MXPA95000115A - Derivatives of 1,3-oxazin-4-ona and herbicides that contains them - Google Patents

Abstract

The present invention relates to a 1,3-oxazin-4-one derivative represented by the formula (I): wherein R 1 represents a phenyl group which can be substituted, R 2 represents a hydrogen atom or a lower alkyl group; R3 represents a hydrogen atom, a lower alkyl group, an aralkyl group, R4 and R5 each independently represent a lower alkyl group, and W represents an oxygen atom or a group represented by the formula -N (R6) - in which R6 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group,

Description

"DERIVATIVES OF 1, 3-OXAZIN-4-ONA AND HERBICIDES THAT CONTAIN THEM" Inventors: TAKAKO AOKI, Japanese, domiciled in 9-16 Nishine Minami, 2-Chome, Tsuchiura, Ibaraki 300, Japan; KOUICHI ARAKI, Japanese, domiciled at 11-3 Chuo, 1-Chome Ami Ibaraki 300-03, Japan; ATSUSHI GO, Japanese, domiciled in 1977-7 Osakacho, Ushiku, Ibaraki 300-11, Japan; KEIICHI HAYASHIZAKI, Japanese, domiciled at 3-11 Chuo, 8-Chome, Ami, Ibaraki 300-03, Japan; RIKA HIGURASHI, Japanese, domiciled in 1987-1 Kitahatori, Narita, Chiba 286, Japan; HIDESHI MUKAIDA, Japanese, domiciled at 25-74 Goshogaoka, 5-Chome, Moriya, Ibaraki 302-01, Japan; TETSUYA MURATA, Japanese, domiciled in 3-12 Chuo 8-Chome, Ami Ibaraki 300-03, Japan; NORISHIGE TOSHIMA, Japanese, domiciled at 11-5 Chuo 1-Chome, Ami, Ibaraki 300-03, Japan and YOSHIHIRO USUI, Japanese, domiciled at 14-6 Nagayama 6-Chome, Ryugasaki, Ibaraki 301, Japan.

Cause holder: RHONE-POULENC AGROCHIMIE, French company, registered at 14/20 Rue Pierre Baizet, 69009 Lyon, France BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a new derivative of 1, 3-oxazin-4-one, to a herbicide that contains it and to a new intermediate compound to prepare it. 2. Description of Related Art Certain types of l, 3-oxazin-4-one derivatives, such as 6-methyl-3- (l-methyl-l-phenylethyl) -5-phenyl-2,3-dihydro-4H-i , 3-oxazin-4-one and its herbicidal activities are described, for example, in WO 093/15064. However, the compounds described in the aforementioned international publication differ from the compound of this invention since none of them has an acidic amide substituent in the 3-position of a 1,3-oxazine ring. In addition, the herbicidal activities and the selective toxicities of the known compounds have not been satisfactory.

SUMMARY OF THE INVENTION The authors of the present invention have seriously studied a variety of 1,3-oxazin-4-one derivatives by sintering them and examining their physiological activities. As a result, the authors of the present invention found a novel 1,3-oxazin-4-one derivative having a markedly selective herbicidal activity and exhibiting excellent herbicidal activity for various weeds at very small dosages without providing phytotoxicity to the useful crops. . Thus, the present invention has arisen. According to the present invention, there is provided a 1,3-oxazin-4-one derivative represented by the following general formula (I): (i) wherein R1 represents a phenyl group which may be substituted; Ra represents a hydrogen atom or a lower alkyl group; Rs represents a hydrogen atom, a lower alkyl, an aralkyl group or a phenyl group which may be substituted; R * and R * each independently represent a lower alkyl group, W represents an oxygen atom or a group represented by the formula -N (RS) - wherein R * represents a hydrogen atom, a lower alkyl group , a lower alkenyl group or a lower alkynyl group; a herbicide that contains it; and N-methylene amino acid ester derivative of an intermediate compound for preparing it, which is represented by the following formula (II): (II) wherein R * and R * each independently represents a lower alkyl group; R10 represents a lower alkyl group or an aralkyl group.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The 1,3-oxazin-4-one derivative and the intermediate compound for preparing it according to the present invention represented by the general formula (I) and (II), respectively, are described in detail below . Atoms and groups of the compounds represented in the general formulas (I) and (II) represented by Rx, R2, R1, R4, R5, R "and R1Q defined as described above are illustrated as follows: Phenyl group which may be substituted A phenyl group or a phenyl group which is substituted with a halogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a phenoxy group, a lower alkylthio group, a lower alkylsulfonyl group, a lower haloalkyl group, a lower haloalkoxy group, a lower alkoxycarbonyl group, a lower alkoxy carbonylalkoxy group , an acyl group, a cyano group or a nitro group. Examples of these groups include a phenyl group, a 2-fluorophenyl group, a 3-chlorophenyl group, a 3-dichloro-4-hydroxyphenyl group, a 3-toluyl group, a 2,5-xylyl group, a 3-group -anisyl, a 3-phenoxyphenyl group, a 3-methylthiophenyl group, a 2-chloro-5- (methylsulfonyl) phenyl group, a 3- (trifluoromethyl) phenyl group, a 3,5-bis (di-fluoromethoxy) phenyl group , a 3-methoxycarbonylphenyl group, a 3- (1-ethoxycarbonyl) ethoxyphenyl group, a 3-nitrophenyl group, a cyanophenyl group, a 3-acetylphenyl group, a 2-chloro-5-nitrophenyl group, a 3,5- group dichlorophenyl, a 2-fluoro-4-chlorophenyl group, a 2,5-dichlorophenyl group, a 3, 5-dichloro-4-methylphenyl group, etc. Halogen atom A fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Lower alkyl group A lower alkyl group having one to six carbon atoms can be straight or branched chain, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tere-butyl group, an n-pentyl group, a neopentyl group, a tert-pentyl group or a hexyl group, etc. Lower anonym group A lower alkenyl group having two to five carbon atoms, such as an allyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-methyl group, 2-butenyl, etc. Lower alkynyl group A lower alkynyl group having two to five carbon atoms, such as a 2-propynyl group, a 1-methyl-2-propynyl group, a 2-butynyl group, a 3-butynyl group, etc. Lower alkoxy group A lower alkoxy group whose alkyl moiety has the same meaning as defined above, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentoxy group, etc. Lower alkylthio group A lower alkylthio group whose alkyl moiety has the same meaning as defined above, such as a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a pentthylthio group, etc. Lower Alkylsulfonyl Group A lower alkylsulfonyl group whose alkyl moiety has the same meaning as defined above, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, etc. Lower haloalauyl group A lower haloalkyl group having one to four carbon atoms, such as a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a tri-fluoromethyl group, a 1-chloroethyl group, a 2-iodoethyl group, a group 3-chloropropyl, a 2-methyl-2-chloropropyl group, a 2, 2, 2-trifluoroethyl group, etc. lower haloalkoxy group A lower haloalkoxy group whose alkyl moiety has the same meaning as defined above, such as a trifluoromethoxy group, a difluoromethoxy group, a chlorodifluoromethoxy group, a 2-chloroethoxy group, a group 1,1,2,2- tetrafluoroethoxy, a 3-chloropropoxy group, etc. Alkoxycarbonyl group An alkoxycarbonyl group having approximately two to eight carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, etc. Alkoxycarbonylalkoxy group An alkoxycarbonylalkoxy group having approximately three to ten carbon atoms, such as a methoxycarbonylmethoxy group, a l- (methoxycarbonyl) ethoxy group, a 1- (ethoxycarbonyl) ethoxy group, a l-methyl-3- ( isopropoxycarbo-nil) propyl, etc. Grypo aoyl An acyl group, such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, etc.

