JPS62174065A - Oxazolidinedione derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R<1>-R<3> are H, halogen, NO2, alkykl, alkoxy, alkenyloxy, alkynyloxy or cycloalkyloxy wherein alkyl, alkoxy, alkenyloxy, alkynyloxy or cycloalkykloxy may be replaced, respectively; R<4> and R<5> are H, alkyl or aryl which may be replaced, respectively or R<4> and R<5> are bonded to form polymethylene chain). EXAMPLE:3-(4'-Chlorophenyl)-5-isopropylidene-1, 3-oxazolidine-2, 4-dione. USE:A herbicide. PREPARATION:A carbamic acid ester shown by formula II (R<6> is alkyl) is treated with a base (e.g., tertiary amine or alkali metal alkoxide) to give a compound shown by formula I. The compound shown by formula II is obtained by reacting an aryl isocyanate shown by formula III (Y is isocyanato or chlorocarbamoyl) or carbamoyl chloride with a beta, gamma-unsaturated- alpha- hydroxycarboxylic acid ester shown by formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel oxazolidinedione derivative and a method for producing the same. More specifically, the present invention relates to hydrogen atoms, halogen atoms, nitro groups, alkyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups,
or a cycloalkyloxy group; can form a polymethylene chain; the above alkyl group, alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkyloxy group, and aryl group may be substituted. ] and a method for producing the same.

Various derivatives having a substituent at the 5-position of the oxazolidinedione ring have been known, but no oxazolidinedione derivatives having a substituted methylidene group at the 5-position have been reported due to the difficulty in their synthesis. It has not been.

Furthermore, although many heterocyclic compounds having herbicidal activity have been synthesized to date, and some of them have been put into practical use, oxazolidinediones having practical herbicidal activity have not been known so far.

[Problems to be Solved by the Invention] The present invention provides novel compounds that have both high selectivity and strong herbicidal activity against weeds, and further provides an industrial method for producing these compounds. It is necessary.

[Means for solving the problems] The present inventors have discovered that among oxazolidinedione derivatives, 5
By introducing a methylidene group with various substituents at this position, we have developed a method that exhibits strong herbicidal activity and high selectivity against various weeds.

The object compound of the present invention is represented by the general formula (I), in which R, R and R3 are each independently a hydrogen atom; a nitro group; a halogen atom such as fluorine, chlorine, bromine or iodine; 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 an n-hexyl group, n-heptyl group, or n-octyl group, and this group has one or more halogen atoms. may be substituted with; methoxy group, ethoxy group, n-propoxy group, isopropoxy group; alkoxy group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms such as n-butoxy group and t-butoxy group; This group may be substituted with one or more alkoxycarbonyl groups (2 to 18 carbon atoms), halogen atoms, etc.; carbon atoms such as cyclohexyloxy, cyclopentyloxy, and cyclopropyloxy groups A cycloalkoxy group having a number of 3 to 12, preferably 3 to 8, and may be substituted with one or more lower alkyl groups (having 1 to 5 carbon atoms), a halogen atom, etc.; an allyl group, a methallyl group, 2-12 carbon atoms such as propenyl group, butenyl group, pentenyl group, hexenyl group, etc.
, preferably 2 to 8 linear or branched alkenyl groups, which may be substituted with one or more halogen atoms, etc.; propargyl group, 1-methylpropargyl group, 1,1-dimethylpropargyl group, 2-butynyl group,
A straight or branched alkynyl group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as a 3-butynyl group, 2-pentynyl group, or 3-pentynyl group, substituted with one or more halogen atoms, etc. and R and R5 are each independently a hydrogen atom; A linear or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to B, which may be substituted with one or more halogen atoms, or a phenyl group, p-chlorophenyl group, p-fluorophenyl group. group, m, p-dimethoxyphenyl group, p-methylphenyl group, etc. with 6 or more carbon atoms
10 aryl group, halogen atom, carbon number 1-3
or R and R5 together form a linear or molecular chain polymethylene group having 3 to 10 carbon atoms;

The bonding positions of the phenyl groups of R, R and R3 are not particularly limited, but when two of R1-R3 are other than hydrogen, 2
, 4-12, 5-13, 4-13.5-positions are preferred;
When all three are other than hydrogen, it is preferably at the 2,4.5-1 or 2,4.6-position.

121 Representative compounds represented by formula (1) of the present invention are shown in Table 1.

Table 1 List of Oxylizolidine diane 1
) Table 1 (continued) Table 1 (continued) Table 1 (continued) Table 1 (continued) Table 1 (continued) 1) Abbreviations in the table are as shown below.

n-pr: n-propyl n-05H
11: n-pentyl C5t-+5: phenyl pc, Q-c6 14: p-riphenyl 1-prQ: isopropoxy 2) Compounds marked with *1. The stereochemistry of the double bond at position 5 of the oxazolidinedione ring is a mixture of cis-trans isomers.

When the novel oxazolidinedione derivatives of the present invention are used in paddy fields, they exhibit strong herbicidal efficacy against annual weeds such as barnyard grass, Japanese eel, and Japanese grasshopper, as well as perennial weeds such as Japanese grasshopper, firefly, urticaria, and pineweed. . In addition, it is also possible to selectively kill field weeds such as dogweed, silver grass, foxtail grass, whiteweed, Japanese knotweed, blueberry, purslane, and plantain in fields.

In general, the compounds of the present invention have strong weedicidal activity, do not require a small amount to achieve the desired effect, and have extremely low phytotoxicity to useful cultivated plants. That is, while the compound of the present invention kills weeds of the grass family, such as barnyard grass, grasshopper, and foxtail grass, it causes almost no phytotoxicity to transplanted paddy rice, wheat, corn, etc., which are rice H crops. Similarly, almost no phytotoxicity is observed on crops other than the grass family, such as soybeans and cotton.

The compound of the present invention can be used as a herbicide by blending various carriers, fillers, solvents, surfactants, stabilizers, etc., and formulating it into a desired form, such as a wettable powder, emulsion, powder, granule, etc., by a conventional method. used.

In addition, other active ingredients such as other herbicides, insecticides, fungicides, growth regulators, etc. can also be mixed during formulation.

The amount of the herbicide containing the compound of the present invention varies depending on the application method, timing, type of target plant, etc., but the amount of the compound is 1.
10-5009 per 0 are, preferably 30-300
It is about g.

represented by the general formula (I) of the present invention? ! 'r' Oxaoxazolidinedione Derivative General Formula % Formula % [In the formula, R, R, R, R and R5 are as described above, and R represents a lower alkyl group (C1 to C4). 1q can be easily obtained by treating the carbamic acid ester represented by ] with a base. The reaction is preferably carried out in a conventional organic solvent under heating or reflux.

The first method of the present invention requires that the carbamate ester represented by the general formula (TI>) be treated with a base.The bases used include triethylamine, ]~lipropylamine, Tertiary amines such as tributylamine, N-methylmorpholine, dimethylaniline, aromatic amines such as pyridine, lutidine, pyrimidine, sodium methoxide, sodium ethoxide,
Alkali metal alkoxides such as potassium t-butoxide, mono- to lithium hydrides, alkali metal hydrides such as potassium hydride, or basic inorganic compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. Can you use it? The amount of base used is generally a catalytic amount of -min.

Furthermore, the compound represented by general formula (II), which is a raw material for this reaction, can be easily produced according to the following method.
For example, the general formula [wherein R1, R2 and R3 are as described above, Y
represents an incyanato group or a carbamoyl chloride group. ]
The aryl isocyanate or carbamoyl chloride represented by the general formula % formula % [wherein R4, R51F3 and R6 are as described above]. 1q can be easily obtained by converting a β, γ-unsaturated unsaturated α-hydroxycarboxylic acid ester represented by the formula.

