1.19g, 10mmol) and methyl 2-hydroxy-3-methyl-3-butenoate (2.0g, 15mmo
A solution of l) in benzene (50 ml) was reacted for 2 hours at room temperature. From the NMR and IR spectra of the reaction mixture, the raw material isocyanate disappeared, and the carbamate ester [methyl 2- (N-phenylcarbamoyloxy) -3-methyl-3-butenoate] as an adduct was produced. It was confirmed. 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-oxazolidine-2,4-dione.

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

Example 20: 2-Fluorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-butenoate Example 20 ': 4-Chlorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-heptenoate and 2
Methyl -hydroxy-3-butyl-3-butenoate Example 21: 4-Chlorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-nonenate and methyl 2-hydroxy-3-hexyl-3-butenoate Examples 22: 3,4-dichlorophenyl isocyanate and 2-
Methyl hydroxy-3-methyl-3-butenoate Example 23: Phenylisocyanate and 2-hydroxy-
Methyl 3-ethyl-3-pentenoate Example 24: 3,4-Dichlorophenyl isocyanate and 2-
Methyl hydroxy-3-phenyl-3-butenoate Example 25: 3,4-Dichlorophenyl isocyanate and 2-
Methyl hydroxy-3- (4'-chlorophenyl) -3-butenoate Example 26: Phenylisocyanate and 2-hydroxy-
Methyl 3- (4'-chlorophenyl) -3-butenoate Examples 27 to 31. In the same manner as in Example 19, the corresponding carbamate was synthesized from the following aryl isocyanate and 2-hydroxycarboxylic acid ester, and then the base was prepared. The desired oxazolidinedione derivative was synthesized by treatment.

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

Example 33. Benzene of N- (4-fluorophenyl) carbamoyl chloride prepared from 4-fluoroaniline (2.22g, 20mmol) and trichloromethyl chloroformate and methyl 2-hydroxy-3-methyl-3-butenoate (1.30g, 10mmol) Triethylamine (2 ml) was added to the (50 ml) solution and the mixture was reacted at room temperature for 3 hours. The reaction mixture is then heated to reflux under 3
After reacting for a time, after completion of the reaction, the solvent and the like were completely distilled off, 0.1N hydrochloric acid was added to the obtained reaction mixture, and the mixture was extracted with ether.
After drying, the solvent was completely removed, methanol was added, and the mixture was cooled to obtain white crystals (1.17 g) which were precipitated. It was confirmed by spectrum and the like that this was the desired 3- (4'-fluorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione.

Example 34. The reaction was performed in the same manner as in 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.

Example 35. Ethyl 2-hydroxy-3-methyl-3-butenoate (3.6g, 25mmol) was added to 4-ethylphenylisocyanate prepared from 4-ethylaniline (3.63g, 30mmol) and trichloromethyl chloroformate and benzene (50ml). 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, methanol was added to the resulting mixture, and the precipitated white crystals (3.3 g) were isolated by filtration.
This is 3- (4'-ethylphenyl) from NMR, IR, etc.
-5-isopropylidene-1,3-oxazolidine-2,4-
It was confirmed to be Zeon.

Example 36. 3,5-Dichlorophenyl isocyanate (1.88g, 10mmo
Methyl 2-hydroxy-2-cyclopentenylacetate (1.95g, 15mmol) was added to l) and reacted in a solvent of benzene (30ml). ,
Add triethylamine (0.5 ml) and reflux under benzene for 3
Reacted for hours. The solvent and the like were completely distilled off, and methanol was added to separate precipitated white crystals (1.24 g). It was confirmed from NMR and IR spectra that this was 3- (3 ', 5'-dichlorophenyl) -5-cyclopentyldene-1,3-oxazolidine-2,4-dione.

Example 37. 2-hydroxycarboxylic acid ester is 2-hydroxy-
Examples except that it is methyl 3-ethyl-3-pentenoate
Reaction was carried out in the same manner as in 36 to obtain 3- (3 ', 5'-dichlorophenyl) -5- (3'-pentylidene) -1,3-oxazolidine-2,4-dione.

Example 38. Methyl 2- {N- (2'-chloro-5'-trifluoromethylphenyl) carbamoyloxy} -3-methyl-3-heptenoate and methyl 3-butyl-3-butenoate (1.97g, 5mmol) in toluene (30ml ) Potassium in solution
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 (0.85g)
Separated. From the NMR and IR spectra, this product shows 3- (2'-chloro-5'-trifluoromethylphenyl) -5-isopropylidene-1,3-oxazolidine-
It was confirmed to be 2,4-dione.