An aralkyl group, such as a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-methyl-1-phenylethyl group, a 1-methyl-2-phenylethyl group, a 1-ethyl-2 group phenylethyl, a 3-phenylpropyl group, etc. The groups not specifically mentioned as examples of the above groups can be selected by optional combination based on the above atoms and groups or according to the common sense of this field. Among the compounds represented by the general formula (I) described above, preferred groups of the compound include the compounds of the general formula (I) in which R 1 is a phenyl group, a 2-fluorophenyl group, a 2-chlorophenyl group or a 2-methylphenyl group; RJ is a hydrogen atom, a methyl group or an ethyl group; R1 is a phenyl group; a phenyl group substituted in the 3-position with a substituent selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, a lower haloalkyl group and a lower haloalkoxy group; or a phenyl group substituted at positions 2 and 5 or at positions 3 and 5 with two substituents selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, a lower haloalkyl group or a lower haloalkoxy group; R * and R5 is each independently a methyl group or an ethyl group; W is a group represented by the formula -N- (R ') -, in which the preferred group of R * is a hydrogen atom or a methyl group. The most preferred compound of general formula (I) is the compound represented by the following general formula wherein X1, X2 and X3 each independently represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, a lower haloalkyl group or a lower haloalkoxy group. Specific examples of the compound of general formula (I) above provided by the present invention will be shown in Tables 1 to 5 below. In the Tables, the abbreviations used have the following meanings. Me: methyl group; Et: ethyl group; Pr: n-propyl group; iPr: isopropyl group; Bu: butyl group; iBu: isobutyl group; sBu: sec-butyl group; tBu: tere-butyl group; Hex: hexyl group; Ph: phenyl group; Bn: benzyl group; 2-F-PH: 2-fluorophenyl; Y : without substituent Table 1 Table l (continued) Table 1 (continued) Table i (continued) Table 1 (continued) Table 1 (continued) Table 1 (continued) Table 1 (continued) ) one * NJ ( Table 1 (continued) Table 1 (continued) Table 1 (continued) Table 2 Table 2 (continued) Table 3 Table 3 (continued) Table 3 (continued) Table 4 Table 4 (continued) ? or K) u > u »u» Table 5 The compound according to the present invention can be prepared using any method known in the art. For example, the compound represented by the general formula (1) can be prepared using the following methods.

Method A wherein R1, R, R * and Rs are as defined in the formula-Q the general (1) and R10 is as defined in the general formula (II). The compound of formula (1-2) can be obtained by reacting a compound of formula (II) with a cocaine of formula (III) in the presence or absence of a suitable solvent. The reaction temperature can be determined arbitrarily so that I varied from 90 ° C to 160 ° C or up to the boiling point of the solvent. The solvent, if used, is not particularly limited so long as it is inert with the starting materials under the conditions of Method A, but in view of the reaction temperature, a solvent having a high boiling point is preferable, such as toluene, xylene or mesitylene. Although the reaction time varies depending on the resting conditions, the reaction can be completed generally in 1 to 240 minutes. Although the quantitative ratio of the compounds of formula (II) and (III) is not particularly limited the compound of formula (III) is generally 0.5 to 2 moles, preferably 0.9 to 1.1 moles, per 1 mole of the composed of formula (II). The products of formula (1-2) can be isolated and purified from the reaction mixture using a known Q method, such as extraction, recrystallization or chromatography. The ester derivative of the N-methylene amino acid represented by the general formula (II) shown below and used in the above reaction as starting material is a new compound, which is also included in the present invention. General formula (II): wherein R * and R * each independently represents a lower alkyl group and R1"represents a lower alkyl group or an aralkyl group." Among the compound represented by the general formula (II) described above, preferred groups of the compound include the compounds of general formula (II) in which R * and R5 are each independently a methyl group or an ethyl group, R10 is a methyl group, an ethyl group or a benzyl group Specific examples of the compound of general formula (II) ) provided by the present invention are shown in the following Table 6. In Table 6, the abbreviations used are the same as in the previous Tables.

M) Ul to 3 3 3 3 3 3 3 3 3 -fc_ # • »- • Q_ UJ UJ UJ UJ Q. a. to. to. to. to. Q. Q. Q. 00? m? m m m -O m UJ UJ UJ oi o «0) 0) V tt a > FFFFFFFFF f FFFFFFFF - »- * • fe c 0. 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 5 5 5 5 5 5 2 JJ UJ • o -rl O (fl 3 C 4J or C __ OU ex E VD or O «5 r-l _Q« J H m o m GM The compound of formula (II) can be prepared using any method known in the art. For example, it can be prepared using the following method. wherein R * and Rs are as defined in general formula (I) and R10 is as defined in the general formula (II). The compound of formula (II) can be obtained by reacting one of the amino acid esters of formula (II ') with formalin in the presence or absence of a suitable solvent. The reaction temperature can be determined arbitrarily as long as it varies from 0 to 140 ° C. The solvent, if used, is not particularly limited so long as it is inert to the materials under the conditions of this method, and preferred examples of the solvent include hydrocarbons, such as as toluene or xylene; ethers, such as diethyl ether, diisopropyl ether or tetrahydrofuran.

Although the reaction time varies depending on the conditions, the reaction can be completed generally in 1 hour to 1 day. Although the quantitative ratio of the compounds of formula (II ') and formalin is not particularly limited, 1 to 5 moles, preferably 1.1 to 2 moles, of formalin per 1 mole of the compound of formula (II') is generally used. . The products of formula (II) can be isolated and purified from the reaction mixture using a known method, such as extraction, distillation, recrystallization or chromatography. The amino acid esters of formula (II ') and used in the above reaction as a starting material can be obtained by known methods or similar methods. The compound of formula (II) is often in a state of equilibrium with its trimer at room temperature, and therefore said compound can be present as a mixture of the compound itself, which is monomer, and its trimer. In addition, all compounds may be present in trimer form depending on the conditions. However, the monomer name of said compound whatever its form will be used, for simplicity. The compound of formula (III) is another starting material for synthesizing the compound of formula (1-2) and can be obtained by various methods, for example it can be obtained by the method described in Chem. Pham. Bull., 11 (6), 1896-1901 (1983) or similar methods.

Etodo B wherein R1, Ra, R4 and Rs are as defined in general formula (I) and Rw is as defined in general formula (II). The compound of formula (1-3) can be obtained by hydrolyzing the compound of formula (1-2) with an alkali. Examples of an alkali include a solution of sodium hydroxide or potassium hydroxide. The solvent, if used, is not particularly limited so long as it is inert under the conditions of Method B, and preferred examples of the solvent include alcohols, such as methanol or ethanol; ethers, such as tetrahydrofuran or dioxane. The reaction temperature is preferably air-cooled from room temperature to 80 ° C. The products of formula (1-3) can be isolated and purified from the reaction mixture using a known method, such as extraction, recrystallization or chromatography.

Method C (1-4) (1-3) wherein R1, Ra, R * and R "are as defined in the general formula (I) and the abbreviation Bn means a benzyl group The compound of the formula (1-3) can be obtained by hydrogenating the compound of the formula (1) -4) in the presence of a metallic catalyst Most of the metal catalysts commonly used as a catalyst to promote hydrogenation, such as palladium-carbon, rhodium-carbon or platinum black, can be used as a metallic catalyst for this method.

The solvent used is not particularly limited as long as it is inert under the conditions of the Method C and preferred examples of the solvent include alcohols, such as methanol or ethanol; esters of acetic acid, such as ethyl acetate; and acetic acid. This reaction can be completed under the following conditions; hydrogen atmosphere; normal pressure; room temperature; reaction time from 1 hour to 1 day; and can also be promoted by applying heat and / or pressure. The amount of the added catalyst can be determined arbitrarily according to the reaction rate. The products of formula (1-3) can be isolated and purified from the reaction mixture using a known method, such as extraction, recrystallization or chromatography.