Aryl isocyanates and carbamoyl chlorides represented by general formula (III) are compounds easily obtained from the corresponding aniline derivatives, and examples of aryl isocyanates include phenyl isocyanate and o
, m or p-fluorophenyl isocyanate, 09m
or p-chlorophenylisocyanate O9m or p-
Bromophenyl isocyanate, 09m or 1)-iodophenyl isocyanate, 2,3-dichlorophenylisocyanate, 2,4-dichlorophenylisocyanate-1-, 2,5-dichlorophenylisocyanate, 3
, 4-dichlorophenyl isocyanate, 3,5-dichlorophenylisocyanate, 2,3-difluorophenyl isocyanate, 2.4-difluorophenyl isocyanate, 2.5-difluorophenyl isocyanate, 3.4-difluorophenyl isocyanate, 3.
5-difluorophenyl isocyanate, 2.4-dibromonoenyl isocyanate, 2゜4.6-trichlorophenylisocyanate, 2.4.5-1-dichlorophenylisocyanate, 3e4# 5-trichlorophenylisocyanate, 2.4.6- Dolifluorophenyl isocyanate, 2-chloro-4-fluorophenyl isocyanate, 2-fluoro-4-chlorophenylisocyanate, 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 phenyl isocyanate, 2,4-dichloro-5-fluorophenyl isocyanate, 2,=1. -difluoro-6-chlorophenylcyane 1-, 0, m or p
-methylphenylisocyanate, 0, m or p-ethylphenyl isocyanate, O, m or p-isopropylphenyl isocyanate 1-, O, m or pt-butylphenyl isocyanate-1, 2-chloro-5 -Methylphenyl isocyanate, 2-fluoro-5-methylphenylisocyanate, 4-chloro-5-methylphenylisocyanate, 2-dichloro-4-isopropylphenyl isocyanate, 2,4-dichloro-5-methyl Phenyl isocyanate, 2,4-difluoro-5-methylphenylisocyanate, 2-fluoro-4-chloro-5-methylphenylisocyanate, o, m or p
-methoxyphenylisocyanate, o, m or p-isopropoxyphenylisocyanate, O, m or 0-
1-butoxyphenyl isocyanate, 2-chloro-5
-methoxyphenylisocyanate, 2-fluoro-5
-methoxyphenylisocyanate, 4-chloro-5-
Methoxyphenylisocyanate-1-,2,4-dichloro-5-isopropoxyphenylisocyanate, 2,4
-Difluoro-5-isoproboxyphenylisocyanate-1-, 2-fluoro-4-chloro-5-isopropoxyphenylinocyanate, 2,4-difluoro-5-methoxyphenyl isocyanate, 2.4- dichloro-5
-ethoxyphenylisocyanate, 2-fluoro-4
-Chloro-5-methoxyphenylisocyanate, 2-
Fluoro-4-chloro-5-ethoxyphenyl isocyanate, 2-fluoro-4-bromo-5-isopropoxyphenylisocyanate, 2,4-dichloro-3-t
-butoxyphenylisocyanate, 0, m or p-2
1 to phenyl isocyanate, 2-chloro-4-nitrophenyl isocyanate, 2-fluoro-4-nitrophenyl isocyanate, 2-nitro-4-chlorophenylisocyanate, 2-nitro-4-fluorophenyl isocyanate, 01m or p-tri Fluoromethyl phenyl isocyanate, Olm or p- (fluoromethyl) phenyl incyane-1~, o, m or p- (black methyl) phenyl isocyanate, 0, m or p-
(Promomethyl) phenyl isocyanate 1-12-chloro-5-1-lifluoromethyl phenyl isocyanate, 2-fluoro-5-trifluoromethyl phenyl isocyanate, 4-chloro-5-1-lifluoromethyl phenyl isocyanate, 2-Nitro-4-trifluoromethylphenylisocyanes 1-. 2-trifluoromethyl-4-diherophenyl isocyanate-1, 3.5
-dichloro 4-nitroph I isocyanate, 2-
Nitro-5-methylphenylisocyanate, 3-nitro-4-methylphenylisocyanate, 2-trifluoromethyl-4-promophenylisocyanate, 3,
Substituted phenyl isocyanates such as 5-bis(trifluoromethyl) phenyl isocyanate can be used in the reaction. Furthermore, as carbamoyl chloride derivatives, phenylcarbamoyl chloride, 09m or p-fluorophenylcarbamoyl chloride O, m or p-bromophenylcarbamoyl chloride, 0. m or p-chlorophenylcarbamoyl chloride, 0,m or p-iodophenylcarbamoyl chloride, 2,3-dichlorophenylcarbamoyl chloride, 2,4-dichlorophenylcarbamoyl chloride carbamoyl chloride, 3,4-dichlorophenylcarbamoyl chloride, 3,5-dichlorophenyl Carbamoyl chloride, 2,3-difluorophenylcarbamoyl chloride, 2,4-difluorophenylcarbamoyl chloride, 3,5-difluorophenylcarbamoyl chloride, 4-difluorophenylcarbamoyl chloride,
2, 4. , 6-dolichlorophenylcarbamoyl chloridemoyl chloride, 2-chloro-4-fluorophenylcarbamoyl chloride, 2-fluoro-4-chlorophenylcarbamoyl chloride, 2-chloro-4-bromophenylcarbamoyl chloride, 2-chloro-4-iodo Phenylcarbamoyl chloride, 3,5-dichloro-4-
Fluorophenylcarbamoyl chloride, 3,5-dichloro-4-bromophenylcarbamoyl chloride 4-dichloro-6-fluorophenylcarbamoyl chloride,
O, m or p-methylphenylcarbamoyl chloride,
0, m or p ~ isopropylphenylcarbamoyl chloride 5-methylphenylcarbamoyl chloride, 2-fluoro-5-methylphenylcarbamoyl chloride chloride phenylcarbamoyl chloride 0-5 ~ methylphenylcarbamoyl chloride, O, m
or p-methoxyphenylcarbamoyl chloride, 0,
m or p-■toxyphenyl rubbermoyl chloride, o
, m or pt-butoxyphenylcarbamoyl chloride, 2-chloro-5-methoxyphenylcarbamoyl chloride, 2-fluoro-5-methoxyphenylcarbamoyl chloride, 4-chloro-5-methoxyphenylcarbamoyl chloride, 2, 4-dichloro-5isopropoxyphenylcarbamoyl chloride, 2,4-dichloro-
5-methoxyphenylcarbamoyl chloride, 2.4-
Dichloro-5-ethylhexyphenylcarbamoyl chloride, 2,4-difluoro-5-isopropoxyphenylcarbamoyl chloride, phenylcarbamoyl chloride, 2-fluoro-4-chloro-5- Ethoxyphenylcarbamoyl chloride Propoxyphenylcarbamoyl chloride, 2-fluoro-4-chloro-5-t-butoxyphenylcarbamoyl chloride, 2-chloro-4-fluoro-5-methoxyphenylcarbamoyl chloride, 2-fluoro-4-bromo-5 -isopropoxyphenylcarbamoyl chloride, 0, m or p-nitrophenylcarbamoyl chloride, 2-chloro-4-nitrophenylcarbamoyl chloride, 2-fluoro-4-nitrophenylcarbamoyl chloride, 2-nitro-4-fluorophenylcarbamoyl chloride Lophenylcarbamoyl chloride, 0, m or pt-
Lifluoromethylphenylcarbamoyl chloride, O, m or p-(chloromethyl)phenylcarbamoyl chloride, O, m or p-
(bromomethyl)phenylcarbamoyl chloride, 2-
Chloro-5-trinorolomethylphenylcarbamoyl chloride, 2-fluoro-5-trifluoromethylphenylcarbamoyl chloride, methylphenylcarbamoyl chloride, 2-nitro-4
-Trifluoromethylphenylcarbamoylchloridrophenylcarbamoyl chloride, 2-nitro-4-trifluoromethyl-5-methoxyphenylcarbamoyl chloride, 3,5-dichloro-4-nitrophenylcarbamoyl chloride, 2-nitro-5-methylphenyl Substituted phenylcarbamoyl chloride such as carbamoyl chloride, 2-trifluoromethyl-rubamoyl chloride, 3,5-bis(]-lifluoromethyl)phenylcarbamoyl chloride can be used. Furthermore, the 2-hydroxycarboxylic acid ester represented by the general formula (IV) can be easily produced from inexpensive commercially available raw materials.
-Methyl hydroxy-3-methyl-3-butenoate, 2-
Methyl hydroxyate-3-methyl pentenoate, 2-
Methyl hydroxy-3-ethyl-3-butenoate, methyl 2-hydroxy-3-ethyl-3-pentenoate, methyl 2-hydroxy-3-butyl-3-butenoate, 2-hydroxy-3-methyl- Methyl 3-heptenoate, Methyl 2-hydroxy-3-methyl-3-nonenoate, Methyl 2-hydroxy-3-hexyl-3-butenoate, Methyl 2-hydroxy-3-(1'-cyclopentenyl)acetate ,
2-Hydroxy-3-(1'-cyclohexenyl)methyl acetate, 2-hydroxy-3-(1'-cyclohebutenyl)methyl acetate, 2-bitroxy-3-(
1'-cyclododecenyl)acetic acid, 2-hydroxy-3-
Methyl butyl-3-pentenoate, methyl 2-hydroxy-3-ethyl-3-heptenoate, 2-hydroxy-3
-Methyl pentyl-3-octenoate, 2-hydroxy-
Methyl 3-phenyl-3-butenoate, 2-hydroxy-
Methyl 3-phenyl-3-pentenoate, Methyl 2-hydroxy-3-phenyl-3-hexenoate, Methyl 2-hydroxy-3-(4'-chlorophenyl)-3-butenoate, 2-hydroxy-3-( Methyl 4'-fluorophenyl)-3-butenoate, 2-hydroxy-3-(4
Methyl '-bromophenyl)-3-butenoate, 2-hydroxy-3-(3').

Methyl 4'-dimethoxyphenyl)-3-butenoate, 2
-Hydroxy-3-(3',4'-dichlorophenyl)-3-butenoic acid methyl, 2-hydroxy-3-
Methyl (4'-methylphenyl)-3-butenoate, 2-
Hydroxy-3-(4'-chlorophenyl)-3-
Methyl pentenoate, 2-hydroxy-5-(4'-fluorophenyl)-3=methyl pentenoate, 2-hydroxy-3-(3').

Methyl 5'-dichloro)-3-butenoate and lower alkyl esters thereof such as ethyl ester, isopropyl ester, isobutyl ester, and t-butyl ester can be used. The reaction is expressed by the general formula (
The compound of 1) and the compound of general formula (IV) in an organic solvent,
The compound of general formula (n) can be produced by conducting the reaction at room temperature to continuous flow temperature, optionally in the presence of a base (see Reference Examples 1 to 3 below).

As the carbamic acid and ester represented by the general formula (I), for example, 2-(N-phenylcarbamoyloxy)-
Methyl 3-methyl-3-butenoate, ethyl 2-(N-phenylcarbamoyloxy)-3-methyl-3-butenoate, 2-(N-phenylcarbamoyloxy)-3-methyl to 3-butene isobutyl acid, 2- (N-(2'-
Chlorophenyl)carbamoyloxy)-3-methyl-3
-Methyl butenoate, 2-(N-(2'-fluorophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(3'-fluorophenyl)carbamoyloxy)-3-methyl-3 -Methyl butenoate, 2- (N-(2'-bromophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-
(N-(4'-chlorophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-
(4'-fluorophenyl)carbamoyloxy)-
Methyl 3-methyl-3-butenoate, 2-(N-(4'
-bromophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(2',4'
-dichlorophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(2',5
'-dichlorophenyl)carbamoyloxy)-3-
Methyl-3-butenoate, 2-(N-(3',
4'-dichlorophenyl)carbamoyloxy)-3
-Methyl-3-butenoate, 2- (N-(3'
, 5'-dichlorophenyl)carbamoyloxy)-
Methyl 3-methyl-3-butenoate, 2- (N-(2'
.