The starting compounds of Examples 1-38 above were prepared according to Reference Examples 1-4 below.

Reference example 1. 2,4-Dichloro-5-isopropoxyphenylisocyanate (1.72g, 7mmol) and methyl 2-hydroxy-3-methyl-3-butenoate (1.04g, 8mmol) in benzene (20m
l) The solution was heated to reflux for 2 hours. By separating and purifying the obtained reaction mixture with a silica gel column, 2-
Methyl {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. A solution of N- (2,4-difluorophenyl) carbamoyl chloride (2.58 g, 20 mmol) in benzene (30 ml) was added with methyl 2-hydroxy-3-methyl-3-butenoate (3.0 g, 23 mmo).
l) was added, then N-methylmorpholine (2.5 ml) was added, and the mixture was reacted at room temperature for 3 hours. After the reaction was completed, 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 by a silica gel column to give 2- {N- (2 ', 4'-difluorophenyl). ) Methyl carbamoyloxy} -3-methyl-3-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), 5.15 (s, 1
H), 5.30 (d, 1H), 6.78 (m, 2H), 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 (3.80g, 20.2mmo
l) and a solution of methyl 2-hydroxy-3-methyl-3-butenoate (3.05 g, 23.5 mmol) in toluene (80 ml) are reacted under heating under reflux for 5 hours, and the resulting reaction mixture is separated and purified by a silica gel column. Therefore, 2- {N-
(2 ', 4'-Dichlorophenyl) carbamoyloxy}-
Methyl 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, 1H), 7.35 (m, 2H), 8.13
(D, 1H).

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

Hereinafter, another production method of the present invention will be described in Examples 39 to 46.

Example 39 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (0.72g, 2.5mmol) in acetonitrile (30ml) 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 further reacted under reflux for 1 hour. After completion of the reaction, 0.1N-hydrochloric acid was added to weakly acidify the mixture, 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%) Example 40 3- (2'-Fluoro-4'-bromo-5-hydroxyphenyl) -5- (sec-butylidene) -1,3-oxazolidine-2,4-dione (0.26g, 0.82mmol) in acetonitrile (25ml) 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 reaction was continued for 1 hour. By the same operation as in Example 1, 3- (2′-fluoro-4 ′)
-Bromo-5-propargyloxy) -5- (sec-butylidene) -1,3-oxazolidine-2,4-dione (0.24
g, 77%).

Example 41 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (0.57g, 2.0mmol) and potassium carbonate (0.27g) Solution of 1-butyn-3-ol in p-toluenesulfonic acid (0.
5 g, 2.2 mmol) and a catalytic amount of benzyltoluethyl ammonium bromide (about 20 mg) were added, and the mixture was 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.

Example 42 3- (2 ', 4'-Dichloro-5'-hydroxyphenyl) -5- (sec-butylidene) -1,3-oxazolidine-2,4-dione (1.58 g, 5.0 mmol) in acetonitrile (3
Potassium carbonate (0.69 g) was added to the solution (0 ml) and the mixture was heated under reflux for 2 hours. Then ethyl 2-bromopropionate (0.93
g, 5.1 mmol) was added and the mixture was refluxed for 1 hour. After the reaction was completed, ether was added to the solution, and the mixed solution was washed with 1N-hydrochloric acid,
After drying, the solvent was distilled off. By separating and purifying the obtained oily matter 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 73) %) Was obtained.

Example 43 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (2.85 g, 10 mmol) in isopropyl iodide (3 ml) and A solution of potassium carbonate (3.5 g) in acetonitrile (50 ml) 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-2,4-dione (Compound 27) (3.10 g, yield 95%) was confirmed (Compound 27) .

Example 44 3- (2'-Fluoro-4'-chloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (175 mg, 0.61 mmol) in DMF (10 m
l) Potassium carbonate (42 mg) was added to the solution, and the mixture was stirred at room temperature for 3 hours. Then 2,3-dichloro-1-propene (0.5 ml)
Was added and the mixture was 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-4'-chloro-5- (2 "-chloroallyl) oxyphenyl} -5-
It was isopropylidene-1,3-oxazolidine-2,4-dione.