Method P wherein R1, R2, R ', R4, R5 and W are as defined in general formula (I). The compound of formula (I) can be obtained by reacting the compound of formula (1-3) with carbon tetrachloride and triphenylphosphine followed by treatment with the compound of formula (IV) in the presence of a base. The reaction temperature is preferably from room temperature to about 140BC or up to the boiling point of the solvent for the first process above, and 0βC to about 60aC for the second process. The solvent used is not particularly limited so long as it is inert under the conditions of Method 0, and preferred examples of the solvent include halogenated hydrocarbon solvents, such as carbon tetrachloride, chloroform or methylene chloride; hydrocarbon solvents, such as toluene, xylene or mesitylene; and ether solvents, such as diethyl ether, tetrahydrofuran or dimethoxyethane. Examples of a base include tertiary amines, such as triethylamine, diisopropylethylamine or pyridine; inorganic bases, such as sodium hydroxide or sodium carbonate. If required, the base can also be applied as a solution or as a salt formed with the compound of formula (IV). In addition, when the compound (IV) is an amine, an excess of said compound of the formula (IV) can also be used as the base. The products of formula (I) can be isolated and purified from the reaction mixture using a known method, such as extraction, recrystallization or chromatography.

Method E wherein R1, Ra, R4, R5 and W are as defined in general formula (I). The compound of formula (I) can be obtained by reacting the compound of formula (1-3) with carbonyldiimidazole followed by treatment with the compound of formula (IV) or a salt thereof. The reaction temperature is preferably 0 cc at about 60 ° C for the first process above and from the room temperature to about 100 ° C or up to the boiling point of the solvent for the second process.

The reaction time is generally from 0.5 to 24 hours. The solvent used is not particularly limited so long as it is inert under the conditions of Method E, and preferred examples of the solvent include halogenated hydrocarbon solvents, such as carbon tetrachloride, chloroform or methylene chloride; hydrocarbon solvents, such as toluene, xylene or mesitylene; ethereal solvents, such as diethyl ether, tetrahydrofluoride or dimethoxyethane; ketone solvents, such as acetone or methyl ethyl ketone; and polar aprotic solvents, such as acetonitrile, M, -dimethylformamide or N, N-dimethylacetoamide. The products of formula (I) can be isolated and purified from the reaction mixture using a known method, such as extraction, recrystallization or chromatography.

Method F wherein R1, R2, R4 and R * are as defined in formula (I); R "is a primary or secondary lower alkyl group or an aralkyl group, Z is a halogen atom, a p-toluenesulfonyloxy group, a methylsulfonyloxy group, a trifluoromethylsulfonyloxy group or a group which can be a good elirable group by the reaction nucleophile represented by the formula OSOjOR 11. The compound of formula (1-5) can be obtained by reacting the compound of formula (1-3) with the com-Q formula of formula (V) in the presence of a base. it is preferably from room temperature to about 140 ° C. or up to the boiling point of the solvent The solvent used is not particularly limited, so long as it is inert under the conditions of Method F and preferred examples of the solvent include polar aprotic solvents, such as such as N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile or acetone, ethereal solvents, such as tetrahydrofuran or dioxane, alcohols, such as Q methanol or ethanol; and the mixture of water and the aforementioned solvents. Examples of base include inorganic carbonate bases, such as potassium carbonate, potassium bicarbonate, sodium carbonate or sodium bicarbonate; inorganic bases, -. such as sodium hydroxide or potassium hydroxide; sodium methoxide; and sodium hydride. If required, the base can also be applied as a salt formed with the compound of formula (1-3). The product represented by the general formula (I-5) can be isolated and purified from the reaction mixture using a known method, such as extraction, recrystallization or chromatography.

Method G wherein R1, Ra, R3, R4, Rβ and W are as defined in the general formula (I) and R1J is a lower alkyl group. The compound represented by the general formula d ~ 7) can be obtained by oxidizing the compound of formula (1-6) with a suitable oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide, m-chloroperbenzoic acid, sodium roetaperiodate, peracetic acid and potassium permanganate. The reaction temperature is preferably from 03C to about 140aC or up to the boiling point of the solvent. The solvent used is not particularly limited as long as it is inert under the conditions of Method G and preferred examples of the solvent include halogenated hydrocarbon solvents, such as 1,2-dichloroethane, carbon tetrachloride, chloroform or methylene chloride; methanol; acetic acid; Water; and its mixtures. The product represented by the general formula (I-7) can be isolated and purified from the reaction mixture using a known method, such as extraction, recrystallization or chromatography.

Method H wherein R1, Ra, Ra, R4 and R "are as in formula (I); R" is a primary or secondary lower alkyl group, a lower aralkenyl group or a lower alkynyl group; Z is as defined in the general formula (V).

The compound of formula (1-9) can be obtained by reacting the compound of formula (1-8) with the compound of formula (VI) in the presence of a base. The reaction temperature is preferably from room temperature to about 140BC or up to the boiling point of the solvent. The solvent used is not particularly limited so long as it is inert under the conditions of Method H and preferred examples of the solvent include polar aprotic solvents, such as N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile or acetone; ethereal solvents, such as tetrahydrofuran or dioxane; alcohols, such as ratanol or ethanol; and the mixture of water and the aforementioned solvents. Examples of bases include inorganic carbonate bases, such as potassium carbonate, potassium bicarbonate, sodium carbonate or sodium bicarbonate; inorganic bases, such as sodium hydroxide or potassium hydroxide; sodium methoxide; and sodium hydride. Q The products of formula (1-9) can be isolated and purified from the reaction mixture using a known method, such as extraction, recrystallization or chromatography. The compound of general formula (I) according to the present invention has strong herbicidal activities against many kinds of weeds and phytotoxicities very weak for useful crops. When the compound represented by the general formula (I) is used as a herbicide, it is mixed with a vehicle, diluent or additive and agricultural adjuvant and horticulturally acceptable by a known method, giving it while the form of formulation that is used generally as agricultural chemical, for example, wettable powder, granule, water-dispersible granule, concentrate for emulsion or concentrate for suspension. The compound can be mixed or used together with other agricultural chemicals, for example, fungicides, insecticides, miticides, herbicides, plant growth regulators, fertilizers and soil conditioners. "In particular, the mixed use with other herbicides can lead not only to the reduction in the dose, reduction in the workforce, but also to the extension of the herbicide spectrum attributable to cooperative activities and to improved effects attributable to synergistic activities by both * "Agents" are hereinafter mentioned, for example, as specific examples of other usable herbicides in a state such that they are mixed with the compounds of the present invention represented by the general formula (I) (the parenthetical word means common names unless otherwise defined.) Carbamate Herbicides 3, Methyl 4-dichlorophenylcarbamate (S ep), isopropyl 3-chloroprophenylcarbamate (Clorprofam), S- (4-chlorobenzyl) -diethylthiocarbamate (Bentiocarb), N, N-hexamethylethiocarbamate S-ethyl (Molinate ), S- (l-methyl-l-phenylethyl) -piperi-din-1-carbothioate (Dimepiperate), N-ethyl-N- (1,2-dimethylpro-pyl) -thiolcarbaraate of S-benzyl (Esprocarb), N- (3-methylphenyl) -carbamic acid 3- (methoxycarbonyl) aminophenyl (Fenmedifam), ethyl 3-phenylcarbamoyloxyphenylcarbamate (Desmedifam), etc. Herbicides of urea 1- (a, a-diraethylbenzyl) -3- (4-methylphenyl) urea (Dimron), 3- (3,4-dichlorophenyl) -l, l-dimethylurea (Diuron), 1,1-dimethyl- 3- (,, α-trifluoro-m-tolyl) urea (Fluometuron), 3- [4- (4-chlorophenoxy) phenyl] -l, 1-dimethylurea (Cloroxuron), 3- (3,4-dichlorophenyl) - l-methoxy-1-methylurea (Linuron), 3- (4-chlorophenyl) -l-methoxy-1-methylurea (Monolinuron), 3- (4-bromo-3-chlorophenyl) -l-methoxy- l-methylurea (Clorbromuron), l- (at, a-dimethylben-cyl) -3- (2-chlorobenzyl) urea (code number JC-940), etc. Haloacetamide 2-chloro-2 ', 6'-diethyl-N-methoxymethylacetanilide (A-lachlor), N-butoxymethyl-2-chloro-2', 6'-diethylacetanilide (Bu-tachlor), 2-chloro -2 ', 6'-diethyl-N- (2-propoxyethyl) acetanilide (Pretilachlor), 2-chloro-N-isopropylacetanilide (Propachlor), etc.