4'-difluorophenyl)carbamoyloxy)-3
-Methyl-3-butenoate, 2-(N-(2',
4'-dibromophenyl)carbamoyloxy)-3
-Methyl-3-butenoate, 2- (N-(2'
-chloro-4'-fluorophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(
N-(2'-bromo-4'-fluorophenyl) force! Methyl 2-(N-(2'-bromo-4'-chlorophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(2',4',6'-trichlorophenyl)carbamoyloxy)-3-methyl-3
-methyl butenoate, 2- (N-(2', 4', 6
'-trifluorophenyl)carbamoyloxy)-
Methyl 3-methyl-3-butenoate, 2-(N-(2'
, 4', 6'-tribromophenyl)carbamyloxy)-3-methyl-3-butenoate, 2-(
Methyl N-(3',5'-dichloro-4'-fluorophenylthyl-3-butenoate, 2-(N-(3')
-chloro-4'-methylphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N- (
Methyl 3'-fluoro-4'-methylphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-
(N-(4'-methylphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N
- (4'-ethylphenyl)carbamoyloxy)
-Methyl-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-(4'-trifluoromethylphenylcy)-3-methyl-3-butenoic acid methyl, 2-(N-
Methyl (3',5'-his(trifluoromethyl)phenyl)carbamoyloxy]-3-methyl-3-butenoate, 2-(N-(2'-chloromethylphenyl)carbamoyloxy)-3-methyl-3- Methyl butenoate, 2-(N-(4'-bromomethylphenyl 3-methyl-3-butenoate, 2-(N-(2'-
(nitrophenyl)carbamoyloxy)-3-methyl-3
-Methyl butenoate, 2-(N-(3'-nitrophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(4'-nitrophenyl)carbamoyloxy)-3-methyl -Methyl butenoate, 2-(N
-(2',4'-dinitrophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(
Methyl N-(3',5'-dinitrophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-
(N-(2'methoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-
(4'-Me[-xyphenyl)carbamoyloxy)
-Methyl-3-methyl-3-butenoate, 2- (N- (
Methyl 2'-chloro-5'-trifluoromethylphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(2'-trifluoromethyl-41-bromophenyl)carbamoyloxy)-3-
Methyl-3-butenoate, 2-(N- (3'
-methyl trifluoromethyl-4'-fluorophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2
-(N-(2'-chloro-4'-nitrophenyl)carbamoyloxy)-methyl-3-methyl-3-butenoate, 2-(N-(2'-chloro-5'-methoxyphenyl)carbamoyloxy)- 3-methyl-3-
Methyl butenoate, 2-(N-(3'-nitro-
4'-Methylphenyl)carbamoyloxy)=methyl 3-methyl-3-butenoate, 2-(N-(4'-nitro2'-trifluoromethylphenyl)carbamoyloxy)-3-methyl-3-butenoate , 2- (N
- Methyl (2'-nitro4'-trifluorophenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(4'-nitro3'-trifluoromethylphenyl)methyl 3-butenoate , 2- (N- (3'-Me1
~methyl xy-5'-trifluoromethylphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-
(N-(2'-methoxy-5'-nitrophenyl)carbamoyloxy)-methyl-3-methyl-3-butenoate, 2-(N-(2',4'-dichloro-5-methoxyphenyl)carbamoyloxy)- Methyl 3-methyl-3-butenoate, 2-(N-(4'-chloro-2'-fluoro-5-methoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2
- (N- (4'-bromo-2'-fluoro-
Methyl 5-ethoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(2',4
'-Dichloro-5'-methoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(
Ethyl N-(2',4'-dichloro-5'-ethoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(2',4'-dichloro-5-isopropoxyphenyl) Isobutyl carbamoyloxy)-3-methyl-3-butenoate, 2-(
Methyl N-(2',4'-dichloro-5'-t-butoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(2').

4'-dichloro-5'-hexyloxyphenyl)
Isobutylcarbamoyloxy)-3-methyl-3-butenoate, 2-(N-(4'-chloro-2'-fluoro-5'-methoxyphenyl)carbamoyloxy)-3
-Methyl-3-butenoate, 2- (N- (4'
-ethyl-chloro-2'-fluoro-5'-ethoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(4'-chloro-2'-fluoro-5'-isopropoxyphenyl) Methyl carbamoyloxy)-3-methyl-3-butenoate, 2-(N
- (4'-chloro-2'-fluoro-5' -
Isobutyl (isopropoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2- (N- (4'
-chloro-2'-fluoro-5' -t-butoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2- (N-(4'-chloro-2'
-Fluoro-5'-isobutoxyphenyl)carbamoyloxy)-3-methyl-3-methylpentenoate, 2
- (N-(4'-chloro-2'-fluoro-5
'-methosylphenyloxy)-3-methyl-3-pentenoate, 2-
(N- (4'-chloro-2'-fluoro-5
2-(N-(4'-chloro-2'-fluoro-5'-isopropoxyphenyl>carbamoyloxy)-3-methyl-3- Methyl pentenoate, 2-(N-(4'-chloro-2'-fluoro-5'-isopropoxyphenyl)carbamoyloxy)-3-octyl-3-isobutyl pentenoate, 2
-(N-(4'-chloro-2'-fluoro-5'
-t-butoxyphenyl)carbamoyloxy)-3-methyl-3-pentenoate, 2- (N-(4'
-chloro-2'-fluoro-5'-methoxyphenyl)carbamoyloxy)-3-ethyl-3-butyrate, 2-(N-(4'-chloro-2'-fluoro-5'-isopropoxyphenyl) Isobutyl carbamoyloxy)-3-ethyl-3-butenoate, 2-
(N- (4'-chloro-2' ~ fluoro-5'
-ethoxyphenyl)carbamoyloxy)-3-ethyl-3-butenoic acid methyl, 2-(N- (4'-chloro-2'-fluoro-5' -isopropoxyphenyl)carbamoyloxy)-3-octyl 3-ethyl-
Methyl 3-fudate, 2-(N-(4.--chloro-2
--Fluoro-5'-isopropoxyphenyl)carbamoyloxy)-3-butenoate, isobutyl, 2-(N'(
4'-chloro-2'-fluoro-5'-t-butoxyphenyl)carbamoyloxy)-3-ethyl-3-
Methyl butenoate, 2-(N- (4'-chloro-3
' -methoxyphenyl〉carbamoyloxy)-methyl-3-methyl-3-butenoate, 2-(N-(4'-ri-3'-methoxyphenyl)carbamoyloxy)
Isobutyl -3-methyl-3-butenoate, 2- (N-
Ethyl (4'-chloro-3'-ethoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate,
2-(N-(4'-chloro-3'-isopropoxyphenyl)carbamoyloxy)-3-methyl-3
-Methyl butenoate, 2- (N- (4'-chloro-3'-isopropoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate, 2- (N
- (4'-chloro-3'-pentyloxyphenyl)carbamoyloxy)-3-methyl-3-butenoic acid isobutyl, 2- (N- (4'-chloro-3'
-hexyloxyphenyl)carbamoyloxy)-3
-isobutyl-methyl-3-butenoate, 2-(N-(4'
-isobutyl-chloro-3'-hebutyloxynonyl)carbamoyloxy)-3-methyl-3-butenoate,
2- (N- (4'-chloro-3'-octylleoxyphenyl)carbamoyloxy)-3-methyl-
Isobutyl 3-butenoate, 2-(N-(4'-chloro-3'-nonyloxynonyl)carbamoyloxy)-3-methyl-3-butyl inbutyl, 2-(N
- (4'-fluoro-3'-methoxyphnyl)
Methyl carbamoyloxy)-3-methyl-3-butenoate, 2-(N-(4'-fluoro-3'-isopropoxyphenyl)carbamoyloxy)-3-methyl-3
-inbutylbutenoate, 2-(N-(4'-fluoro-3'-octyloxyphenyl)carbamoyloxy)-3-methyl-3-butyl ethyl, 2-(
Methyl N-(4'-chloro-3'-isopropoxyphenyl)carbamoyloxy)-3-methyl-3-pentenoate, 2-(N-(4'-chloro3')
-isopropoxyphenyl)carbamoyloxy)-3
-Methyl-3-hexenoate, 2- (N- (4
'-fluoro-3'-isopropoxyphenyl)
Methyl carbamoyloxy)-3-methyl-3-heptenoate, 2- (N- (4'-chloro-3'-isopropoxyphenyl)carbamoyloxy)-3-methyl-3-octenoate, 2- (N- ( 4'-
Methyl chloro-3'-isopropoxyphenyl)carbamoyloxy)-3-octyl-3-butenoate, 2-
(N-(4'-chloro-3'-isopropoxyphenyl)carbamoyloxy)-3-octyl-3-octenoic acid isobutyl, 2-(N-(4'-fluoro-3'-isopropoxyphenyl)carbamoyloxy)- Methyl 3-methyl-3-pentenoate, 2-(N-
Isobutyl (4'-fluoro-3'-isopropoxyphenyl)carbamoyloxy)-3-dodecyl-3-pentenoate, methyl 2- (If (4'-fluorophenyl)carbamoyloxy)-3-methyl-3-pentenoate, Methyl 2-(N-(4'-fluorophenyl)carbamoyloxy)-3-ethyl-3-butenoate, Isobutyl 2-(N-(4'-chlorophenyl)carbamoyloxy)-3-ethyl-3-butenoate,
Methyl 2-(N-(4'-chlorophenyl)carbamoyloxy)-3-methyl-3-pentenoate, 2-(N-
Methyl (4'-bromophenyl)carbamoyloxy)-3-ethyl-3-butenoate, 2-(N-(4'-bromophenyl)carbamoyloxy)-3-methyl-3-pentenoate, 2-(N- Methyl (2',4'-dichlorophenyl)carbamoyloxy)-3-ethyl-3-pentenoate, 2-(N-(4'-chlorophenyl)carbamoyloxy)-2-(1''-cyclohexenyl)methyl acetate, 2 - Methyl (N-(4'-chlorophenyl)carbamoyloxy)-3-methyl-3-heptenoate, 2-(N-(4'-chlorophenyl)carbamoyloxy)-3-butyl-3-butenoate, 2-( Methyl N-(4'-chlorophenyl)carbamoyloxy)-3-methyl-3-nonenoate, 2
- (N-(4'-Rylophenyl)carbamoyloxy)-3-hexyl-3-butenoic acid methyl, 2-(N
-phenylcarbamoyloxy)-3-ethyl-3-methylpentenoate, 2-(N-(3', /l'-dichlorophenyl)carbamoyloxy)-3-phenyl-
Methyl 3-butenoate, 2-(N-(3',4'
-dichlorophenyl)rubamoyloxy)-3-(4″
-chloro-phenyl)-3-butenoic acid methyl, 2- (
N-(3'.

5'-dichlorophenyl)carbamoyloxy)-5-
Methyl (/l″ltwoorophenyl)-3-butenoate,
2- (N-(3',5'-dichlorophenyl)
Carbamoyloxy)-3-(4″-fluorophenyl)
-methyl-3-butenoate, 2-(N-(2'-fluoro-4'-chloro-5'-isopropoxyphenyl)
Carbamoyloxy)-3-(4″-fluorophenyl)
Methyl -3-butenoate, 2-(N-phenylcarbamoyloxy)-3-(4'-chlorophenyl)-3-butenoate, 2-(N-(4'-chlorophenyl)carbamoyloxy)-3-ethyl -methyl 3-pentenoate, 2-(N-(4'-fluorophenyl)rubamoyloxy)-3-methyl-3-methyl pentenoate,
Methyl 2-(N-(4'-fluorophenylbamoyloxy)-3-ethyl-3-butenoate, 2-(N-
(3',5'-dichlorophenyl)carbamoyloxy)-2-(1''-cyclopentenyl)methyl acetate, 2-(N-(2'-fluoro-4'-chloro-51-isopropoxyphenyl)carba[yloxy) -2-(1″-cyclo=49-hexenyl)methyl acetate, 2-(N-(2′).