Example 45 3- (2'-fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl) -5-isopropylidene-
1,3-oxazolidine-2,4-dione (3.43g, 10mmol)
K ₂ CO ₃ (1.38 g, 10 mmol) was added to a methanol (50 ml) solution of and the mixture was heated to reflux for 1 hour. Then, the solvent was completely removed under reduced pressure, and acetonitrile (50 ml) was newly added. Further, propargyl bromide (5 ml) was added and the mixture was reacted at room temperature for 2 hours. The reaction mixture was treated as in Example 1 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.

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'-fluoro-4'-chloro-5'-sodium oxyphenyl) -5-isopropylidene-1,3-oxazolidine-
A white solid of 2,4-dione was obtained. Then, acetonitrile (10 ml) and methyl iodide (1 ml) were added to this product, 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. 3- (2'-Fluoro-4'-chloro-5'-methoxyphenyl) -5- was obtained by adding a small amount of methanol to this and cooling.
White crystals (1.42 g, yield 95%) of isopropylidene-1,3-oxazolidine-2,4-dione were obtained.

According to the method of Examples 39 to 46, the compounds 30 to 30 shown in Table 1
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 Examples 39 to 46 will be described in Reference 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 (1.38 g, 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. There was obtained 3,3-oxazolidine-2,4-dione (1.60 g). ¹ H-NMR (CDCl ₃ , TMS, ppm): δ 2.06 (3H, s), 2.29 (3H, s), 5.78 (1H, br s), 6.98 (1
H, d), 7.25 (d, 1H).

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

M.P .: 133-135 ° C.

Reference example 5 3- (2 ′, 4′-dichloro-5′-) synthesized from 2,4-dichloro-5-methoxycarbonyloxynitrobenzene as a starting material and in the same manner as in Reference Examples 6, 9, 10 and 4. Methoxycarbonyloxyphenyl) -5-
Potassium carbonate (0.69 g, 5 mmol) was added to a solution of isopropylidene-1,3-oxazolidine-2,4-dione (3.60 g, 10 mmol) in dry methanol (100 ml), and the mixture was refluxed for 2 hours. By performing the same processing as in Reference Example 1, 3- (2 ', 4'-
Dichloro-5'-hydroxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (1.72
g) was obtained. 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 (KBr disk, cm ^-1 ): 3400,1820,1739,1690.

M.P .: 166-168 ° C.

Reference example 6 2-Fluoro-4-chloro-5-methoxycarbonyloxynitrobenzene (52.1g, 0.24mol) in ethanol (600ml) was added platinum dioxide (1.5g) and hydrogen gas absorption stopped under 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.
From the NMR spectrum, this was confirmed to be almost pure 2-fluoro-4-chloro-5-methoxycarbonyloxyaniline. This product can be purified by silica gel column chromatography,
It can be used as it is for 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 = 8H
z), 6.92 (1H, d, J _HF = 10Hz).

Reference example 7 2-Fluoro-4-bromo-5-methoxycarbonyloxynitrobenzene (30.4 g, 0.1 mol) in ethanol (3
Platinum dioxide (1.0 g) was added to the solution (00 ml), and the mixture was stirred under a hydrogen atmosphere until absorption of hydrogen 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 (CCl 4 -}} , TMS, ppm): δ 3.83 (3H, s), 5.01 (2H, br s), 6.63 (1H, d, J HF = 7.6H
z), 7.06 (1H, d, J _HF = 9.8Hz).

Reference example 8 A 500 ml three-necked flask equipped with a dropping funnel and a distillation apparatus was charged with a solution of trichloromethyl chloroformate (15 ml, 125 mmol) in ethyl acetate (150 ml), and 2-fluoro-4-synthesized by the method shown in Reference Example 4. A solution of bromo-5-methoxycarbonyloxyaniline (28.0 g, 113 mmol) in ethyl acetate was added dropwise over 20 minutes. After completion of dropping, the mixture was heated to 80 ° C. and ethyl acetate was distilled off. After cooling, carbon tetrachloride (150m
l) was added to remove insoluble matter, and the solvent was distilled off from the solution under reduced pressure to give 2-fluoro-4-bromo-5-methoxycarbonyloxyphenylisocyanate (29.1 g,
A brown solid with a yield of 94% was obtained. ¹ H-NMR (CCl ₄ , TMS, ppm): δ 3.87 (3H, s), 6.89 (1H, d, J _HF = 6.8Hz), 7.31 (1H, d, J
_HF = 8.6Hz).