Herbicides 3 'amide, 4'-dichloropropionanilide (Propanil), 2-bromo-N- (1, l-dimethylbenzyl) -3, 3-dimethylbutanamide (Bromobutide), 2-benzothiazol-2-yloxy-N-methylacetanilide (Mefenacet ), N, N-dimethyldiphenylacetamide (Difenamid), etc. Dinitrophenyl 4,6-dinitro-o-cresol (DNOC), 2-tert-butyl-4,6-dinitrophenol (Dinoterb), 2-sec-butyl-4,6-dinitrophenol (Dinoseb), N, N-diethyl-2,6-dinitro-4-trifluoromethyl-1-m-phenylenediamine Q (Dinitraraine), a, a, α-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine (Trifluralin), 4 -methyl-sulfonyl-2,6-dinitro-N, N-dipropylaniline (Nitralin), N- (l-ethylpropyl) -2,6-dinitro-3,4-xylidine (Pendimetalin), etc. Phenoxy herbicides 5-2,4-dichlorophenoxyacetic acid (2,4-D) acid 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 4-chloro-o-tolyloxyacetic acid (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid (MCPB), acid 4 - (2,4-dichlorophenoxy) utyric (2,4-DB), 2- (4-chloro-o-tolyloxy) propionic acid (Mecoprop), 2- (2,4-0-dichlorophosinoxy) propionic acid (Dichlorprop), (RS) -2- [4- (2,4-Dichlorophenoxy) phenoxy] -propionic acid (Diclofop) and its esters, (RS) -2- [4- (5-trifluororaethyl-2-pyridyloxy) phenoxy] propionic acid (Fluazifop) and its esters, 2 (2,4-dichloro-3-methylphenoxy) -propionanilide (Clomeprop), 4-chloro-2-methylphenoxy-thioacetate 5 of S-ethyl (phenothiol), 2- (2-naphthoxy) -propionanilide (Naproanilide), etc. Carboxylic acid herbicides 2,2-dichloropropionic acid (Dalapona), trichloroacetic acid (TCA), 2,3,6-trichlorobenzoic acid (2,3,6-TBA), 3,6-dichloro-o-anisic acid (Dicamba) ), 3-amino-2,5-dichlorobenzoic acid (Cloramben), etc. Herbicides of organic phosphorus 0- (2-nitro-5-phenylphenyl) -N-sec-butyl-phosphoramidatioate of O-ethyl (Butamifos), S- (2-benzenesulfonylamino-Qyl) phosphorodithioate of 0,0-diisopropyl (SAP), S- (2-methylpiperidin-1-yl) -carbonyl-ethyl (Piperophos) 0,0-dipropyl-phosphorodithioate, etc. Benzonitrile herbicides 2,6-dichlorobenzonitrile (Diclobenil), 3,5-dibromo-5-hydroxybenzonitrile (Bromoxinil), 4-hydroxy-3,5-diiodobenzonitrile (Ioxinil), etc. Herbicides of diphenyl ether (2,4-dichlorophenyl) -4-nitrophenyl ether (Nitrophen), 2,4,6-trichlorophenyl-4'-nitrophenyl ether (Clornitrofen), 2,4-dichlorophenyl-3-methoxy- 4-nitro-phenyl-ether (Clometoxifen), methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (Bifenox), 4-nitrophenyl-a,, α-trifluoro-2-nitro-p-tolyl-ether (Fluorodifen), 2-chloro-4-trifluoromethylphenyl-3-ethoxy-4-nitrophenyl ether (Oxyfluorfen), 5- (2-chloro-a, or, -trifluoro-p-tolyloxy) -5 2- nitrobenzoic acid (Acifluorfen), etc.