4'-dichloro-5'-isopropoxyphenyl)
carbamoyloxy)-2-(1”-cyclododecenyl)methyl acetate, 2-(N-(2′-chloro-5
'-Trifluoromethylphenyloxy)-3-methyl-3-pentenoate, 2-
Methyl [N-(2'-chloro-5'-trifluoromethylphenyl)carbamoyloxy)-3-butyl-3-butenoate, 2-(N-(2'-chloro-5
'-Trifluoromethylphenyl)carbamoyloxy)-3-methyl-3-pentenoic acidyl, 2- (N-
Isobutyl (2'-chloro-5'-t-lifluoromethylphenyl)carbamoyloxy)-3-methyl-3-pentenoate, 2-(N-(2'-chloro-5'-
trifluoromethylphenyl)carbamoyloxy)-3
-Butyl-3-butenoic acid isobutyl, 2- (N- (
2'-fluoro-4'-chloro-5'-isopropoxyphenyl)carbamoyloxy)-3-butyl-
Methyl 3-butenoate, 2-(N-(2'-fluoro-4'-isopropoxyphenyl)carpamoyloxy)-3-butyl-isobutyl-3-butenoate, 2-
(N-(2'-fluoro4'-chloro-5'
-isopropoxyphenyl)carbamoyloxy)-3
-Methyl-3-pentenoate, 2-(N-(2'
-fluoro-4'-chloro-5'-isopropoxyphenyl)carbamoyl)-3-methyl-3-pentenoate, isobutyl, 2-(N-(3',5'-
dichlorophenyl)carbamoyloxy) -3-(4'
-Methyl [10benzyl)-3-butenoate, 2-(
N-(3',5'-dichlorophenyl)carbamoyloxy)-3-(4''-fluorobenzyl)-3-butenoic acidyl, 2-(N-(3',5'-dichlorophenyl)carbamoyloxy)-3-( 3", 5"
-dichlorobenzyl)-3-butenoic acid isobutyl, 2
-(N-(3',5'-dichlorophenyl)carbamoyloxy)-3-methyl-4-(4''-dichlorophenyl)-3-butenoate, 2-(N-(3',
5'-dichlorophenyl)carbamate)-3
-Edyl butenoate, 2-(N-(3').

Examples include isobutyl 5'-dichlorophenyl>carbamoyloxy)-3-methyl-4-(3'',5''-dichlorophenyl)-3-butenoate, which can be used as the starting material '4Q1 for the reaction of the present invention.

In addition, when carrying out the reaction of the present invention, the general formula (
By treating the carbamate ester represented by general formula (II) produced by the reaction of compounds III) and (IV) with a base without isolating it from the reaction system,
The desired oxazolidinedione derivative represented by the general formula (I) can be produced.

The organic solvents used in this reaction include aromatic solvents such as benzene, toluene, and quintylene, dioxane,
Examples include ether solvents such as tetrahydrogen 70ran, dimethoxyethane, alcohol solvents such as methanol, ethanol, and isopropyl alcohol, and solvents such as ethyl acetate, dimethylformamide, and dimethyl sulfoxide.

Further, in carrying out the reaction of the present invention, after the reaction is completed, the solvent can be removed from the reaction mixture and the mixture can be purified by fractionation using a silica gel column, etc. However, insoluble solvents,
For example, a pure oxazolidinedione derivative can be easily isolated by adding an alcoholic solvent, cooling if necessary, and separating the precipitated crystals in a furnace.

Among the compounds represented by the general formula (1) of the present invention, the following general formula (I') I? 1 [In the formula, R1, R2, R4 and
(represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group or cycloalkyl group that is the same as)
] is produced by the second method below. That is, the general formula % formula % [wherein R, R, R and R5 are as described above, M
is a hydrogen atom or an alkali metal] and a phenol derivative represented by the general formula % () [wherein R7 is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group or cycloalkyl group,
Y is a leaving group] [In the general formula (V), when M is a hydrogen atom, the reaction is carried out in the presence of a base].

Preferably, the reaction is carried out in an organic solvent. Examples of organic solvents include aliphatic hydrocarbons such as hexane, heptane, and ligroin, aromatic hydrocarbons such as benzene, toluene, and xylene, diethyl ether, diisopropyl ether,
Ethers such as dioxane, tetrabitrofuran, and ethylene glycol dimethyl ether; carbons such as acetone and methyl ethyl ketone; nitrites such as acetonitrile and isobutyronitrile; and amides such as N,N-dimethylformamide. 5A yellow compounds such as , dimethyl sulfoxide, sulfolane, etc., or mixtures thereof can be used.

When M is a hydrogen atom in general formula (V), general formula (V
The base used in the reaction with the compound of
Pyridine, triethylamine, N.

Organic bases such as N-dimethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, sodium acetate,
An alkali metal carboxylic acid salt such as potassium acetate can be used.

In addition, when a chloride, bromide, or sulfonic acid ester is used as the compound represented by the general formula (Vl) in this reaction, the compound may be an iodide such as potassium iodide or sodium iodide, or a compound represented by the formula (Vl). ammonium bromide, benzyltriethylammonium bromide,
Alternatively, the progress of the reaction can be accelerated by adding a quaternary ammonium salt such as iosite, and the compound of the present invention can be obtained in good yield.

After completion of the reaction, the product can be obtained by conventional post-treatment, and if necessary, it can be purified by column chromatography, recrystallization, etc.

In addition, the compound represented by the general formula (Vl) that is a raw material for this reaction is one that is easily available or one that can be easily prepared from commercially available raw materials, such as methylbromide, methyl iosito, edyl bromide, delu iosito, isopropyl bromide, Alkyl halogen compounds such as isopropyl iosito, butyl bromito, butyl iosito, 5eC-butyl bromito, cyclohexyl iosito, cyclohexyl bromide, cyclopentyl bromide, cyclopentyl iosito, cyclopropyl bromide, propargyl chloride, propargyl bromide, propargyl iosito, 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, 1-bromo-2-pentyne,
6-chloro-1-hexyne, 1-bromo-3-pentyne, 3-bromo-1-butyne, 3-chloro-1-butyne,
Acetylene compounds such as 4-bromo-1-butyne, allyl bromide, allyl chloride, methallyl bromide, clodel chloride, crotyl bromide, 1,3-dichloro-1
-Propene, 2,3-dichloro-1-propene, 4-bromo-3-methyl-1-butene, prenylbromide, 3
- Olefin compounds such as bromo-3-methyl-1-butene and 2,3-dibromo-1-butene, ethyl 2-bromoacetate, ethyl 2-chloroacetate, methyl 2-bromopropionate, ethyl 2-bromoacetate, Substituted alkyl halogen compounds such as isopropyl 2-bromoacetate, 2'-ethyl)hexyl 2-bromopropionate, or propargyl alcohol, 1-butyn-3-ol, 3-
Methyl-1-butyn-3-ol, 1-butyn-4-ol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, methyl chloride,
Alcohols such as methyl lactate and common lower aliphatic alcohols such as Nisdel sulfonate, p-toluenesulfonate, and benzenesulfonate ester can be used.

The above general formula (V) which is a raw material for producing the compound of the present invention
The phenol derivative represented by the general formula [wherein R11
, R and R5 have the same meanings as above, and R8 represents a lower alkyl group having 1 to 1 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ] can be easily produced by treating the carbonate ester derivative represented by the formula in a common organic solvent in the presence of a base. (Reference examples 4 to 12 below)
(Reference) Furthermore, in carrying out the reaction of the present invention, the above general formula <
A metal salt of a phenol derivative (when M is an alkali metal in general formula (V)) obtained by treating a compound of By reacting with the compound shown, the 1,3-oxazolidine-2,4-dione derivative represented by the general formula (■') can be produced.

Further, the oxinosilidinedione derivative represented by the general formula <vn> can be produced by the method shown below.

(X) 0 (XI) K) 60 - That is, the nitrobenzene derivative (■) (in the formula, R1 and R2 represent the same meanings as above; R8 represents a lower alkyl group or an aralkyl group) is converted to platinum oxide, platinum - carbon, palladium - reduced in the presence of a catalyst such as carbon,
Aniline derivative (IX) (wherein R1, R2 and R8
has the same meaning as above. ), which can then be easily converted into isocyanate derivative (X) by treatment with phosgene gas or trichloromethyl chloroformate.
(In the formula, R1, R2 and R8 have the same meanings as above.) Next, this isocyanate derivative (X) and β, γ-unsaturated glycolic acid ester (XI) (in the formula, R4 and R5 represent the same meanings as above, and R9 represents a lower alkyl group having 1 to 4 carbon atoms) ), optionally in the presence of a base, to prepare carbamate ester derivatives (XI[>
(In the formula, R1°R2, R4, R5, R8 and R9 have the same meanings as above.)

This carbamate ester derivative is then cyclized using tertiary amines such as triedelamine and tributylamine, inorganic bases such as potassium carbonate and sodium methoxide, or carboxylic acid salts such as sodium acetate as a base. By doing so, an oxazolidinedione derivative (VI[>) can be produced.

Hereinafter, the present invention will be explained in more detail with reference to Examples, Reference Examples, and Experimental Examples. Physical property values and spectral measurements of the compounds synthesized in Examples 1 to 38 are shown in Tables 2 and 3.

Example 1゜Methyl 2-(N-4'-chlorophenyl)carbamoyloxy)-3-methyl-3-butenoate (2,71L
10...mo, f! Triethylamine (1,0m>) was added to a benzene (50d) solution of ) and heated under reflux for 5 hours.The solvent was completely removed under reduced pressure, methanol was added, and the precipitated white crystals (1,879>) were isolated by filtration. From NMR and IR, this product was found to be 3-(4'-
It was confirmed that it was chlorophenyl)-5-isopropylidene-1,3-oxazolidine-2,4-dione.