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

Reference example 9 2-Fluoro-4-chloro-5-methoxy-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. -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 (KBr disk, cm ^-1 ): 2260,1770.

Reference example 10 2-Fluoro-4-chloro-5'-methoxycarbonyloxyphenylisocyanate (2.45 g, 10 mmol) and ethyl 2-hydroxy-3-methyl-3-butenoate (1.44) synthesized by the methods shown in Reference Examples 6 and 9 were used. g, 10 mmol) in benzene (50 ml) was added with a catalytic amount of triethylamine and stirred at room temperature for 0.5 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 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%) was obtained. ¹ H-NMR (CDCl ₃ , TMS, ppm): δ 1.29 (3H, t), 1.84 (3H, br s), 3.93 (3H, s), 4.24 (2
H, q), 5.14 (1H, m), 5.23 (1H, m), 5.45 (1H, s), 7.20
(1H, d), 7.0 to 7.35 (1H, br s), 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-
Methyl hydroxy-3-methyl-3-pentenoate was heated to reflux in a benzene (50 ml) solvent for 1 hour. 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 (3H, 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 resulting oily matter 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, 1
H), 7.42 (1H, d).

The compounds of the present invention obtained as shown in Examples are
As described above, it has excellent performance as a herbicide.

When the compound of the present invention is used as a herbicide, it can be used as it is, but generally, one or several kinds of auxiliary agents can be mixed and used as the herbicide of the present invention. Usually, as an auxiliary agent, various carriers, fillers, solvents, surfactants, stabilizers and the like may be mixed and used by formulating in a conventional manner, for example, in the form of wettable powder, emulsion, powder, granules and the like. preferable.

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, etc. are suitable, and one kind or a mixture of two or more kinds thereof is used.

Further, as the extender, clay such as kaolin and bentonite, talc such as talc and pyrophyllite, diatomaceous earth, mineral powder such as oxide such as white carbon and soybean powder, CM
Vegetable powders such as C are 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 has particularly excellent effects.

Further, the herbicide using the compound of the present invention, other active ingredients that do not inhibit the herbicidal activity of the present active ingredient, for example, other herbicides, insecticides, fungicides, plant growth regulators or the like are used in combination. 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 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 R100C (manufactured by Toho Kagaku Co., Ltd.) is uniformly mixed and ground to obtain a wettable powder.

Formulation Example 3 (granule) 5 parts of the compound of the present invention, 35 parts of bentonite, 55 parts of talc,
A mixture of 5 parts of sodium lignin sulfonate is uniformly mixed and ground, then water is added and kneaded, and granulated by an extrusion granulator, and then dried and granulated to obtain granules.

Test Example 1 (Effect on Paddy Field Weeds) Paddy field soil was filled in a Wagner pot of 1 / 5,000 are, and seeds of fly, eel and hemisophyllum 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 as a granule according to Formulation Example 3 was
A predetermined amount of water was surface-treated to give 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 Herbicidal rate: Percentage of residual grass (%) 0: 81 to 100 1: 61 to 80 2: 41 to 60 3: 21 to 40 4: 6 to 20 5: 0 to 5 Chemical damage: Growth rate − : None ＋: Slight harm ++ ： Small harm +++ ： Medium harm ++++ ： Severe harm × ： Withered Test Example 2 Wagner pots of 1 / 5,000 are were filled with upland soil, and weeds were sown with seeds of crabgrass, polygon, indica, and corn, cotton or soybean as crops,
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 50,25,20,1
Disperse it evenly over the cover soil to give 0, 12.5, 5g, and after treatment 2
On day 0, the herbicidal effect and phytotoxicity 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) A field soil was filled in a Wagner pot of 1 / 5,000 are, and weeds such as barnyardgrass, crabgrass, sardine, 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 sprayed uniformly to the test plants at a spray water volume of 100 l / 10a. On the 20th day after the treatment, the herbicidal effect and phytotoxicity (on wheat, soybean, corn) were evaluated in the same manner as in Test Example 1. The results are shown in Table 8.