Triazine herbicides 4-amino-3-methyl-6-phenyl-l, 2,4-triazin-5 (4H) -one (Metamitron), 4-amino-6-tert-butyl-3-methylthio-l, 2 , 4-triazin-5- (4H) -one (Metribuzin), 2-chloro-4,6-bis- (ethylamino) -l, 3,5-triazine (Simazine), 2-chloro-4-ethylamino-6 -isopropylamino-1,3,5-triazine (atrazine), 2,4-bis (ethylamino) -6-methylthio-1,3,5-triazine (symmetry), 2,4-bis (isopropylamino) -6-methyl -thio-1, 3,5-triazine (Proraetrine), 2- (1, 2-diraethylpropylaraine) -4-ethylamino-6-methylthio-l, 3,5-triazine (dimethamethrin), etc. Sulfonylurea herbicides 2-chloro-N- [4-methoxy-6-methyl-1,3,5-triazin-2-yl) ami-nocarbonyl] benzenesulfonamide (Clorosulfuron), 2-. { [((4,6-dimethoxypyrimidin-2-yl) aminocarbonyl) aminosulfonyl] methyl) benzoate methyl (Bensulfuron methyl), 2-. { [(4-chloro-6-methoxy-pyrimidin-2-yl) -aminocarbonyl] aminosulfonyl} ethyl benzoate (ethyl chlorimuron), etc. Diazine herbicides 4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yl-p-toluenesulfonate (pyrazolate), 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5- phenacyloxypyrazole (Pirazoxifene), 1,3-dimethyl-4- (2,4-dichloro-3-methyl-benzoyl) -5- (4-methylphenacyloxy) pyrazole (Benzofenap), etc. Other herbicides 3,6-dichloropyridine-2-carboxylic acid (Clopira-lid), 4-amino-3,5,6-trichloropyridine-2-carboxylic acid (Pichloram), 5-amino-4-chloro-2- phenyl-pyridazin-3 (2H) -one (Chloridazin), 3-cyclohexyl-l, 5,6,7-tetrahydrocyclo-pentenopyrimidin-2,4 (3H) -dione (Lenacil), 5-bromo- 3-sec-butyl-6-methyluracil (Bromacil), 3-tert-butyl-5-chloro-6-methyluracil (Terbacil), 3-isopropyl- (lH) -2, 1, 3-benzothiadiazin-4 (3H) -one-2, 2-dioxide (Bentazone), N-1-naphthylphthalamic acid (Naptalam), etc. As the agriculturally or horticulturally acceptable carrier (s) or diluent (s) used in the formulation of the compound (s) of this invention alone or in combination with another herbicide (s), it is used (n) Solid vehicle (s) or liquid (s) generally used in agriculture. Examples of solid carriers or diluents include clays represented by kaolinites, montmorillonites, - illites, polygroskites, etc. more specifically pyrophyllite, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica, talc, etc.; and other inorganic substances, such as gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium lime, phosphorus lime, zeolite, silicic anhydride, synthetic calcium silicate, etc .; organic substances of vegetable origin, such as soy flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose, etc .; natural or synthetic polymers, such as coumaron resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal, damara gum, etc .; waxes, such as carnauba wax, beeswax, etc .; or urea and the like. Examples of suitable liquid carriers or diluents include paraffinic or naphthenic hydrocarbons, such as kerosene, mineral oil, spindle oil, white oil, etc .; aromatic hydrocarbons, such as xylene, ethylbenzene, eumeno, methylnaphthalene, etc .; chlorinated hydrocarbons, such as trichlorethylene, raonoclorobenzene, o-chlorotoluene, etc .; ethers, such as dioxane, tetrahydrofuran, etc .; ketones, such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; esters, such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate, etc .; alcohols, such as petanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexa-nol, benzyl alcohol, etc .; ether alcohols, such as ethylene glycol ethyl ether, diethylene glycol butyl ether, etc .; polar solvents, such as dimethylformamide, dimethylsulfoxide, etc., or water. In addition, surfactants and other auxiliary agents can be used for various purposes, such as emulsification, dispersion, humidification, dilution, dilation, destruction control in combination, stabilization of the active ingredients, improvement of fluidity, prevention of corrosion, prevention of freezing, etc., of the compounds of the invention. As the surfactant, one of any type of nonionic, anionic, cationic and amphoteric surfactant can be used. In general, nonionic and (or) anionic surfactants are used. Examples of suitable nonionic surfactants include polymerization products by the addition of ethylene oxide with higher alcohols, such as lauryl alcohol, stearyl alcohol, oleyl alcohol, etc .; polymerization products by the addition of ethylene oxide with alkylnaphtols, such as butylnaphthol, octylnaphthol, etc .; polymerization products by the addition of ethylene oxide with higher fatty acids, such as palmitic acid, stearic acid, oleic acid, etc .; higher fatty acid esters of polyvalent alcohols, such as sorbitan cone and polymerization products by addition of ethylene oxide therewith; etc. As suitable anionic surfactants, there may be mentioned, for example, alkyl sulfate salts, such as sodium lauryl sulfate, amine salts of sulfuric acid ester of oleyl alcohol, etc., alkylsulfonate salts, such as sodium dioctyl sulfosuccinate, sodium 2-ethylhexylsulfonate, etc. , arylsulfonate salts, such as sodium isopropylnaphthalensulfo-nate, sodium methylenebisnaphthalene sulfonate, sodium ligninsulfo-nate, sodium dodecylbenzenesulfonate, etc., and the like. In addition, in order to improve the properties of the formulations, improve the effects, etc., the herbicides of this invention can be used in combination with polymers and other auxiliary agents, such as casein, gelatin, albumin, glue, sodium alginate. , carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinyl alcohol, etc. The vehicles or diluents described above and the various auxiliary agents are used alone or in combination with others depending on the purpose, taking into account the formulation forms, the conditions of application, etc. The content of the active ingredients in the various formulations of this invention thus prepared can vary widely depending on the forms of formulation., and the suitable content is in the range generally from 0.1 to 99% by weight, and preferably from 1 to 80% by weight, which is more suitable. The wettable powder contains compounds of the active ingredient in generally 25 to 90% amounts, the remainder being solid carriers or diluents and wetting agents for dispersion. If necessary, colloidal protective agents, defoaming agents, etc. may be added. The granule contains, for example, the compounds of the active ingredient in amounts generally of 1 to 35%, the rest being solid carriers or diluents and surfactants. The active ingredient compounds can be uniformly mixed with solid carriers or diluents uniformly, or fixed or adsorbed uniformly on the surfaces of solid carriers or diluents. It is preferred that the diameter of the granules be in the range of about 0.2 to 1.5 mm. The concentrate for emulsion contains, for example, Q generally from 5 to 30% of the compound of the active ingredient, and furthermore approximately 5 to 20% by weight of emulsifiers, the rest being liquid vehicles or diluents. If necessary, dispersing agents and anticorrosive agents can be added. The concentrate for suspension contains, for example, compounds of the active ingredient in amounts generally of 5 to 50%, and in addition of 3 to 10% by weight of wetting agents for dispersion, the remainder being water. If necessary, protective colloidal agents, preservatives, defoaming agents, etc. may be added. The compounds of this invention can be used as herbicides as such or in any of the formulation forms described above. The herbicides of this invention can be applied in effective amounts to various sites to be protected, for example, farmland, such as rice fields and uplands, or uncultivated land, before weed germination or weeds. in various stages from after germination to the growth period. The dose is in general, as quantity of active ingredients, in the order of 0.1 to 10,000 g / ha, preferably 1 to 5000 g / ha. The dose can be varied depending appropriately on the kind of target weeds, their stages of growth, places of application, climate, etc. The compound of formula (I) and the herbicide provided by this invention have strong herbicidal activities against many kinds of weeds and phytotoxicities very weak for useful crops, as will be evident from the test examples described below. For example, the compound of this invention exhibits excellent herbicidal effects at very low doses over a broad time interval from germination to the annual growth period including annual weeds, such as Echinochloa crus-galli, Cyperus difformis, Monochoria or vaginalis, Rotala indica, Lindernia procumbens, Dopatrium junceum, Eleocharis acicularis and Alisma canaliculatum, and perennial weeds, such as Scirpus juncoides and Cyperus serotinus, simultaneously showing high security for the paddy rice plant. The compound of the present invention is characterized in that when it is applied to the ground or to the stem and leaves, it presents high herbicidal activities on various weeds that cause problems also in the highlands, perennial and annual cyperse weeds, such as Cyperus rotundus, Cyperus esculontus, Cyperus brevifo-lius, Cyperus microiria and Cyperus iria and Echinochloa crus-galli, Digitaria sanguinalis, Setaria viridis, Poa annua, Sorghum halepense, Avena sativa and Alopecurus myosuroides as well as broadleaf weeds such as Polygonum lapathifo-lium, Amaranthus viridis and Chenopodium album, which simultaneously show high safety for soy, cotton, sugar beet, corn, upland rice plants, wheat, etc. In addition, the compound according to the present invention can be used not only in rice fields, and highlands, but also in orchards, mulberry trees, turf and uncultivated lands. In addition, when the compound according to the present invention is used in combination with other known agricultural chemicals that have herbi-cides activities, they exhibit complete herbicidal effects on weeds that are difficult to control with each of the compounds applied alone, and control effectively diverse weeds for synergistic herbicidal effects at doses at which a single compound is not effective, and are very safe for paddy rice, soybean, cotton, sugar beet, corn, upland rice plantation, wheat , etc. so that they can provide herbicides that are very useful in agriculture.

EXAMPLES Next, the examples will describe in more detail the production of the compounds of formula (I) and the intermediate of formula (II).

Example 1 Q Preparation of 2-. N-methyleneamino. Methyl 2-methyl butyrate (Compound n. 2-15) Methyl 2-amino-2-ethylbutyrate (2.62 g) was poured dropwise at room temperature to 37% formalin (2.27 g) and the mixture was stirred for 4 hours . Then . the reaction mixture was dissolved in ether and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated to give the title compound (2.80 g).

Q Example 2 Preparation of methyl 2-methyl-2-.6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1,3-oxazin-3-yl-butyrate f Compound n ° 6511 To a mixture of 2,2,6-trimethyl-5-phenyl-4H-l, 3-di-oxin-4-one (2.18 g) and methyl 2- (N-methyleneamino) -2-methylbutyrate (1.5 g) 20 ml of xylene was added and the mixture was refluxed for 1 hour. The solvent was evaporated and the residue was purified by chromatography on a column of silica gel to provide the title compound (2.4 g). Example 3 Preparation of 2-methyl-2-f6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1,3-oxazin-3-yl-butyric acid compound No. 650. To a solution of methyl 2-methyl-2- (6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-l, 3-oxazin-3-yl) -butyrate (1.91 g) ) in 20 ml of ethanol was added at room temperature 30 ral of aqueous NaOH (0.3N). After stirring for 24 hours, the ethanol was evaporated and the mixture was acidified by hydrochloric acid. The precipitate was filtered off and dried 15providing the compound of the heading (1.36 g).

Example 4 Preparation of benzyl 2-f-methyleneamino-2-methylpropionate (Compound na 2-1Q) 20 A benzyl 2-amino-2-methylbutyrate (12.96 g) was dropped at room temperature 37% formalin (7.62 g) and the mixture was stirred for 4 hours. The reaction mixture was dissolved in ether and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated to obtain the title compound (13.7 g).