Example 2゜Cρ 2- (N-(2',4'-dichloro-5'-
Methyl isopropoxyphenyl)carpamoyloxy)-3-methyl-3-butenoate (1,82g, 5.0m
Sodium methoxide (0,1y>) was added to a solution of mo, Q ) in benzene (50d), heated under reflux for 1 hour, and then the solvent was distilled off. Methanol (20d) was added and after cooling, white crystals (1 , 109), which is 3-(2',4'-dichloro-5'-isopropoxyphenyl)-5-isopropylidene-1,3
-Oxazolidine-2,4-dione by NMR
Confirmed from IR.

Example 3゜2-(N-(2'-fluoro-4'-chloro-
5'-isopropoxyphenyl)carbamoyloxy)
Methyl-3-methyl-3-butenoate (1,799゜5
Sodium methoxide (0,1y) was added to a solution of mmo, ll) in toluene (50 mj), and the mixture was heated under reflux for 2 hours.

Then, the solvent was completely distilled off, methanol (20 ml) was added, and after cooling, the precipitated white crystals (0,989) were separated. This product was found to be 3-(2'-
It was confirmed that it was fluoro-4'-chloro-5'-impropoxyphenyl)-5-isopropylidene-1,3-oxazolidine-2,4-dione.

65 Example 4゜Methyl 2-(N-(2',4'-difluorophenyl)carbamoyloxy)-3-methyl-3-butenoate (1,43 g, 5 mmo, I)) in toluene (
Add sodium methoxide (50m!) to the 30ml solution.
J) was added, and the mixture was heated under reflux for 3 hours. The solvent was completely removed under reduced pressure and methanol was added to precipitate white crystals (0
, 76 g) was isolated by filtration. It was confirmed by NMR and IR that this product was 3-(2',4'-difluorophenyl)-5-isopropylidene-1,3-oxazolidine-2,4-dione.

Methyl 2-(N-(4'-fluorophenylmoyloxy)-3-ethyl-3-butenoate and 2-(N-
(2',/!'-dichlorophenyl)carbamoyloxy)-methyl-3-methylpentenoate mixture (
1.40 y, 5 mmo. Q > benzene (30
(3) N-methylmorpholine (0.5 mff) was added to the solution, and the mixture was reacted under heating under reflux for 3 hours. The solvent was completely distilled off, then methanol was added to precipitate white crystals (1.05
9) was isolated. This product was found to be 3- by NMR and IR.
(2',4'-dichlorophenyl)-5-(2
'butylidene)-1,3-oxazolidine-2,/I-
It was confirmed that it was Zeon.

Examples 6-10.

A corresponding oxazolidinedione derivative was synthesized from the following carbamate ester in the same manner as in Example 1.

Example 6: Methyl 2-(N-(4'-bromophenyl)carbamoyloxy)-3-ethyl-3-butenoate and 2-(N-(4'-bromophenyl)carbamoyloxy)-3-methyl-3- Methyl pentenoate Example 7: 2-(N-(2'.4'-dichlorophenyl)carhamoloxy)-3-methyl-3
-Methyl butenoate Example 8: 2-(N-(/l'-fluorophenyl)carbamoyloxy)-3-methyl-3-butenoate Example 9: 2-(N-<II'-chlorophenyl>carbamoyloxy)- Methyl 3-edy-3-butenoate and 2-(N-(4'-chlorophenyl)carbamoyloxy)-3-methyl-3-pentenoate Example 10: 2-(N-(2'-di[・
Example 1
1-14 Corresponding oxazolidinedione derivatives were synthesized from the following carbamate esters in the same manner as in Example 2.

Example 11: 21N-(2',4'-dichlorophenyl)carbamoyloxy)-3-methyl-3
-Methyl butenoate Example 12: 2-(N-(2',4'.

6'-i~lichlorophenyl)carbamoyloxy)-
3-Methyl-3-butemethymedyl Example 13:
21N-(2',4'-dichloro1phenyl)carhamoloxy)-3-ethyl-3-pentenoate Example 14: 2-(N-(/'I'-chlorophenyl)carhamoloxy12-(1'-cyclo Hexenyl) methyl acetate Example 15.

C. l+ 2,4-dichlorophenylisocyanate (4.16
g, 22.2 mmoF) and 2-hydroxy-3~
Methyl medyl-3-butenoate (5.72 9.44
A solution of mmoρ) in benzene (BOme) was reacted under heating under reflux for 2.5 hours. From the NMR and IR spectra 1 to 1 of the reaction mixture, the raw material isocyanate was completely quenched, and the adduct carbamate ester [2-(N
- (2', 711'-dichlorophenyl)carhamyloxy)-3-methyl-3-7 methyl thenate]
Eight people confirmed that it was generated. Next, [・Riumme]・oxide (100 my) was added, and the mixture was heated under reflux for 5 hours. Then, the solvent was distilled off, methanol (2h+j>) was added, and after cooling, the precipitated white crystals (3,3:IJ) were separated by furnace.

This product is 3-(2') based on NMR, IR, etc.

1'-dichlorophenyl)-5-isopropylidene-]
, ]3-oxazolidine-2,4-dio.

Example 16゜2-Fluoro-4-chloro-5-isopropoxyphenylisocyanate (2.30 g, 10 mmo, f!
) and Medel 2-hydroxy-3-methyl-3-butenoate (3.0 g, 23 mmo!J>) in toluene (5
The solution was reacted at 80°C for 3 hours. The IR and 1111-1-N spectra of the reaction mixture showed that isocyane-1 was completely lost and the adduct carbamate ester (2-( It was confirmed that methyl N-2'-fluoro-4'-chloro-5'-isopropoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate] was produced.Then, sodium methoxide (0,
1y> was added, and the mixture was reacted for 5 hours under heating and reflux. The solvent was completely distilled off and the resulting reaction mixture was mixed with methanol (1 (7
After cooling, the precipitated white crystals (1,499) were separated from the furnace.This crystal was identified as 3-(2'-fluoro-4'-chloro-5'-isopropoxyphenyl)-5 by NMR and IRN spectra. -isopropylidene-1,3
-Oxazolidine-2,4-dione was confirmed.

Example 11゜ρO The reaction was carried out in the same manner as in Example 15 except that 3,5-dichlorophenyl isocyanate was used as the isocyanate, and 3 (31,5'-dichlorophenyl)-5-
Isopropylidene-1,3-oxazolidine-2,4-
I got Zeon.

73 Example 18°C The reaction was carried out in the same manner as in Example 15 except that methyl 2-hydroxy-3-ethyl-3-pentenoate was used as the 2-hydroxycarboxylic acid ester.
-dichlorophenyl)-5-(3'-pentylidene)-
1,3-oxazolidine-2,1-dione was obtained.

1 row 19゜phenylisocyanate-1"-(1,199,10mmo
. From the NMR and ■R spectra of the reaction mixture, the raw material isocyanate disappeared, and the adduct carbamate ester (2
-(N~phenyl-rubamoyloxy)-3=methyl-3
-Methyl butenoate] was confirmed to be produced. Then, triethylamine was added and the mixture was allowed to react under benzene reflux for 3 hours. Then, crystals (1.51 g) were obtained from the solvent. This product was confirmed to be 3-phenyl-5-isopropylidene-1°3-oxazolidine-2,4-dione by NMR, IR, etc.

Examples 20 to 26 In the same manner as in Example 15, the corresponding carbamate ester was synthesized from the following aryl isocyanate and 2-hydroxycarboxylic acid ester, and then treated with a base to obtain the desired ox1-nozolidinedione derivative. Synthesized.

Example 20: 2-fluorophenyl isocyanate and methyl 2-hydroxy-3-methyl-3-butenoate Example 20': 4-chlorophenylisocyanate 1
~ and methyl 2-hydroxy-3-methyl-3-heptenoate and methyl 2-hydroxy-3-butyl-3-butenoate Example 21: 4-chlorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-nonenoate and Methyl 2-hydroxy-3-hexyl-3-butenoate Example 22: 3.4-dichlorophenylisocyanate and methyl 2-hydroxy-3-methyl-3-butenoate Example 23; 7T nylisocyanate and 2-hydroxy- Methyl 3-ethyl-3-pentenoate Example 24: 3,4-dichlorophenylisocyanate and methyl 2-hydroxy-3-phenyl-3-butenoate Example 25: 3,4-dichlorophenylisocyanate and 2-hydroxy-5- Methyl (4'-chlorophenyl)-3-butenoate Example 26: Phenyl isocyanate and methyl 2-hydroxy-5-(4'-chlorophenyl)-3-butenoate Example 27-31° Same as Example 19 The desired oxazolidinedione derivative was synthesized by synthesizing the corresponding carbamate ester from the following aryl isocyanate and 2-human oxycarboxylic acid ester and treating it with a base.

Example 27: 4-chlorophenylisocyanate-1
~ and methyl 2-hydroxy-3-ethyl-3-pentenoate Example 28: 4-fluoro7-nylisocyanate and methyl 2-hydroxy-3-methyl-3-butenoate Example 29: 3,5-dichlorophenyl Isocyanate and methyl 2-hydroxy-5-(4'-chlorophenyl)-3-butenoate Example 30: 4-chlorophenyl isocyanate and methyl 2-bitroxy-3-methyl-3-butenoate Example 31: 4-fluorophenyl Isocyanate and methyl 2-hydroxy-3-ethyl-3-pentenoate and methyl 2-hydroxy-3-ethyl-3-butenoate = 78- Example 32°CO 3,5-dichloroaniline (3, 24g, 20mm
N-(3,5-dichloro)I-nyl)carbamoyl chloride prepared from trichloromethyl chloroformate and methyl 2-hydroxy-3-methy,-3-butenoate (1,30 g, 10 mmo, l) Triethylamine (2 m (! )) was added to a benzene (50 m1) solution of
was added and allowed to react at room temperature for 3 hours. The precipitated triethylamine hydrochloride was separated in a furnace to remove the solvent and excess triethylamine. It was confirmed from the NMR and IR spectra of the mixture that methyl 2-(N-(3',5'-dichlorophenyl)carbamoyloxy)-3-methyl-3-butenoate was produced. Next, 1~lium methoxide (50m9) was added and the mixture was reacted under heating under reflux for 3 hours. After the reaction was completed, the solvent was completely distilled off, 0.1 Nji acid was added to the resulting reaction mixture, and the mixture was extracted with ether. After drying, the solvent was completely removed, and then methanol was added to precipitate white crystals (1°803). This one is 3-
It was confirmed that (3' + 5'-dichlorophenyl)-5-isopropylidene-1°3-oxazolidine-2,4-dione was available.