Front page continuation (72) Inventor Shoin Nagato 3-13-13-106, Kahama, Adachi-ku, Tokyo (56) Reference US Patent 3995049 (US, A) US Patent 3966750 (US, A)

Claims (11)

[Claims] 1. A general formula [Wherein, R ^1, R ² and R ³ independently of one another are hydrogen, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group or a cycloalkyl group; R ⁴ and R ⁵ is independently of each other a hydrogen atom, an alkyl group, an aryl group or R ⁴ and R ⁵ can be integrated together to form a polymethylene chain, provided that R ¹ , R ² , R ³ and R ⁵ are hydrogen at the same time. It cannot be an atom: the above alkyl group, alkoxy group, alkenyloxy group,
An alkynyloxy group, a cycloalkyloxy group and an aryl group may be substituted]. 2. R ¹ , R ² and R ³ are independently of each other a hydrogen atom; a halogen atom, a nitro group; a linear or branched alkyl group having 1 to 8 carbon atoms [substituted by 1 or 2 or more halogen atoms. Or an oxazolidinedione derivative according to claim 1, which is a linear or branched alkoxy group having 1 to 8 carbon atoms. 3. R ⁴ and R ⁵ independently of one another are a hydrogen atom; a linear or branched alkyl group having 1 to 8 carbon atoms;
An aryl group of 10 [which may be substituted with one or more halogen atoms]; or R ⁴ and R ^{5 which} are integrated to form a linear or branched polymethylene group having 3 to 10 carbon atoms The oxazolidinedione derivative according to claim 1 or 2. 4. R ¹ , R ² and R ³ independently of one another are a hydrogen atom; a halogen atom; a C 1-8 alkyloxy group which may be substituted with a C 2-18 alkyloxycarbonyl; An alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with a halogen atom; a straight chain having 2 to 8 carbon atoms which may be substituted with 1 or 2 or more halogen atoms, or A branched alkenyl group; an oxazolidinedione according to claim 1, which is a linear or branched alkynyl group having 2 to 8 carbon atoms which may be substituted with one or more halogen atoms. Derivative. Wherein R ⁴ and R ⁵ independently of one another are hydrogen atoms or the claims, wherein the first term or the fourth term, wherein a linear or branched alkyl group having 1 to 8 carbon atoms Oxazolidinedione derivative of. 6. A general formula [Wherein, R ^1, R ² and R ³ independently of one another are hydrogen, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group or a cycloalkyl group; R ⁴ and R ⁵ is independently of each other a hydrogen atom, an alkyl group, an aryl group or R ⁴ and R ⁵ can be combined together to form a polymethylene chain; R ⁶ is an alkyl group; the above alkyl group, alkoxy group, Alkenyloxy group,
An alkynyloxy group, a cycloalkyloxy group, or an aryl group may be substituted], wherein the carbamic acid ester represented by the formula is treated with a base. [Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above]
A method for producing an oxazolidinedione represented by: 7. The method according to claim 6, wherein the reaction is carried out in an inert organic solvent at room temperature to reflux temperature. 8. The base used is an organic tertiary amine; an aromatic amine; an alkyl metal alkoxide; an alkali metal hydride; an alkali metal hydroxide; or a basic inorganic salt. The method according to claim 6 or 7. 9. General formula [Wherein R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group or a cycloalkyloxy group; and R ⁴ and R ⁵ are Independently of each other, a hydrogen atom, an alkyl group, an aryl group or R ⁴ and R ⁵ may be integrated together to form a polymethylene chain; the above alkyl group, alkoxy group, alkenyloxy group,
The alkynyloxy group, cycloalkyloxy group and aryl group may be substituted; M is a hydrogen atom or an alkali metal] and a phenol derivative represented by the general formula R ⁷ -Y [wherein R ⁷ is substituted or An unsubstituted linear or branched alkyl group, an alkenyl group, an alkynyl group, or a substituted or unsubstituted cycloalkyl group, and Y is a leaving group], [M is a hydrogen atom] In the presence of a base], the general formula [Wherein R ¹ , R ² , R ⁴ , and R ⁵ are as described above, and R ³ ′ is −
O-R ⁷ (R ⁷ is as described above)]. 10. The method according to claim 9, wherein the reaction is carried out in an inert organic solvent. 11. A base used when M in the above general formula is a hydrogen atom is an organic tertiary amine; an aromatic amine;
The method according to claim 9 or 10, which is an alkali metal alkoxide; an alkali metal hydride; an alkali metal oxide; or a basic inorganic salt.