Example 5 Preparation of 2-methyl-2- (6-methyl-5-phenyl-2,3-dihydro-4-o-n-4H-i.3-oxazin-3-yl. -benzyl propionate. Compound n'fiA'S A mixture of 2,2,6-trimethyl-5-phenyl-4H-l, 3-di-oxin-4-one (13.97 g) and benzyl 2- (N-methyleneamino) -2-methylpropionate (13, 8 g) 130 ml of xylene was added and the mixture was refluxed for 2 hours.The solvent was evaporated and the residue was purified by chromatography on a silica gel column to give the title compound (21.1 g).

EXAMPLE 6 Preparation of 2-methyl-2-p6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-l.3-oxa2In-3-yl-propionic acid f Compound N-fi: a solution of 2-methyl-2- (6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1, 3-oxazin-3-yl) -propionate benzyl (21.1 g) in 100 ml of ethanol was added 1 g of 5% Pd on carbon and hydrogenated at room temperature under normal pressure. After the ethanol was evaporated, saturated aqueous sodium bicarbonate was added to the mixture and the catalyst was filtered off. The filtrate was acidified by hydrochloric acid. The precipitate was filtered off and dried to give the title compound (10.8 g).

EXAMPLE 7 Preparation of ethyl 2-methyl-2-yl-6-methyl-5-phenyl-2,3-dihydrn-i-oyn-4H-1,3-oxazin-3-yl-propionate (Compound No. < ... To a mixture of 2-methyl-2- (6-methyl-5-phenyl-2, 3-dihydro-4-oxo-4H-1, 3-oxazin-3-yl) -propionic acid (0, 83 g) and potassium carbonate (0.45 g) in 4 ml of dimethylformamide (DMF) was added ethyl iodide (0.56 g) and the mixture was stirred at 60 ° C. for 5 hours.The reaction mixture was poured into water and extracted with ethyl acetate.The organic layer was washed with brine, dried over magnesium sulfate and evaporated.The residue was purified by chromatography on a column of silica gel to provide the title compound (0.87 g). .

EXAMPLE 8 Preparation of 2-RETHYL-2-F6-METHYL-5-Phenyl-2. 3,5-dichlorophenyl-4-oxo-4H-l-3-oxazin-3-yl-propionate (Compound n "5Qv) To a suspension of 2-methyl-2- (6-methyl-5-Q-phenyl-2) acid, 3-dihydro-4-oxo-4H-1, 3-oxazin-3-yl) -propionic acid (1.1 g) in 14 ml of CCl4-CH, Cla (1: 1) was added triphenylphosphine (1.38). g) and then the mixture was refluxed for 40 minutes. The reaction mixture was ice-cooled and 3,5-dichlorophenol (0.65 g) and triethylamine 5 (0.4 g) were added slowly and then stirred at room temperature for 1 hour. After evaporation of the solvent, the residue was dissolved in ethyl acetate. The insoluble products were filtered and the filtrate was evaporated. The residue was purified by chromatography on a silica gel column to give the title compound (0.7 g).

Example 9 Preparation of N-phenyl-2-methyl-2- (6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1,3-oxazin-3-yl-propanamide (Compound n »11 To a suspension of 2-methyl-2- (6-methyl-5-pheny1-2, 3-dihydro-4-oxo-4H-1, 3-oxazin-3-yl) -propionic acid (0.83 g) in 10.4 ml of CC14-CH_C12 (1: 1) triphenylphosphine (1.04 g) was added and the mixture was then refluxed for 40 minutes. The reaction mixture was cooled with ice and aniline (0.28 g) and triethylamine (0.3 g) were added slowly, and then stirred at room temperature for 1 hour. After evaporation of the solvent, the residue was dissolved in ethyl acetate. The insoluble products were separated by filtration and the filtrate was evaporated. The residue was purified by chromatography on a silica gel column to give the title compound (0.58 g).

Example 10 Preparation of N-. .5-dichlorophenyl-2-methyl-2- (6-methy] -phenyl-2,3-dihydro-4-oxo-4H-1,3-oxazin-3-yl) -propanamide (Compound No. 271 The title compound (1.05 g) was prepared in the same manner as described in Example 9 except that 3,5-dichloroaniline was used as the starting material.

EXAMPLE 11 Preparation of N- (3-trifluoromethylphenyl) -2-methyl-2- (6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1,3-oxazin-3) il-pronanamide (Compound no. 93) The title compound (0.72 g) was prepared from the raarase raanera that was described in Example 9 except that 3-trifluororaethylaniline was used as the starting material.

Example 12 Preparation of N-isopropyl-2-methyl-2-f6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1,3-oxazin-3-yl? -propanamide (Compound No. SQal A Solution of 2-methyl-2- (6-phenyl-5-phenyl-2,3-dihydro-4-oxo-4H-1, 3-oxazin-3-yl) -propionic acid (0.83 g) in 6 ml of tetrahydrofuran (THF) was added carbonyldiimidazole (0.59 g). After stirring at room temperature for 30 minutes, isopropylamine (0.23 g) was added and the reaction mixture was stirred at 60 SC for 5 hours. It was then poured into water and extracted with ethyl acetate.The organic layer was washed with brine, dried over magnesium sulfate and evaporated.The residue was purified by chromatography on a column of silica gel to provide the title compound. (0.38 g).

Example 13 Preparation of N- (.5-dichlorophenyl) -N-methyl-2-methyl-2- (6- Q methyl-5-phenyl-2,3-dihydro-4-QX? -4H-1 .3-oxazin- 3-yl) -propanamide (Compound No. 302) A solution of N- (3,5-dichlorophenyl) -2-phenyl-2- (6-methyl-5-phenyl-2,3-dihydro-4-oxo) -4H-1, 3-oxazin-3-yl) -propanatride (0.6 g) in 2 ml of DMF was cooled in an ice bath and U 60% sodium hydride in oil (0.06 g) was added. The mixture was stirred at room temperature for 30 minutes and methyl iodide (0.31 g) was subsequently added and the mixture was stirred at room temperature for 5 hours. Then the reaction mixture was poured into water and 2Q extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate and evaporated. The residue was purified by chromatography on a silica gel column to give the title compound (0.51 g). Example 14 Preparation of N- (4-methylsulfonylphenyl) -2-methyl-2- (6-methyl- *; - phenyl-2,3-dihydro-4-oxo-4H-1 .3-oxazin-3-yl 1 -paranopanaraide (Compound na 1511 A solution of N- (4-Rethylthiophenyl) -2-methyl-2- (6-phenyl-5-phenyl-2,3-dihydro-4-oxo-4H-l, 3-oxazin- 3-yl) -propane-mide (0.6 g) in 12 ml of 1,2-dichloroethane was cooled in an ice bath and 70% metachloroperbenzoic acid (0.8 g) was added. At room temperature for 24 hours, the reaction mixture was washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and evaporated The residue was purified by chromatography on a silica gel column to provide the title compound (0.5 g).

Example 15 Preparation of Nr 2-fluoro-5-ftrifluoromethyl lphenyl-2-methyl-2- (6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1 .3-oxa 2 N-3-yl. propanamide (Compound No. 363. The title compound (0.93 g) was prepared in the same manner as described in Example 9, except that 2-fluoro-5- (trifluoromethyl) aniline was used as the starting material The physical properties of the various compounds prepared by methods similar to those described in the Axis-Píos are shown in Tables 1 to 6 above, and the ^ H-NMR data of these compounds are shown in Tables 7 and 8 below. .