Example 33゜〇-80=4-fluoroaniline (2.22g, 20 mno,
Q) and trichloromethyl chloroformate J:
-(4-Fluorophenyl) To a solution of carbamoyl chloride methyl (1.30 g, 10 mmoj) in benzene (50 ml) was added triethylamine (2 mL) and reacted at room temperature for 3 hours.Then, the reaction mixture was heated under reflux for 3 hours. After the reaction was completed, the solvent was completely distilled off, 0.IN hydrochloric acid was added to the resulting reaction mixture, and the mixture was extracted with ether. After drying, the solvent was completely removed, and then methanol was added and the mixture was cooled to precipitate. A white crystal (1.173) was obtained. Spectra and other data showed that this was the desired 3-(4'-fluorophenyl)-5-isopropylidene-1,3-oxazolidine-2,/I-dione. I confirmed it more.

81 one Example 34.

H3 Same as Example 27 except that a mixture of methyl 2-hydroxy-3-ethyl-3-butenoate and methyl 2-ditroxy-3-methyl-3-pentenoate was used as the 2-hydroxycarboxylic acid ester J. The reaction was carried out in the same manner, and 3-
(4'-Fluorophenyl)-5-isobutylidene-1,3-oxazolidine-2,/1-dione (o.4
1y) was obtained.

Example 35゜n 4-edylaniline (3.63g, 30 mmoF
) and Kurogi Ml to 4-
2-hydroxy-3- to ethyl phenyl isocyanate
Ethyl methyl-3-butenoate (3,69,25mmo,
I! ) in a solvent of benzene (50%) and pyridine (1%
,0rII! The mixture was heated to reflux in the presence of water. After 2 hours, the solvent was completely distilled off, methanol was added to the resulting mixture, and the precipitated white crystals (3.3 g) were isolated by filtration. NMR, IR, etc. showed that this product was 3-( It was confirmed that it was 4'-ethylphenyl>-5-isoprop[1-pyridecy-1,3-oxazolidine-2,7'l-dione.

Example 36゜ρ0 3.5-dichlorophenylisocyanate (1,88g
, 10 mmo, Q) to methyl 2-hydroxy-2-cyclopentenyl acetate (1,95tt, 15 m
After confirming that benzene (reacting in 3(W) solvent and isocyanate by spectroscopy) was added and carbamate ester was produced.
Triethylamine (0.5 ml) was added and the mixture was reacted for 3 hours under refluxing benzene. Completely distill off the solvent etc.
8/L-tanol was added to remove the precipitated white crystals (1.24 g). This product was confirmed to be 3-(3',5'-dichlorophenyl)-5-cyclopentylane-1,3-oxazolidine-2,4-dione from NMR and IR spectra.

Example 37゜ρ0 2-hydroxycarboxylic acid ester is 2-hydroxy-
The reaction was carried out in the same manner as in Example 36, except that methyl 3-ethyl-3-pentenoate was used, and 3-(3',5'-
dichlorophenyl)-5-(3'-pentylidene)-1
, 3-ogizazolidine-2,4-dione was obtained.

Criminal case 38゜2 (N-<2'-chloro-5'-trifluoromethylphenylthyl-3-heptenoate and methyl 3-butyl-3-butenoate (1.97 g, 5 mmO.I))
Potassium-t-butoxide (50#Ig) was added to a toluene (30d) solution of the mixture, and the mixture was reacted under heating under reflux for 2 hours.

After the reaction was completed, the solvent was distilled off, and methanol was added to the resulting mixture, which was then cooled. The precipitated white crystals (0.859) were erased. This substance was confirmed to be 3-(2'-chloro-5'-1helifluoromedylphenyl)-5-isopropylidene-1,3-oxazolidine-2,4-dione from NMR and IR spectra. 8 times.

The starting compounds of Examples 1 to 38 above were replaced with the following Reference Examples 1 to 1.
Manufactured by.

Reference example 1゜2.4-dichloro-5-isopropoxyphenylisocyanate (1,72 g, 7 mmoρ) and methyl 2-hydroxy-3-methyl-3-butenoate (1,04 g,
8 mmo! ! A solution of > in benzene (20 mff) was heated under reflux for 2 hours. By separating and purifying the obtained reaction mixture using a silica gel column, 2-(N-
Methyl (2',4'-dichloro-5'-isopropoxyphenyl)carbamoyloxy)-3-methyl-3-butenoate (0,67ff) was obtained as a colorless and transparent oil.

1H-NMR (CD(J-TMS, pp
m): δ1.37(d, 6H, J=6Hz>,
1.82 (d.

3H, J= 1.5H2), 3.72(S, 3
H>.

4.53 (sept, 1 t1. J =
6Hz), 5. δ7(q, IH, J=
1.5Hz), 5.17(br, s.

11-1>, 5.30 (s, 1H), 7.1
3(br, s.

IH), 7.25 (s, 1H), 7.8
7 (s.

1H).

IR(neat, cm-1>: 3350.17
40.1410.1210°860.

Reference example 2゜N-(2,4-difluorophenyl)carbamoyl chloride (2.58 g, 20 mmoN > benzene (
30d) Methyl 2-hydroxy-3-methyl-3-butenoate (3,0y, 23 mmo, Q) was added to the solution, and then N-methylmorpholine (2,5 mff) was added and reacted at room temperature for 3 hours. After completion of the reaction, water was added to separate the organic layer, and after drying, the solvent was distilled off. The reaction mixture obtained was separated and purified using a silica gel column to obtain 2-(N-(2').

4'-difluorophenyl)carbamoyloxy)-3
-Methyl-3-butenoate (3,99 g) was obtained.

11-1-NMR (CDC, Q3-TMS, I
')r)m): δ1.80(d, 3H>, 3
．． 71 (S, 3H).

5.03 ((1, IH), 5.15 (s,
1H).

5.30 (d, 1H> , 6.78 (
m, 2H>.

7.07 (br, S, IH), 8.03 (
m, IH).

IR(neat, cm-1>: 3350.17
/10.1/130.1220°850.

Reference example 3゜2.4-dichlorophenylisocyanate (3,80g
, 20.2 mmo, O) and methyl 2-human xy-3-methyl-3-butenoate (3,05 L 23.5 mm
2-(N-(2'
,/l'-dichloro]■yl)carbamoyloxy)-3-methyl-3-butenoate (4,02 g) was obtained as a colorless and transparent oil.

1111-1-N (CDC, I! 3-TMS, r
) pm): δ1.85 (d, 3H), 3.7
8(s, 3H).

5.23 (Q, IH> , 5.23 (br,
s, 1H).

5.48 (S, IH), 7.12 (m, 11
-(> 7.35 (m, 2H), 8.13 (d, IH
>.

TR(neat, cm-1>: 3350.17
38.1/120.1215°855°Table 3 Oxazolidinedione - Spectrum measurement results Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (Continued) Table 3 (Continued) Table 3 (Continued) Table 3 (Continued) 1) Compounds marked with an * are oxazolidinedione rings 5
The stereochemistry of the double bond at position 25 is a mixture of cis-trans isomers.

Other manufacturing methods of the present invention will be explained below in Examples 39 to 46.

Example 39 Hydroxyphenyl)-5-isopropylidene-1,3
-oxazolidine-2,4-dione (0,723,2,
5 mmo, lJ) of acetonyl-lyl (30 m1 >
Add sodium carbonate (0.1 JJ) to the solution and add 1
It took a while to react. Then propargyl bromide (0,3
67,3, o mmoρ) was added thereto, and the reaction was further allowed to proceed for 1 hour under rapid flow. Reaction completed Shun 0. The mixture was made weakly acidic by adding IN-hydrochloric acid, extracted with chloroform, dried, and the solvent was distilled off to obtain a pale yellow oil. This product was purified by silica gel column chromatography to obtain pure 3-(2'
-fluoro-4'-chloro-5'-propargyloxyphenyl)-5-isopropylidene-1,3-oxazolidine-2°4-dione was obtained. (Yield 0.539,
Yield 65%) Example 40 3-(2'-fluoro-4'-bromo-5-hydroxyphenyl)-5-(sec-butylidene)-
1,3-oxazolidine-2,4-dione (0,26, 0.82 mmo, f)) in acetonitrile (25
Potassium carbonate (0,119>) was added to the r/If solution and reacted for 1 hour under reflux.Propargyl bromide (0,19,0,83 mmo, c) was then added and reacted 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 (0,249,17%)
I got it.

Example 41 3-(2'-fluoro-4'-chloro-5' ~
hydroxyphenyl)-5-isopropylidene-1,3
-oxazolidine-2,4-dione (0,57q, 2.
0mm0. Q) and potassium carbonate (0,279>) in acetonitrile (30d>) and 1-butyn-3-ol p-toluenesulfonic acid ester (0.5 g, 2.2...
About 20 m3 of benzyltriethylammonium bromide (contacted with mo, ff)] ffi was added, and the mixture was heated under reflux for 15 hours.

After the reaction was completed, ether was added and the solution was washed with 1N hydrochloric acid.
After drying, the solvent was distilled off to obtain a pale brown oil.

By separating and purifying this product by silica gel column chromatography, 3-(2'-fluoro-
4'-chloro-5'-(1''-methylpropargyl)oxyphenyl)-5-isopropylidene-1,3-
Oxazolidine-2,4-dione (0,349, yield 5
0%) was obtained.

Example 42 3-(2',4'-dichloro-5'-hydroxyphenyl)-5-(sec-butylidene)-1°3-oxazolidine-2,4-dione (1,58 g, 5
．． 0mmo, f! Potassium carbonate (0.69 g) was added to a solution of ) in acetonitrile (30 m ), and the mixture was heated under reflux for 2 hours.

Then ethyl 2-pro[propionate (0,939,5
, 1 mmo, lJ) was added and the mixture was roughly refluxed for 1 hour. After the reaction was completed, ether was added to the solution, the mixed solution was washed with 1N hydrochloric acid, and after drying, the solvent was distilled off. By separating and purifying the obtained oil using a silica gel column,
3-(2',4'-dichloro-5'-(1"
-ethoxycarbonylT-thyl)oxyphenyl) -5
-(sec-butylidene)-1゜3-oxazolidine-
2,4-dione (1,51 dione, yield 73%) was obtained.