Table 7 Table 7 (continued) Table 7 (continued) Comp 'H-NMR (300MHz) d (ppm) D.soi.en.e CDCl, TMS = 0ppm No 92 165 (s.6H), 196 (s.3H), 531 (s, 2H), 711 736 ( m, 6H), 748-760 (m, 2H), 823 (brs.1H), 837 (d, 1H) 93 172 (s.6H), 196 (s 3H), 531 (s, 2H), 721 -742 (m, 7H), 765 (d, 1H), 785 (brs, 1H), 864 (brs 1H) 94 171 (s, 6H), 196 (s, 3H), 531 (s, 2H), 721 -739 (m, 5H), 753, 762 (ABq, 4H), 873 (brs.1H) 95 165 (s.6H) .197 (s.3H) .532 (s, 2H) .722-736 (m , 5H), 741 (brd, 1H), 769 (brd.1H), 841 (brs, 1H), 8.86 (brs.1H) 96 168 (s, 6H), 196 (s.3H), 532 (s. 2H), 7.21-7.37 (m.5H) .7.49 (brs, 1H), 796 (brs, 1H), 892 (brs.1H) 102 167 (s, 6H) .1.95 (s.3H) .5.32 (s) .2H) .6.40 (t.1H), 6.99-710 (m, 2H). 716-736 (m.6H) .840 (dd, 1H), 845 (brs.1H) 103 170 (s, 6H) .195 (s, 3H) .530 (s, 2H) .6.50 (t.1H) , 680-683 (m, 1H). 719-739 (m, 7H), 750 (brs.1H), 8.53 (brs.1H) 104 170 (s.6H), 195 (s.3H) .530 (s.2H), 6.43 (t, 1H) .704,748 (ABq, 4H). 722-739 (m.5H), 846 (brs.1H) 110 167 (s.6H) .1.94 (s, 3H), 529 (s.2H) .690 (m, 1H), 720-7.37 (m. 7H), 757 (brs.1H) .857 (brs.1H) 123 165 (s.6H), 194 (s.3H), 531 (s, 2H) .721-7.36 (m, 7H), 757-765 (m.1H), 787 (brs.1H), 8.64 (brs.1H) 124 171 (s.6H), 1.96 (s.3H), 5.30 (s, 2H) .720-739 (m, 5H), 756.7.63 (ABq.4H), 890 (brs.1H) 127 167 (s.6H) .1.99 (s.3H) .5.39 (s.2H) .712 (ddd, 1H) .718-734 (m, 5H) .761 (t.1H), 819 (dd.1H) .8.81 (dd.1H) .1101 (brs.1H) 128 170 (s.6H) .1.96 (s.3H), 532 (s.2H) ) .7.21-7.45 (m.6H) .785-7.92 (m, 2H), 833-8.37 (m.1H), 8.74 (brs.1H) 129 171 (s, 6H) .196 (s.3H), 532 (s.2H) .720-740 (m, 5H) .767.8.15 (ABq, 4H), 906 (brs.1H) 131 169 (s.6H), 1.98 (s, 3H) .535 (s. 2H) .722-7.38 (m.5H), 8.64 (t.1H) .8.67 (d.2H), 925 (brs.1H) 135 168 (s.6H) .196 (s.3H) 384 (s. 3H) .542 (s.2H) .702 (ddd.1H), 718-735 (m.5H) .749 (ddd.1H) .798 (dd.1H) .871 (dd.1H) .1152 (brs .1H) 137 165 (s, 6H) .192 (s, 3H) .3.85 (s.3H) .5.28 (s.2H) .720-735 (m.5H), 757, 792 (ABq.4H). 865 (brs.1H) 138 137 (t.3H) .169 (s.6H) .195 (s , 3H) .435 (q.2H) .5.31 (s.2H), 720-738 (m.6H), 774 (d.1 H) 788 (dd.1H) .799 (brs.1H), 839 ( brs.1H) Table 7 (continued) Table 7 (continued) Table 7 (continued) Table 8 Next, various embodiments of formulations are mentioned using the compound of this invention. In the following formulations, all "parts" are by weight.

Formulation example 1 (Concentrate for emulsion) Compound na 1 20 parts Xylene 63 parts Calcium dodecylbenzene sulphonate 7 parts Polyoxyethylethenyl phenyl ether 5 parts Dimethylformamide 5 parts The above materials were mixed and dissolved uniformly, so that 100 parts d concentrate was obtained for emulsion.

Formulation example 2 (Wettable powder) Compound nB 1 20 parts Kaolinite 70 parts Calcium ligninsulfonate 7 parts Condensate of alkylnaphthalenesulfonic acid 3 parts The above materials were mixed and ground using a jet mill, so as to obtain 100 parts of wettable powder.

Formulation Example 3 (Concentrate for suspension) Compound n 1 1 20 parts di (2-ethylhexyl) sodium sulfosuccinate 2 parts Polyoxyethylene-nonylphenyl ether 2 parts Defoaming agent or, 5 parts Propylene glycol 5 parts Xanthan gum or,, 01 parts Water 70, 49 parts The above materials were crushed and uniformly mixed using a wet-type, raind type ball mill to obtain 100 parts of concentrate for suspension.

Formulation example 4 (Granule) Na component 1 part di (2-ethylhexyl) sodium sulfosuccinate 2 parts Bentonite 30 parts Talco 67 parts The above materials were sufficiently mixed, kneaded with the addition of a suitable amount of water and granulated with a granulator to obtain 100 parts of a granule. The herbicidal effects of the compound of this invention will be explained below in accordance with the test examples.

Test example 1 (Application to paddy land) 500 ml agner sherds were filled with paddy land from, adequate amounts of water and chemical fertilizers were added and it was kneaded into a rice field. A strain of paddy rice plant (Koshihikari variety) which was composed of a pair of two seedlings, which had previously grown in a greenhouse to the two-leaf stage, were transplanted to each pot in a population of one strain per pot. In addition, in each sherd, predetermined amounts of seeds of Echinochloa crus-galli, Monochoria vaginalis, Lindernia procumbens and Scirpus juncoides, respectively, were seeded and filled with water to a depth of 3 cm. The next day, wettable powders were prepared using the compounds shown in Table 9 below, according to Formulation Example 2, and diluted with an appropriate amount of water so that they contained active ingredients in an amount of 50 g / ha. . They were applied by drip with a pipette. After 21 days of application of the chemicals, the herbicidal effects on each weed and the phytotoxicity for rice paddy plants were evaluated according to the following criteria. The results obtained are shown in Table 9 below.

Evaluation criteria (11 degrees) Table 9 In Tables 9-12 the abbreviations of the weeds are as follows. Weed A: Echinochloa crus-galli Weed B: Monochoria vaginalis c Weed C: Lindernia procumbens Weed D: Scripcus juncoides Weed E: Digi taria sanguinalis Weed F: Setaria viridis Weed G: Abutilon theophrasti 1Q Weed H: Xanthium strumarium Weed I: Polygonum lapathifolium Weed J: Datura stramonium Test Example 2 (Foliar Application in Rice Fields) 15 500 cma wagner plows were filled with paddy land, suitable amounts of water and chemical fertilizers were added and kneaded to make it a paddy state. A strain of paddy rice plant (Koshihikari variety) that was composed of a pair of 0 seedlings, which had previously grown in a greenhouse to a two-leaf stage, was transplanted into each pot in a stock per pot stock. In addition, predetermined quantities of seeds of Echinochloa crus-galli, Monochoria vaginalis, Lindernia procum-5 bens and Scirpus juncoides, respectively, were seeded in each sherd and filled with water to a depth of 3 cm. After having grown the plants in a greenhouse until Echinochloa crus-galli reached a 1.5 leaf stage, wettable powders were prepared using the compounds shown in Table 10 below according to Formulation Example 2, and diluted with an adequate amount of water so that they contained active ingredients in an amount of 100 g / ha. They were applied by drip with a pipette. After 21 days of the application of the chemicals, the herbicidal effects on each weed and the phytotoxicity for paddy rice plants were evaluated according to the criteria shown in Test Example 1 above. The results obtained are shown in Table 10 below.