Example 43 3-(2'-fluoro-4'-chloro-5'-
Hydroxyphenyl)-5-isopropylidene-1.3
-oxazolidine-2,4-dione (2,859,10
mmo, l! > and isopropylioside (3 ml) and potassium carbonate (3.5 g) in acetonitrile (50
m! The solution was heated and rapidly flowed for 3 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, 1N hydrochloric acid was added, and the mixture was extracted with ether.

After drying, the ether was distilled off under reduced pressure, and methanol was added to the resulting oil, which was then cooled.

The precipitated crystals were isolated by filtration. This one is 3-(
2'-fluoro-4'-chloro-5'-isopropoxyphenyl)-5-isopropylidene-1,3-
Oxazolidine-2,4-dione (compound 27) (
3,10y, yield 95%) (Compound 27).

Example 44 3-(2'-fluoro-4'-chloro-5'-
hydroxyphenyl)-5-impropylidene-1,3
-Oxazolidine-2,4-dione (175m5゜0.
Potassium carbonate (4211+9) was added to a solution of 61 mmoj ) in DMF (10 mj), and the mixture was stirred at room temperature for 3 hours.

Then, 2.3-dichloro-1-1-day pen (0.5d) was added and stirred roughly for 1 hour at room temperature. After the reaction was completed, the solvent was 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 and cooled. White crystals precipitated (80 m5,
Yield: 36%) is the target 3-(2'-fluoro-4
'-ri■ro5<2LL-chloroallyl)oxyphenyl)-5-isopropylidene-1,3-oxazolidine-2,4-dione.

-111 Example 45 3~(2'-)゛ruoro4'-chloro-5'-
methoxycarbonyloxyphenyl)-5-isopropylidene-1,3-oxazolidine-2゜4-dione (3
, 43g, 10 mmo, l! > methanol (50
m! 2 CO3 (1.38 g, 10 mm
oJ! ) and heated under reflux for 1 hour. Then, the solvent was completely removed under reduced pressure, and fresh acetonitrile (50I
n! Added more. Furthermore, propargyl bromide (5d)
was added and allowed to react at room temperature for 2 hours. The reaction mixture was prepared in Example 1.
3-(2'-fluoro-
4'-chloro-5'-propargyloxyphenyl)-5-isopropylidene-1,3-oxazolidine-
2,4-dione (0,899, yield 28%) was obtained.

Example 46 Oily (approximately 60%) sodium hydride (5.0 mm 0.l
)) was washed with hexane to remove the solvent, dry tetradidrofuran (10 m) was added, and then 3-(2'-
Fluoro-4'-chloro-5'-hydroxyphenyl)-5-isopropylidene-1゜3-oxazolidine-2,4-dione (1,43 g, 5.0 mmoρ) was added and the mixture was heated at room temperature until hydrogen evolution stopped. Stirred. By removing the solvent, 3-(2'-fluoro-4'
-chloro-5'-sodiumoxyphenyl)-5-
Isopropylidene-1,3-oxazolidine-2,4-
A white solid of dione was obtained. Next, acetonitrile (10 mff) and methyl iodide (1 ml) were added to this mixture, and the mixture was heated and stirred for 3 hours. After the reaction was completed, 0.000 m of hydrochloric acid was added to make it weakly acidic, extracted with chloroform, and after drying, the solvent was distilled off. A pale yellow oil was obtained by evaporation, and by adding a small amount of methanol to this and cooling it, 3-(2'
-fluoro-4'-chloro-5'-methoxyphenyl)-5-isopropylidene-], ]3-oxazolidine-2,4-dio white crystals (1,429, yield 95
%) was obtained.

Compounds 30-56 shown in Table 1 were synthesized according to the methods of Examples 39-46. The physical properties and spectral measurements of the obtained compound are shown in Tables 4 and 5.

The production of the starting compounds used in Examples 39 to 46 will be explained below using Reference Examples 4 to 11.

3-(2′) synthesized by the method shown in Reference Example 12 below
-fluoro-4'-chloro-5'-methoxycarbonyloxyphenyl)-5-isoglopylideneco,
3-oxazolidine-2,4-dione (3,/149.
10 mmo, Q) of dry methanol (100 mN”
) solution with potassium carbonate (1,38y, 10 mmoN
) was added and 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 crude oil was purified by column chromatography to obtain pure 3-(2'-fluoro-
4'-chloro-5'-didroxyphenyl)-5-
Isopropylidene-1゜3-oxazolidine-2,4-
Zeon (1,609>) is wearing a helmet.

= 115 − + 1−1−NMl−1−N, f! 3. Ding MS, p
pm> :δ2.06(3H,S),
2.29 (3t1.S), 5.
78 (117 br s), 6.98
(1t1.d), 7.25(d,1H
>.

IR (KBr disk, cm”>: 3425
．． 1820.1738゜1685゜M, P,: 133-135゜C8 Reference Example 5 Same as the method shown in Reference Examples 6, 9゜10 and 4 using 2.4-dichloro-5-methoxycarbonyloxynitrobenzene as a raw material. 3-(2',
4'-dichloro-5'-methoxycarbonyloxyphenyl)-5-isopropylidene-1,3-o,xazolidine-2,4-dione (3,6057, lo m
Potassium carbonate (0,699,5 mmo, Q
) was added and refluxed for 2 hours. By treating in the same manner as in Reference Example 1, 3-(2',/I'-dichloro-5
'-Hydroxyphenyl)-5-isopropylidene-1
,3-oxazolidine-2,4-dione (1,729)
I got it.

1-NMR (CDCρ, TMS, I
) concave): δ2.03 (3H,s > , , 2.
27 (3t(,S), 6.90(1H,
s>, 7.48 (IH, s>.

IR (KBr disk, cm-1): 340
0.1B20.1739°1690°M, P: 1B6-168°C6 Reference Example 6 2-Fluoro-4-chloro-5-methoxycarbonyloxynitrobenzene (52,19,0,2/1mO, [
! ) in ethanol (600 d> solution of platinum dioxide (1
, 53) was added and the reaction was allowed to proceed at room temperature under a hydrogen cloud at normal pressure until the absorption of hydrogen gas stopped. After the reaction was completed, the catalyst was separated, and the solvent was distilled off from the resulting pale yellow transparent solution under reduced pressure.
A deep brown oil was obtained. This product was confirmed by NMR spectrum to be substantially pure 2-fluoro-4-chloro-5-methoxycarbonyloxyaniline. This product can be purified by silica gel column chromatography and used as it is in the next reaction.

11-I-NMR (CDCN 3. TMS, pp
m): δ3.8B(3H,s>, 4.13(2H
, br s).

6.48 (IH, d, JHF-811Z),
6.92 (IH.

d, Jll [=10H2).

-11R- Reference Example 7 Platinum dioxide (1, Og) was added to a solution of 2-fluoro-4-bromo-5-methoxycarbonyloxynitrobenzene (30,49,0,1 mOρ) in ethanol (300d), and under a hydrogen atmosphere, The mixture was stirred until hydrogen absorption stopped. After the reaction, the catalyst was separated and the solvent was distilled off from the solution under reduced pressure to obtain a brown solid of 2-fluoro-4-bromo-5-methoxycarbonyloxyaniline (28, 0
g) is 1q.

1 Tol-NMR (CCU-, TMS, ppm
): δ3.83(3H,s>, 5.01 (2
H, br s).

6.63 (1H, d, JH, -7,6H2),
7.06 (IH, d, Jl = 9.8Hz).

-11Q = Reference Example 8 Trichloromethyl chloroformate (15rd,
A 2-fluoro-4-bromo-5-methoxycarbonyloxyaniline solution synthesized by the method shown in Reference Example 4 was added dropwise thereto over 20 minutes. After the dropwise addition was completed, the mixture was heated to 80°C and ethyl acetate was distilled off. Carbon chloride (150d) after cooling
2-fluoro-4-bromo-5-methoxycarbonyloxyphenyl isocyanate (29.1 g
A brown solid was obtained (yield 94%).

+1J' l-1-NMR (CC.G, TMS, p
pm): δ3, 87(31-1, s>, 6.89(
IH, d, JHF=6,8 Hz), 7.31
(IH.d, JIIF=8.6 Hz).

IR (KBr disk, cm”): 226
0. 1770.

Reference Example 9 The method shown in Reference Example 3 was performed using 2-fluoro-4-chloro-5-methoxycarbonyloxyaniline (21.9 g, 10 mmoρ) and trichloromethyl chloroformate (lht') in the same manner as in Reference Example 7. 2-fluoro-4-chloro-5-methoxycarbonyloxyphenyl isocyanate (20.69, yield 84%) synthesized by
) was obtained.

1T I NMR (CDC.l! 3, T
MS, ppm): δ3, a8 (3H,S),
6.97 (IH, d).

7, 37 (IH, d).

IR (K Br disk, cm”>: 226
0.1770° Reference Example 10 2-Fluoro-4-chloro-5'-methoxycarbonyloxyphenylisocyanate (2,459,1 mmo, l!) synthesized by the method shown in Reference Examples 6 and 9.
) and ethyl 2-hydroxy-3-methyl-3-butenoate (1,44 g, 10 mno, l!) in benzene (
50d> A catalytic amount of triethylamine was added to the solution and stirred at room temperature for 0.5 hour. After the reaction was completed, the solution was washed with 1N hydrochloric acid, and the organic layer was dried and concentrated under reduced pressure. The resulting pale yellow oil was separated and purified using a silica gel column to obtain N-(2-fluoro-4-chloro-5-methoxycarbonyloxyphenyllbonyl) methallyl ester (yield: 85%).

11-(-NMR (CD(j!3, TMS
．． ppm): 61, 29 (3H, t>,
1.84 (3H, brs).

3, 93 (3H, S), 4.24 (2H. q)
, 5.14 (1 H, m) , 5.23 (I
H, m), 5.45 (IH, s), 7.20 (I
H. d), 7.0-7, 35 (1H, br s),
8.10 (IH, d).