Table 10 Test example 3 (Application to highland land) Plastic craters of 900 craa were filled with upland soil, in which a predetermined quantity of seeds of Echinochloa crus-galli, Digita-ria sanguinalis, Setaria viridis, Abutilon theophrasti, Xanthium strumarium, Polygonum lapathifolium and Datura stratum were planted. monium, respectively, and soil was placed on them to a thickness of 1 cm. On the day following the seeding, wettable powders were prepared using the compounds shown in Table 11 below according to Formulation Example 2, and diluted with an appropriate amount of water of ration containing active ingredients in an amount of 1 kg / he has. They sprayed evenly on the surface of the earth. After 21 days of application of the chemicals, the herbicidal effects on each seed were evaluated according to the criteria shown in Test Example 1 above. The results obtained are shown in Table 11 below.

Table 11 Test Example 4 (Foliar application in the highlands) 900 cma plastic pots were filled with highland soil, in which predetermined amounts of seeds of Echinochloa crus-galli, Digi taria sanguinalis, Setaria viridis, Abutilon theophrasti, were planted. Xanthium strumarium, Polygonum lapathifolium and Datura stramonium, respectively, and soil was placed on them up to a thickness of 1 cm. After having allowed the plants to grow in greenhouse until each plant reached a stage of 2 to 4 leaves, wettable powders were prepared using the compounds shown in Table 12 below according to Formulation Example 2, and were diluted with an adequate amount of water so that they contained active ingredient in an amount of 1 kg / ha. They were sprayed uniformly on the surface of the leaves. After 21 days of application of the chemicals, the herbicidal effects on each weed were evaluated according to the criteria shown in Test Example 1 above. The results obtained are shown in Table 12 below.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property:

Claims (23)

REIVI PICA? IQ ES

1. A 1,3-oxazin-4-one derivative represented by the following general formula (I): characterized in that R represents a phenyl group which may be substituted; a represents a hydrogen atom or a lower alkyl group; RJ represents a hydrogen atom, a lower alkyl group, an aralkyl group or a phenyl group which may be substituted; R * and R * each independently represent a lower alkyl group, W represents an oxygen atom or a group represented by the formula -N (R *) - wherein R 'represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group.

2. The compound according to claim 1, characterized in that R is a phenyl group, a 2-fluorophenyl group, a 2-chlorophenyl group or a 2-methylphenyl group.

3 . The compound according to claim 1, characterized in that R is a hydrogen atom, a methyl group or an ethyl group.

4. The compound according to claim 1, characterized in that R is a phenyl group; a phenyl group substituted in the 3-position with a substituent selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, a lower haloalkyl group and a lower haloalkoxy group; or a phenyl group substituted at positions 2 and 5 or at positions 3 and 5 with two substituents selected from 1Q group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, a lower haloalkyl group and a lower haloalkoxy group. The compound according to claim 1, characterized in that R 4 and R 5 are each independently a group 15 methyl or an ethyl group. 6. The compound according to claim 1, characterized in that W is a group represented by the formula -N (R) - wherein R * is a hydrogen atom, a lower alkyl group, a lower alkenyl group or a group lower alkynyl. 7. The compound according to claim 1, characterized in that W is a group represented by the formula -NH- or -N (CH,) -. 8. A l, 3-oxazin-4-one derivative represented by the following general formula (1-1): () characterized in that X, X and X each represent independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, a lower haloalkyl group or a lower haloalkoxy group. 9. The compound according to claim 8, characterized in that X is a fluorine atom, X is a hydrogen atom and X3 is a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, a group lower haloalkyl or a lower haloalkoxy group. 10. The compound according to claim 8, characterized in that X is a hydrogen atom, X is a trifluoromethyl group and Xa is a hydrogen atom. 11. An N-methylene-amino acid ester derivative represented by the following general formula (II): characterized in that P and rtJ each independently reregister a lower alkyl group, R10 represents a lower alkyl group or an aralkyl group. 12. The herbicide, characterized in that it contains a 1,3-oxazin-4-one derivative represented by the general formula (I) of claim 1 as an active ingredient. 13. A herbicidal composition, characterized in that it comprises an effective amount of a 1,3-oxazin-4-one derivative represented by the general formula (I) of claim 1 and an agriculturally and horticulturally acceptable carrier and / or diluent. 14. Herbicidal compositions according to claim 13, characterized in that they further comprise a third herbicidally active ingredient, such as a carbamate derivative or a urea derivative or a haloacetamide derivative or an amide derivative or a dinitrophenyl derivative or a phenytoxy derivative or a carboxylic acid derivative or an organophosphorus compound or a benzonitrile derivative or a diphenylether derivative or a triazine derivative or a sulphonylurea or a diazine or a triazine. 1

5. Herbicidal compositions according to claim 14, artxreri / vdas because the third active ingredient is chosen from 2, 4-D, 2,4-DB, Acifluorfen, Alachlor, Atrazine, Bentiocarb, Bensulfuron methyl, Bentazone, Benzofenap, Bife-nox, Bromacil, Broraobutide, Bromoxinil, Butachlor , Butamifos, Clorimutrón ethyl, Clopiralid, Clometoxinil, Cloroprofam, Cloroxurón, Clorbroraurón, Cloramben, Cloridazón, Clomeprop, Clornitrofén, Clorosulfuron, Clometoxifén, Code number JC-940, Dalapona, Desmedifam, Dicaraba, Diclorprop, Diclofop, Diclobenil, Diraetamethrin, Dimepiperato , Difenamid, DNOC, Dinoterb, Dinoseb, Dinitramine, Dimron, Diuron, Dirauron, Esprocarb, Fluazifop, Fluoraeturon, Fluorodifen, Ioxinil, Lenacil, Linuron, Mecoprop, Mefenacet, Metamitron, Methoxycarbonyl, Metribuzin, Molinate, Monolinuron, MCPB, MCPA, MCPA Thioethyl, Naproanilide, Naptan, Nitralin, Nitrophen, Oxyfluorfen, Pendimethalin, Fenmedifam, Phenothiol, Picloram, Piperophos, Pretilachlor, Prometryn, Propaclor, Propanil, Pirazolate, Pirazoxifen, SAP, Simaz ina, Symmetrin, SK-23, S ep, Trifluralin, TCA, Terbacil and Tiobencarb. 1

6. Herbicidal compositions according to any one of claims 1 to 15, C-a_3Cterized because they comprise between 0.1 and 99% (w / w) of active ingredient, preferably between 1 and 80%. 1

7. Herbicidal compositions according to claim 16, characterized in that they are in the form of a powder that hardens 25 to 90% active ingredient. 1

8. Herbicidal compositions according to the re? V_jtd-C-C-U-n 16, cararterized perché are in the form of a graph that aj? Μ- * 3? E 1 to 35% active ingredient. 1

9. Compositions herbicides according to the rivide-sci-ín 16, face tt-ri arrias perqué are in the form of a ctxio-ptracb for epuls m comprising 5 to 30% active ingredient. 20. Herbicidal compositions according to the r-eivjjidicac-LCn 16, characterized perqué are in the form of a suspension that rpr-rde 5 to 50% of active ingredient. 21. A method for suppressing weeds in one place, characterized in that an effective amount of a composition according to any one of claims 14 to 20 is applied to the place requiring reprehension of the weed. 22. A method for suppressing growth of male-oas in a place, characterized because ca? This method is applied to the inactivation site according to any one of claims 14 to 20, wherein the application rate of the active ingredient is between 1 and 5000 g / ha. 23. A method according to claim 14, Characterized in the place where rice is planted or planted. In testimony of which I sign the present in this City of Mexico D.F., on January 2, 1995. By: RHONE-POULENC AGROCHIMIE Attorney .