Reference Example 11 2-Fluoro-4-bromo-5-methoxycarponyloxyphenylisocyanate-1 (2.74 g, 9,5 mmo.I) synthesized by the method shown in Reference Examples 7 and 8
! ) and a small excess of methyl 2-hydroxy-3-methyl-3-pentenoate were heated and flowed rapidly in benzene (50 m> solvent for 1 hour. The reaction mixture was washed with 1N hydrochloric acid, and after drying, the solvent was distilled off. The obtained oil was separated and purified using a silica gel column to obtain N-(2'-fluoro-4-bromo-5-methoxycarbonyloxyphenyl (1' - methoxycarbonyl-2'-methyl-2'
-butenyl ester (2.47 g, yield 57%) was obtained.

1H-NMR (CC.tl4, TMS,
ppm): δ1, 6γ(3H, S), 1.70(
31-(, d), 3.70(31-(, S),
3.87 (3H.S), 5.27<1 day, s
> , 5.68 (1 F-1. m), r. .

(1'l-f, brs), 7.27(1f-(,
d), 8.03 (1 day, d).

Reference Example 12 “N synthesized by the method shown in Reference Examples 6, 9 and 10
A solution of -(2-fluoro-4-chloro-5-methoxycarbonyloxyphenyl)carbamic acid (1'-ethoxycarbonyl) (1.95 g, 5.0 mmon) in benzene (
Add a catalytic amount of sodium acetate to 20InR) and add 12FR
It refluxed for a while.

After the reaction was completed, the solution was washed with 1N hydrochloric acid, dried, and the solvent was distilled off. The obtained oil was purified using a silica gel column to obtain 3-(2'-fluoro-4'-
[10-5'-methoxycarbonyloxyphenyl)-5-impropylidene-1,3-oxazolidine-
2,4-dione (1,273, yield 74%) was obtained.

1-NMR (CDC, Q 3 , -rM
s, pl)m) : δ2.05(3H,S)
, 2.28(3H,S), 3.95(3H,s>
, 7.32 (d, 11-() , 7.42(
1 to 1. d).

Table 5 'I-l-1-N spectra 1 to 1 of 1,3-oxazolidine-2,7I-dione derivatives
Table 5 (continued) Table 5 (continued) Table 5 (continued) Table 5 (continued) Table 5 (continued) Table 5 (continued) 1) Compounds marked with an * are oxazolidine sions The stereochemistry of the double bond at position 5 of the ring is a mixture of cis-trans isomers.

-136 The compound of the present invention obtained as shown in Example 1 is
As mentioned above, it has excellent performance as a herbicide.

When using the compound of the present invention 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 types of adjuvants. Usually, the adjuvants are formulated with various carriers, fillers, solvents, surfactants, stabilizers, etc. in the form of wettable powders, emulsions, powders, granules, etc., using conventional methods. preferable.

Examples of solvents that are one of the adjuvants in herbicides using the compounds 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 or a mixture of two or more of these may be used.

In addition, as fillers, mineral powders such as clays such as kaolin and bentonite, talcs such as talc and pyrophyllite, diatomaceous earth, oxides such as white carbon, soybean powder, and C
Vegetable powders such as MC are preferred, and one or a mixture of two or more of these is used.

Additionally, surfactants may be used as spreading agents, dispersants, emulsifiers, and penetrants. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

These surfactants are used singly or as a mixture of two or more depending on the purpose.

Preferred methods of using the herbicide using the compound of the present invention include soil treatment, water surface treatment, foliage treatment, etc. Particularly excellent effects can be achieved by application before the germination of weeds to be controlled or when the weeds are young.

In addition, the herbicide using the compound of the present invention may be used in combination with other active ingredients that do not inhibit the herbicidal activity of the active ingredient, such as other herbicides, insecticides, fungicides, plant growth regulators, etc. It is also possible to use them together.

Next, the present invention will be explained in more detail by giving formulation examples of herbicides using the compounds of the present invention and test examples of the herbicidal effects of the herbicides, but the present invention is limited to those illustrated in these specific examples. It is not something that will be done. Note that parts indicate parts by weight.

Formulation Example 1 (Emulsion) 20 parts of the compound of the present invention, 75 parts of xylene, 90 parts of Tsurpol
5 parts of 0△ (manufactured by Toho Chemical Co., Ltd.) were mixed uniformly to form an emulsion.

Formulation example 2 (hydrating powder) 50 parts of the compound of the present invention, 125 parts of diatom, 22 parts of clay,
A mixture of 3 parts of Lunox R100C (manufactured by Toho Chemical Co., Ltd.) was evenly mixed and ground to obtain a wettable powder.

Formulation example 3 (granules) 5 parts of the compound of the present invention, 35 parts of bentonite, 55 parts of talc
5 parts of sodium ligninsulfonate) was uniformly mixed and pulverized, water was added and kneaded, and the mixture was made into granules using an extrusion granulator, followed by drying and sizing to form granules.

Test Example 1 (Efficacy against paddy field weeds) A Wagner pot with a size of 1/5000 are filled with paddy soil, and this was filled with seeds of Japanese barnyard grass,] Nagi, Jimemimisohagi, and rice seedlings at the 3rd to 4th leaf stage (variety: Ni Nihonbare). ) 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 was 50.25 per area.
．． 20°10, 12.5.5S? A predetermined amount was treated on the water surface so that

Thirty days after the granule treatment, the herbicidal effect on the test plants and the chemical damage to rice were investigated using the following criteria, and the results shown in Table 6 were obtained.

Judgment criteria Grass killing rate: Maximum percentage of remaining grass (%) O: 81~io.

1: 61-80 2: 41-60 3: 21-40 4: 6-20 5: O-5 Medicinal damage: Growth rate 1-0+: Toyoi++: Kosho+++: Nakayoshi 10++10: Quality book ×: Death Table 6 -14,2- Table 6 Table 6 (Continued) Table 6 (Continued) Table 6 (Continued) Table 6 (Continued) -14,7- Table 6 (Continued) Table 6 (Continued) Table 6 (Continued) Test Example 2 A Wagner pot with a size of 1/5,000 ares was filled with field soil, and the weeds such as crabgrass, knotweed, and dogfish were grown, and the crops were corn, cotton, or soybean. Seeds were sown and covered with 1 cm of soil.

The next day, the diluted solution of the hydrating powder shown in Formulation Example 2 was prepared with an active ingredient of 50.25.20.10.12.5.5.
Spread it evenly on the covered soil so that it becomes 9, and 20 days after treatment,
The herbicidal effect and phytotoxicity were investigated in the same manner as in Test Example 1. The results are shown in Table 7.

Table 7 Table 7 (continued) Table 7 (continued) Table 7 Effects of field soil treatment Table 7 (continued) Table 7 (continued) Table 7 (continued) Table 7 (continued) ) Table 7 (Continued) Test Example 3 (Effects of foliage treatment) Fill a Wagner pot with a size of 1/5000 are filled with field soil, and add weeds such as barnyard grass, crabgrass, knotweed, dogweed, and white grass. was sown, and after 20 days, a chemical solution of a predetermined concentration of each test compound prepared in the emulsion shown in Formulation Example 1 diluted with water was applied to the stems and leaves of the weeds that had grown. The test plants were uniformly sprayed with a water amount of /10a. 20 days after treatment, the nail herbicidal effect and phytotoxicity (on wheat, soybeans, and corn) were evaluated in the same manner as in Test Example 1. The results are shown in Table 8.

-111, R- Table 8 Table 8 Table 8 Table 8 (continued) Table 8 (continued) Table 8 (continued) Table 8 (continued) Table 8 (continued) Table 8 (continued) Procedural amendment (method) January 1, 1986 Patent Application No. 9'11 2LI-l Flo No. 3,
Relationship with the case of the person making the amendment Applicant Address Name Qlr III =t A t#]
Omi + Oihi ψ 70,000′ Seritake 4, agent

Claims (11)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, 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; R^4 and R^5 are each independently a hydrogen atom, an alkyl group, an aryl group, or R^4 and R^5 taken together can form a polymethylene chain; the above alkyl group, alkoxy group, alkenyloxy group,
An oxazolidinedione derivative represented by an alkynyloxy group, a cycloalkyloxy group, or an aryl group may be substituted. (2) R^1, R^2 and R^3 are each independently a hydrogen atom; a halogen atom, a nitro group; a straight or branched alkyl group having 1 to 8 carbon atoms [with one or more halogen atoms; The 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 are independently hydrogen atoms;
Straight chain or branched alkyl group having 1 to 8 carbon atoms; 6 carbon atoms
~10 aryl groups (optionally substituted with 1 or 2 or more halogen atoms); or R^4 and R^5 taken together are a linear or branched polymethylene group having 3 to 10 carbon atoms The oxazolidinedione derivative according to claim 1 or 2, characterized in that: (4) R^1, R^2 and R^3 are each independently a hydrogen atom; a halogen atom; an alkyloxy group having 1 to 8 carbon atoms which may be substituted with an alkyloxycarbonyl having 2 to 18 carbon atoms; ; C1-C5 alkyl group or C3-8 cycloalkyl group optionally substituted with a halogen atom; C2-8 straight chain optionally substituted with one or more halogen atoms or a branched alkenyl group; an oxazolidine according to claim 1, which is a straight or branched alkynyl group having 2 to 8 carbon atoms and optionally substituted with one or more halogen atoms. Dione derivative. (5) The compound according to claim 1 or 4, wherein R^4 and R^5 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. Oxazolidinedione derivative. (6) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, 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, alkenyloxy group, alkynyloxy group or cycloalkyloxy group; R^4 and R^
5 can be independently a hydrogen atom, an alkyl group, an aryl group, or R^4 and R^5 can be combined to form a polymethylene chain; R^6 is an alkyl group; the above alkyl group, alkoxy group, alkenyloxy group,
There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ ( I ') [In the formula, R^1, R^2, R^3, R^4 and R^5
is as described above]. (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) Claim 6, characterized in that 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. or the method described in paragraph 7. (9) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, 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; R^4 and R^5 are each independently a hydrogen atom, an alkyl group, an aryl group, or R^4 and R^5 together 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 the general formula R^7-Y [wherein R^7 is is a substituted or unsubstituted linear or branched alkyl group, alkenyl group, or alkynyl group, or a substituted or unsubstituted cycloalkyl group, and Y is a leaving group. In the case of hydrogen atoms, the reaction is carried out in the presence of a base] General formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I ′) [In the formula, R^1, R^2, R^4 , R^5 is 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) When M in the above general formula is a hydrogen atom, the base used is an organic tertiary amine; an aromatic amine; an alkali metal alkoxide; an alkali metal hydride; an alkali metal oxide; or a basic inorganic salt. The method according to claim 9 or 10, characterized in that: