MXPA96006690A - New process for preparing esx derivatives of oxymes of acid 2,6-di (4,6 dimetoxipirimidin-2-il) oxybenzo - Google Patents

Abstract

The present invention relates to a process for preparing a 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime derivative represented by the following formula (I): wherein R 1 represents hydrogen, halogen , cyano, nitro, alkyl with 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyloxy with 2 to 6 carbon atoms, alkylthio with 1 to 4 carbon atoms, amino that can be substituted with alkyl of 1 to 4 carbon atoms, aryl, aryloxy, acyl with 1 to 4 carbon atoms or acyloxy with 1 to 4 carbon atoms, n means an integer between 1 to 5, R2 represents hydrogen, halogen , cyano, nitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkoxycarbonyl, alkenyloxycarbonyl with 2 to 4 carbon atoms, alkylaminocarbonyl with 1 to 4 atoms of carbon, di (C1-4 alkyl) aminocarbonyl, aryl methylaminocarbonyl, heteroarylmethylaminocarbonyl, or phenyl which may be substituted with R 1, characterized in that a compound having the following formula (V), in which R represents hydrogen or an alkali metal cation, and R 1, R 2 and n are as defined above, it is reacted with a pyrimidine derivative having the following formula (VI) in which Z represents halogen, alkylsulfonyl or arylsulfonyl with from 1 to 4 carbon atoms

Description

NEW PROCESS FOR PREPARING ESX DERIVATIVES OF OXIMA DE ACID 2,6-DI (4,6-DI ETOXIPYRIMIDIN-2-IL) OXYBENZOIC DESCRIPTION OF rA TMVB ^ PTnM TECHNICAL FIELD The invention relates to a new process for preparing an ester derivative of pyrimidyloxybenzoic acid oxime having herbicidal activity . More specifically, the present invention relates to a novel process for preparing a 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime ester derivative represented by the following formula (I): wherein Ri represents hydrogen, halogen, cyano, nitro, alkyl with 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyloxy with 2 to 6 atoms carbon, alkylthio with 1 to 4 carbon atoms, amino which can be substituted with alkyl having 1 to 4 carbon atoms, aryl, aryloxy, acyl with 1 to 4 carbon atoms or acyloxy with 1 to 4 atoms of carbon, n means an integer between 1 to 5, R 2 represents hydrogen, halogen, cyano, nitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, carbon, alkoxycarbonyl, alkenyloxycarbonyl with 2 to 4 carbon atoms, alkylaminocarbonyl with 1 to 4 carbon atoms, di (C 1-4 alkyl) aminocarbonyl, aryl ethylaminocarbonyl, heteroarylmethylaminocarbonyl, or phenyl which may be substituted with Ri. definitions of the substituents of the compound of the formula (I) , the term "alkyl" which is used alone or in the form of a compound term such as "alkylthio" or "alkylaminocarbonyl" means a straight or branched saturated hydrocarbon radical, for example methyl, ethyl, n-propyl, isopropyl, various isomers of butyl, etc .; the term "alkoxy" means methoxy, ethoxy, n-propoxy, isopropoxy, or various butoxy isomers, etc .; the term "alkenyl" which is used alone or in the form of a compound term such as "alkenyloxy" means straight or branched alkene, for example vinyl, 1-propenyl, 2-propenyl, various butenyl isomers, etc .; and the term "halogen" means fluorine, chlorine, bromine or iodine, etc. The present invention also relates to a novel intermediate that can be used in the process of preparing the compound of the formula (I) and to processes for preparing it. PREVIOUS TECHNIQUE The compound of the formula (I) as mentioned above has an excellent herbicidal activity on a broad spectrum of herbs, broadleaf shrubs, annual or perennial shrubs. Specifically, it has a superior effect on rice planted directly to prevent annual pests and pests in question including farm herbs. Therefore, it has already been subject to an application as a new compound with the process for its preparation by the present inventors (see European patent application No. 658549). According to the aforementioned patent application 7: -. - is, the compound 1eae _ .:. Of the formula (I) can be prepared by performing an esterification reaction of a 2,6-disubstituted benzoic acid derivative of the following formula (II) with an arylketone oxime compound of the following formula I.III) represented in the following reaction scheme A: Reaction scheme A: (II) in which Ri, R2 and n are defined as described above. However, since the carboxyl group in the benzoic acid derivative of the formula (II) is severely hindered spherically, it can not actively react with the bulky arylketone oxime in the esterification reaction under a conventional reaction condition. Therefore the above reaction has the problem that it must be carried out under special and uneconomic reaction conditions in order to raise the reaction yield. DETAILED DESCRIPTION OF THE INVENTION Thus the inventors of the present invention have studied extensively to develop a process that is more efficient and more direct than the previous method having the above mentioned problems. Accordingly, we have identified that the desired compound of the formula (I) can be prepared in high yield without special reaction conditions by using a compound represented by the following formula (V) as a starting substance, and then shaped the present invention : wherein Ri, R2 and n are as defined above, and R represents hydrogen or an alkali metal cation. Thus it is an object of the present invention to provide a novel process for preparing the desired compound of the formula (I), as defined above. It is another object of the present invention to provide a novel intermediate that can be used for the preparation of the compound of the formula (I) and processes for preparing the intermediate. BEST METHOD OF EMBODIMENT OF THE INVENTION In one aspect, the present invention relates to a better process.) To prepare the compound of the formula (I) using the compound of the formula (V) as a starting material. The preparation process according to the present invention can be briefly represented by means of the following reaction scheme B.

(V) (VI) in the reaction scheme B, Ri represents hydrogen, halogen, cyano, nitro, alkyl with 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyloxy with 2 to 6 carbon atoms, alkylthio having from 1 to 4 carbon atoms, amino which can be substituted with alkyl having 1 to 4 carbon atoms, aryl, aryloxy, acyl with 1 to 4 carbon atoms or acyloxy with 1 to 4 carbon atoms, n means an integer between 1 to 5, Rz represents hydrogen, halogen, cyano, nitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkoxycarbonyl, alkenyloxycarbonyl with 2 to 4 carbon atoms, alkylaminocarbonyl with 1 to 4 carbon atoms, di (C 1-4 alkyl) aminocarbonyl, arylmethylaminocarbonyl, heteroarylmethylcarbonyl, or phenyl which may be substituted with Rx Z represents halogen, alkylsulfonyl or arylsulfonyl with from 1 to 4 carbon atoms, and R represents hydrogen or an alkali metal cation. As can be seen from the above reaction scheme B, the present invention provides a process for preparing the desired 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime ester derivative of the formula (I) characterized in that the compound of the formula (V) as defined above, is reacted with a pyrimidine derivative of the formula (VI). Henceforth the process according to reaction scheme B will be specifically explained. The reaction according to reaction scheme B can preferably be carried out in a solvent. As the appropriate solvent for this purpose, one or more selected from a group consisting of ethers such as tetrahydrofuran, diethyl ether, etc. may be mentioned. polar solvents such as dimethylformamide, dimethylsulfoxide, etc., halogenated hydrocarbons such as dichloromethane, carbon tetraeloride, etc., and aromatic hydrocarbons such as benzene, toluene, etc., and tetrahydrofuran or dimethylformamide is preferred among them. The reaction can also be carried out in the presence or absence of a base. As a basis for this purpose, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydride, sodium hydrocarbonate, etc., preferably potassium carbonate or hydride hydride, may be used. sodium. The reaction can generally be carried out in a normal temperature range up to 150 ° C, preferably 50 to 80 ° C. According to the process of the present invention as described above, the pyrimidyloxybenzoic acid oxime ester derivative of the formula (I) having a herbicidal activity can conveniently be obtained under a mild reaction condition with a good yield. While the compound of the formula (V) used as a starting substance in the above reaction scheme B can be prepared from a new derivative of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-4H- (1, 3) -benzodiaoxin-4-one represented by the following formula (IV): in which R3 and R4 independently represent hydrogen, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms with 1 to 6 halogen atoms, benzyl, or phenyl which may be substituted with one or two groups selected from 1 to 5 halogen atoms and / or alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 to 2 carbon atoms and nitro, or R3 and R4 together represent an alkylene chain with from 2 to 6 carbon atoms which may be substituted with 1 to 5 halogen atoms and / or alkyl having 1 to 4 carbon atoms, R also represents in which Q represents sulfur, oxygen or NRβ (Re represents hydrogen or alkyl co of 1 to 4 carbon atoms), Re, Re and RT independently represent hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or haloalkyl with 1 to 2 carbon atoms which may be substituted with 1 to 5 halogen atoms, or Re and Re together represent a benzo-benzene benzene ring, in which the ring of benzene can be substituted with one or two groups selected from 1 to 5 halogen atoms and / or alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, haloalkyl with 1 to 2 carbon atoms , cyano and nitro, RT represents hydrogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms with 1 to 5 halogen atoms or an alkylbenzene ring, X and Y independently represent oxygen or sulfur, Rio, Rn, R12 and R13 independently ent They represent hydrogen, alkyl with 1 to 4 carbon atoms or haloalkyl with 1 to 4 carbon atoms with 1 to 5 halogen atoms, and m means 0 or 1. The process for preparing the compound of the formula (V ) from the 5- (4,6-dimethoxypyrimidin-2-yl) oxy-4H- (1, 3) -benzodioxin-4-one derivative of the formula (IV) can be represented by the following reaction scheme C: Scheme of reaction ?: (IV) (MI) (V) in the reaction scheme C, R, Ri to R4 and n are as defined above. As can be seen from the above reaction scheme C, the compound of the formula (V) is prepared by reacting the derivative 5- (4,6-dimethoxypyrimidin-2-yl) oxy-4H- (1,3) -benzodioxin- 4-one of the formula (IV) with an oxime or its metal salt of the formula (III) to open the benzodioxine ring. This reaction can be carried out preferably in a solvent. As the solvent suitable for this purpose, one or more selected from the group consisting of ethers such as tetrahydrofuran, diethyl ether, etc., polar solvents such as dimethylformamide, dimethyl sulfoxide, etc., halogenated hydrocarbons such as dichloromethane, tetraeloride, may be mentioned. carbon, etc., and aromatic hydrocarbons such as benzene, toluene, etc., and tetrahydrofuran or dimethylformamine are preferred among them. In this reaction, the use of the same solvent as in reaction scheme B above is conveniently recommended, but control is not indispensable. The reaction can also be carried out in the presence or absence of a base. Particularly, in the case of the oxime compound of the formula (III) is used in the form of a metal salt, the reaction can be carried out satisfactorily without a base. As the appropriate base for this reaction, inorganic bases such as potassium carbonate, sodium carbonate, sodium hydride, sodium hydrocarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc., preferably potassium carbonate or sodium hydride. The reaction temperature can vary within a range of -50 to 150 ° C, however, the reaction is preferably carried out at 0-80 ° C. The oxime compound of the formula (III) as the reactive substance in the reaction scheme C can also be used in the form of a metal salt in which R represents an alkali metal cation. This metal oxime salt can be prepared by reacting the corresponding oxime (III) (R = H) with a corresponding metal compound in a solvent in the presence of a base. As a base for this reaction, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydride, sodium hydrocarbonate, etc., sodium alkoxides such as ethoxide of sodium, sodium ethoxide, sodium t-butoxide, etc., preferably potassium carbonate or sodium hydride. As the solvent for this reaction, one or more selected from a group consisting of ethers such as tetrahydrofuran, diethyl ether, etc. polar solvents such as dimethylformamide, dimethyl sulfoxide, etc., halogenated hydrocarbons such as dichloromethane, carbon tetraeloride, etc., aromatic hydrocarbons such as benzene, toluene, etc., and among them tetrahydrofuran or dimethylformamide are particularly preferred. When the compound of the formula (V) obtained in this way is used to prepare the preferred compound of the formula (I) according to the above reaction scheme B, it can be reacted directly with the pyrimidine derivative (VII) without any isolated procedure, or it can be isolated and purified prior to the reaction with the pyrimidine derivative (VI). In the case of the isolated free process, the reaction mixture obtained from the reaction represented by scheme C can be added dropwise to the solution of pyrimidine derivative (VI) or vice versa. In the course of developing the process for preparing the compound of the formula (I), the inventors of the present invention have also found that the derivatives of 5- (4,5-dimethoxypyrimidin-2-yl) oxy-4H- (1 , 3) -benzodiozin-4-one of the formula (IV) as defined above is a useful intermediate for preparing the compound (I) as well as a new compound. Therefore in another aspect, the present invention relates to this new intermediate and to the process for its preparation. Among the acrylate cyclic compound of the formula (IV), a compound of the formula (IVa) having the substituents R3 and R4 as defined below can be prepared by reacting a known compound of the formula (VII) and a carbonyl compound of the formula (VIII) with thionyl chloride in a solvent in the presence of a catalytic amount of dimethyl inopyridine. The process can be represented by the following reaction scheme D. In this reaction, an ether such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc., a polar solvent such as dimethylformamide, dimethyl sulfoxide, etc., a halogenated hydrocarbon solvent such as dichloromethane, carbon tetraeloride, etc. or a hydrocarbon aromatic solvent such as benzene, toluene, etc., preferably dimethoxyethane or toluene can be used as a solvent. The reaction can be carried out at the normal temperature at 150 ° C, preferably at 50-80 ° C. Reaction scheme D: in the reaction scheme D, R30 and R40 independently represent hydrogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms having 1 to 5 halogen, benzyl or phenyl atoms which can be substituted with one or two groups selected from 1 to 5 halogen atoms and / or alkyl having 1 to 4 carbon atoms, alkoxy with 1 at 4 carbon atoms, haloalkyl with 1 to 2 carbon atoms, or R30 and R40 together represent an alkylene chain with 2 to 6 carbon atoms which can be substituted with 1 to 5 halogen atoms and / or alkyl with from 1 to 4 carbon atoms. Alternatively, the novel cyclic acrylic compound of the formula (IVa) can also be obtained by reacting the known compound of the formula (VII) with the carboxyl compound of the formula (VIII) or an acrylate compound of the formula (IX) ) corresponding to the compound (VIII) in the presence of an acid catalyst and a dehydrating agent, if necessary by removing water or alcohol produced during the reaction as a secondary product by means of distillation, as described in the following scheme Reaction E. When the reaction is carried out in a solvent, an ether such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc., a halogenated hydrocarbon solvent such as dichloromethane, carbon tetraeloride, etc., or a hydrocarbon aromatic solvent such such as benzene, toluene, xylene, etc., preferably benzene or toluene can be used as solvents. If desired, an excessive amount of the acrylate compound can be used instead of the solvent. As a catalyst, cationic acids such as p-toluenesulfonic acid, sulfuric acid, phosphoric acid, etc., Lewis acids such as aluminum chloride, titanium tetraeloride, zinc chloride, zinc chloride, calcium chloride, tin chloride, etc. there may be mentioned: and as the dehydrating agent, organic anhydride such as trifluoroacetic acid anhydride or acetic acid anhydride or sodium sulfate or calcium chloride. The reaction can be carried out at a normal temperature up to 150 ° C, preferably at 80 to 130 ° C. Reaction scheme E: In the reaction scheme E, R30 and R40 are defined as previously described in connection with reaction scheme D, R14 represents alkyl with 1 to 4 carbon atoms, in some chaos, as represented in the following Reaction scheme F, a known compound of the formula (X) (See, Re., Semin.Fac, Sci.Univ.Cagliari, 1978, 48, 2750283) is reacted with the pyrimidine derivative of the formula (VI) in a solvent in the presence of a base to obtain the compound of the formula (IVa) In this reaction, an ether such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc., a polar solvent such as dimethylformamide, dimethyl sulfexide, etc. ., a halogenated hydrocarbon solvent such as dichloromethane, carbon tetrachloride, etc., or an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc., preferably tetrahydrofuran or dimethylformamide can be used as the solvent. temperat Normal temperature at 150 ° C, preferably at 50-80 ° C. Reaction scheme F: in the reaction scheme F, R30 and R40 are defined as previously described in relation to the reaction scheme D, Z is defined as previously described. In addition, the novel cyclic acrylic compound of the formula (IVa) in which both R3 and R4 represent hydrogen can be obtained by reacting the known compound of the formula (VII) with a dihaloethane of the formula (XI) in a solvent in the the presence of a base represented in the following reaction scheme G. In this case the dihalomethane means a haloalkane such as dibromomethane or diiodomethane.

As the base, an inorganic base such as potassium carbonate, sodium carbonate, sodium hydride, sodium hydrocarbonate, sodium hydroxide, potassium hydroxide, etc., preferably potassium hydroxide or sodium hydroxide may be used.; and as the solvent an ether such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc., a polar solvent such as dimethylformamide, dimethyl sulfoxide, water, etc., a halogenated hydrocarbon solvent such as dichloromethane, carbon tetraeloride, etc., or an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc., preferably dimethylformamide, dimethyl sulfoxide or toluene. If necessary, a phase transfer catalyst such as a derivative of tetraalkylammonium salts can be used additionally. The reaction can be carried out at a normal temperature at 150 ° C, preferably at 80-130 ° C. Reaction scheme G: (Vile) in the reaction scheme G, P represents bromine or iodine. Typical examples of the compound of the formula (IVa) prepared according to the process explained above are presented in the following table 1. Table 1 Table 1 (with inuación) Table 1 (continued: Among the cyclic acrylic compound of the formula (IV) above, a compound of the formula (IVb) in which R-represents (in which Q, RB, Re and RT are defined as previously described) can be prepared in accordance with a process characterized in that a compound of the formula (XII) is reacted with a derivative of the formula (XIII) in a solvent in the presence of a base as described in the following reaction scheme H. Reaction scheme H: (XU) (XIU) (IVb) in the reaction scheme H, R3, Re, Re, R-7 and Q are defined as previously described. In the reaction scheme H, an ether such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc., a polar solvent such as dimethylformamide, dimethyl sulfoxide, etc., a halogenated hydrocarbon solvent such as dichloromethane, carbon tetrachloride, etc. , or an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc., preferably tetrahydrofuran dimethylformamide can be used as the solvent. And as a base an inorganic base such as potassium carbonate, sodium carbonate, sodium hydride, sodium hydrocarbonate, etc., preferably potassium carbonate or sodium hydride. This reaction can be carried out at a normal temperature of 150 ° C, preferably 50 to 80 ° C. Typical examples of the compound of the formula (IVb) prepared according to the aforementioned process are presented in the following table 2.

Table 2 Table 2 (with inuación) On the other hand, the compound of the formula (XII) used as the starting material for preparing the compound of the formula (IVb) is novel, and can be prepared by reacting a known 2,6-dihydroxybenzoic acid having the following formula (XV) with thionyl chloride in a solvent in the presence of a catalytic amount of dimethylammonopyridine as described in the following reaction scheme I.

Reaction scheme I: (XIV) (XV) in the reaction scheme I, R3, RB, Re, RT and Q are defined as previously described. In Reaction Scheme I, an ether such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc., a polar solvent such as dimethylformamide, dimethyl sulfoxide, etc., a halogenated hydrocarbon solvent such as dichloromethane, carbon tetraeloride, etc. ., or an aromatic hydrocarbon solvent such as benzene, toluene, xylene, e ::. , preferably dimethoxyethane or toluene can be used as the solvent. The reaction can be carried out at 10-80 ° C, preferably 20 to 30 ° C. Typical examples of the compound of formula XII prepared according to the process explained above are presented in the following table 3.

Table 3 Among the cyclic acrylic compound of the formula (IV) above, a compound of the formula (IVc) in which R__ represents (in which RT, Rio, Rn, R12, R13, X, Y and are defined as previously described) can be prepared as explained in the following reaction scheme J. According to reaction scheme J, a derivative of Diketone having the following formula (XVI) is introduced into the 2,6-dihydrobenzoic acid of the formula (XIV) using a halogenating agent to produce a cyclic acrylate compound having the following formula (XVII) in the first reaction step , the compound (XVII) thus obtained is reacted with a compound having the following formula (XVIII) to produce a compound having the following formula (XIX) in the second step and finally the compound (XIX) thus obtained is reacted with the pyrimidine derivative of the formula (VI) in the third reaction to prepare the compound of the formula (IVc). Scheme of reaction J: (JVc) In the reaction scheme J R3, RT to R13, X, Y, m and Z are defined as previously described. First, in the first reaction step the compound of the formula (XVII) was prepared by means of the reaction of 2,6-dihydrobenzoic acid of the formula (XIV) with the diketone derivative of the formula (XVI) in the presence of a halogenating agent. Suitable halogenating agents for this reaction are phosphorus oxychloride, thionyl chloride, etc. Particularly preferred is phosphorus oxychloride. The reaction of the first stage can preferably be carried out in a solvent. The suitable solvent for this reaction includes ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc., polar solvents such as dimethylformamide, dimethyl sulfoxide, etc., halogenated hydrocarbons such as dimethylformamide, dimethyl sulfoxide, etc., halogenated hydrocarbons such such as dichloromethane, carbon tetraeloride, etc., and aromatic hydrocarbons such as benzene, toluene, xylene, etc.; and a mixture of 2 or more of these solvents can also be used. The reaction temperature of the first stage is not specifically limited, however, it is conventionally desirable to carry out the reaction at 0 to 50 ° C, preferably 10 to 25 ° C for 4 to 6 hours. In the second step of the reaction scheme H, the cyclic acrylic compound (XVII) obtained in the first step is reacted with the compound of the formula (XVII) to produce the compound of the formula (XIX). This reaction is performed to protect the ketone group that has been introduced by the diketone derivative in the first step. The introduction of a protection group by means of the compound of the formula (XVIII) is carried out by means of a conventional ketalization process. That is, the compound (XVII) is reacted with the compound (XVIII) in a solvent in the presence of a catalyst while the water produced during the reaction is continuously removed by means of azotropic distillation. In this reaction, such as the base of pyrimidine hydrochloride, pyridine, p-toluenesulfonic acid, selenium oxide, oxalic acid, adipic acid, trifluoroboron diethyl ether, etc. it can be used, and a mixture of 2 or more of those catalysts can also be used. Among these catalysts, p-toluenesulfonic acid or pyridine can be more preferably used. This reaction can also be carried out in the presence of a solvent, and as the appropriate solvent for this purpose, one or more selected from the group consists of ethers such as tetrahydrofuran, diethyl ether, dimethoxy ethane, etc., polar solvents such as dimethylformamide , dimethyl sulfoxide, etc., halogenated hydrocarbons such as dichloromethane, carbon tetraeloride, etc., and aromatic hydrocarbons such as benzene, toluene, xylene, etc., can be exemplified. Among these solvents, the most preferred are toluene, dimethoxyethane or dichloromethane. The reaction temperature of the second stage is not specifically limited, however, it is conventional to carry out the reaction at 110 to 120 ° C, at which the toluene is distilled azotropically for 2 to 4 hours. In the third step of the reaction scheme J, the compound of the formula (XLX) obtained in the second step is reacted with the pyrimidine derivative (VI) to produce the derivative of 5- (4,6-dimethoxypyridin-2-) il) oxy-4H- (1, 3) -benzodioxin-4-one of the formula (IVc). The reaction of the third stage is preferably carried out in the presence of a base and as the appropriate base for this purpose, an inorganic base such as potassium carbonate, sodium carbonate, sodium hydride, sodium hydrocarbon, etc., can preferably be mention may be made of potassium carbonate or sodium hydride, sodium hydrocarbonate, etc., preferably potassium carbonate or sodium hydride. The reaction can vary in the range of the normal temperature to 150 ° C. Preferably the reaction is carried out at 50 to 80 ° C for 3 to 5 hours Typical examples of the compound of the formula (IVc) prepared according to the process as explained above are presented in the following table A.

Table 4 The present invention will be explained more specifically by means of the following examples. However, it should be understood that the following preparations and examples are intended to illustrate the present invention and do not limit the scope of the present invention in any way.

Preparation 1: Synthesis of sodium salt of acetophenone oxime To a mixture of 4.8 g of sodium hydride (60%) and 300 ml of tetrahydrofuran are slowly added 12 g of acetophenone oxime while maintaining the temperature below 5 ° C and the solution is stirred at normal temperature for 20 minutes. minutes The reaction mixture was then distilled under reduced pressure to give 13g (yield 93.7%) of the title compound with a white color.

IH NMR (DMSO-dβ, 270 MHz): 7.60 (d, 2H), 7.16 (t, 2H), 7.00 (t, 1H), 1.97 (s, 3H) EXAMPLE 1: Synthesis of 2- (furan-2) -yl) -5-hydroxy-4H- [1, 3-benzo-dioxin-4-one 1.54 g of 2,6-dihydrobenzoic acid, 1.0 g of 2-furyl aldehyde and a catalytic amount of dimethylaminopyridine were added to 10 ml of dimethoxyethane. The reaction temperature was reduced to 20 ° C and then 1676 g of thionyl chloride was slowly added dropwise to the reaction solution. After the addition was complete, the mixture was stirred for 4 hours and distilled under reduced pressure to remove the dimethoxyethane. 10 ml of dichloromethane were dissolved in the mixture, 10 ml of the aqueous solution of sodium bicarbonate were added thereto and then this mixture was extracted with 20 ml of dichloromethane. After removing the water contained in the extract over anhydrous magnesium sulfate, the extract is filtered through silica gel and distilled under reduced pressure to produce a solid compound. The compound thus produced was recrystallized from a small amount of dichloromethane and hexane to give 2.2g (9.5 mmol, 95% yield) of the title compound. IH NMR (DCCls, 270 MHz): d 10.1 (s, 0H), 7.55 (s, lH), 7.49 (t, lH), 6.76 (d, lH), 6.72 (s, lH), 6.64 (s, lH ), 6.57 (s.lH), 6.49 (s, LK).

EXAMPLE 2: Synthesis of 2- (furan-2-yl) -5-hydroxy-2-methyl-4H- [1, 3] -benzodioxin-4-one 1.54 g of 2,6-dihydroxybenzoic acid, 1.10 g of 2 Acetylfuran and a catalytic amount of dimethylaminopyridine were added to 10 ml of dimethoxyethane. The reaction temperature was reduced to 20 ° C and then 1.67 g of thionyl chloride were added slowly by dripping and added dropwise to the reaction solution. After the addition was complete, the mixture was stirred for 4 hours and distilled under reduced pressure to remove the dimethoxyethane, 10 ml of dichloromethane was dissolved in the mixture, 10 ml of aqueous sodium bicarbonate solution was added thereto, and This mixture is extracted with 20 ml of dichloromethane. After removing the water contained in the extract over anhydrous magnesium sulfate, the extract is filtered through silica gel and distilled under reduced pressure to produce a solid compound. The compound thus produced was recrystallized from a small amount of dichloromethane and hexane to give 2.31 g (9.39 mmol, 94% yield) of the title compound. IH NMR (CDCls, 270 MHz): d 10.17 (s, OH), 7.5-7.3 (m, 2H), 6.65 (d, lH), 6.52 (d, lH), 6.40 (d, lH), 6.30 (d , lH), 2.10 (ß, 3H). EXAMPLE 3: Synthesis of 5-hydroxy-2- (3-methoxythiophen-2-yl) -4H- [1, 3] -benzodioxin-4-one 1.54 g of 2,6-dihydroxybenzoic acid, 1.26 g of 3-methylthiophene aldehyde and a catalytic amount of dimethylaminopyridine were added to 10 ml of dimethoxyethane. The reaction temperature was reduced to 20 ° C. and then 1.67 g of thionyl chloride were added dropwise to the reaction solution After the addition was complete, the mixture was stirred for 4 hours and distilled under reduced pressure to give the reaction solution. Remove the dimethoxyethane, 10 ml of dichloromethane were dissolved in the mixture, 10 ml of aqueous sodium bicarbonate solution and then the mixture was extracted with dichloromethane, after removing the water contained in the extract over anhydrous magnesium sulfate.The extract was filtered through silica gel and distilled under reduced pressure to produce a solid compound. The compound thus produced was recrystallized from a small amount of dichloromethane and hexane to give 2.3 g (8.78 mmol, 88% yield) of the title compound. IH NMR (CDC1.3, 270 MHz): d 10.18 (S.0H), 7.48 (t, lH, 7.38 (d.lH), 6.89 (d, 1H), 6.79 (s, lH), 6.74 (d, 1H), 6.59 (d, 1H), 2.35 (s, 3H) EXAMPLE 4: Synthesis of 5-hydroxy-2-methyl-2- (lH-pyrrol-2-yl) -4H- [l, 3] - benzodioxin-4-one 1.54g of 2,6-dihydroxybenzoic acid, 1.09g of 2-acetylpyrrole and a catalytic amount of 4-dimethylaminopyridine were added to 10 ml of di-ethoxyethane.The reaction temperature was reduced to 20 ° C and then 1.67g of thionyl chloride was slowly added dropwise.

After the addition was complete, the mixture was stirred for 4 hours and distilled under reduced pressure to remove the dimethoxyethane. 10 ml of dichloromethane were dissolved in the mixture, 10 ml of aqueous sodium bicarbonate solution and then the mixture was extracted with dichloromethane. After removing the water contained in the extract over anhydrous magnesium sulfate, the extract was filtered through silica gel and distilled under reduced pressure to produce a solid compound with a deep violet color. The compound thus produced was recrystallized from a small amount of hexane to obtain 1.93 g (7.88 mmol, 79% yield) of the title compound. IH NMR (CDCls, 270 MHz): dlO .15 (s-OH), 8.32 (br, NH), 7.4 (t, lH), 6.74 (d, 1H), 6.55 (d, 1H), 6.50 (d, lH), 6.25 (d, lH), 6.10 * d, 1H), 2.05 (s, 3H). EXAMPLE 5: Synthesis of 2- (benzofuran-2-yl) -5-hydroxy-2-methyl-4H- [1,3] -benzodioxin-4-one 1.54 g (10 ml) of 2,6-dihydroxybenzoic acid, 1.60 g of benzofuran-2-ylmethyl ketone and a catalytic amount of 4-dimethylaminopyridine were added to 10 ml of dimethoxyethane. The reaction temperature was reduced to 20 ° C and then 1.67 g of thionyl chloride were added dropwise to the reaction solution. After the addition was complete, the mixture was stirred for 4 hours and distilled under reduced pressure to remove the dimethoxyethane. 10 ml of dichloromethane were dissolved in the mixture, 10 ml of aqueous sodium bicarbonate solution and then the mixture was extracted with dichloromethane. After removing the water contained in the extract over anhydrous magnesium sulfate, the extract was filtered through silica gel and stripped under reduced pressure to produce a solid compound. The compound thus produced was recrystallized from a small amount of dichloromethane and hexane to give 2.29 g (7.7 mmol, 77% yield) of the title compound. NMR JH (CDCls, 270 MHz): d 10.11 (s,) H), 7.54-7.21 (m, 5H), 6.77 (ß, lH), 6.58 (t, 2H), 2.15 (s, 3H) EXAMPLE 6: Synthesis of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-2- (f-2-i1) -4H- [1,3] -benzodioxin-4-one 1.16g (5 mmol) of 2- (furan-2-yl) -5-hydroxy-4H- [1, 3] -benzodiozin-4-one prepared in Example 1 and 2.07 g of potassium carbonate were dissolved in 10 ml of dimethylformamide. 1.09 g of 2-methyl-sulfonyl-4,6-dimethoxypyridimide were added, and the mixture was stirred at 80 ° C. After the completion of the reaction was confirmed by TLC, the reaction solution was mixed. with 100 ml of diethyl ether and 100 ml of water and then the organic layer is extracted The water contained in the extract was distilled under reduced pressure The residue was subjected to silica gel column chromatography (eluent: hexane / acetate ethyl acetate = 4/1, v / v) to give 1.57 g (4.2 mmol, yield 85%) of the title compound.MIH NMR (CDCl3, 270 MHz): d 7.53 (t, 1H), 7.42 (s, 1H) 6.95 (d, 2H), 6.52 (d, 1H), 6.45 (s, 1H), 6.38 (d, lH), 5.70 (s, 1H, 3.75 (s, 6H) EXAMPLE 7: Synthesis of 2- ( benzofuran-2-yl) -5- (4,6-dimethoxypyrimidin-2-yl) oxy-2-methyl-4H- [l, 3] -benzodioxin-4-one 0.16g (0.54 mmol) of 2- (benzofuran -2-yl) -5-hydroxy-2-methyl-4H- [l, 3] -benzodiozin-4-one prepared in Example 5 and 40 mg of potassium carbonate were dissolved in 10 ml of dimethylformamide 0.12 g of 2-Methylsulfonyl-4,6-di-ethoxypyridimide were added, and the mixture was stirred at 80 ° C. After the completion of the reaction was confirmed by means of TLC, the reaction solution was mixed with 100 ml of diethyl ether and 100 ml of water, and then the organic layer was extracted. The water contained in the extract was removed over anhydrous magnesium sulfate and then extracted under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 4/1, v / v) to obtain 0.16 g (0.38 mmol, yield 70%) of the title compound. IH NMR (CDCls, 270 MHz): d 7.52-7.42 (m, 3H), 7.29-7.20 (p_, 3H), 7. 00-6.97 (d, 1H), 6.88 (d, 1H), 6.77 (s, lH), 3.62 (s, 6H), 2.11 (s, 3H). EXAMPLE 8: Synthesis of 5- (4, 6-dimethoxypyrimidin-2-yl) oxy-2- (3-methylthiophen-2-yl) -4H- [l, 3] -benzodioxin-4-one 0.42g (1.6 mmol) of 5-hydroxy-2- ( 3-methylthiophen-2-yl) -4H- [1,3] -benzodiozin-4-one prepared in Example 3 and 0.46 mg of potassium carbonate were dissolved in 10 ml of dimethylformamide. 0.60 g of 2-methylsulfonyl-4,6-di ethoxypyridimide were added, and the mixture was stirred at 80 ° C. After the completion of the reaction was confirmed by means of TLC, the reaction solution was mixed with 100 ml of diethyl ether and 100 ml of water, and then the organic layer was extracted. The water contained in the extract was removed over anhydrous magnesium sulfate and then extracted under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 4/1, v / v) to obtain 0.52 g "(1.3mmol, yield 81%) of the title compound. RMH iH (CDCls , 270 MHz): d 7.52 (t, lH), 7.05 (d, 1H), 6.98 (d, 1H), 6.78 (d, lH), 6.7 (d, 1H), 5.71 (s, lH), 3.69 ( s, 6H), 2.3 (s, 3H), 2.04 (s, 3H) EXAMPLE 9: Synthesis of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-2-methyl-2- (l-methylpyrrole-2) -yl) -4H- [l, 3] -benzodioxin-4-one 0.87g (3.35mmol) of 5-hydroxy-2-methyl-2- (1-methylpyrrol-2-yl) -4H- [l, 3 ] -benzodiozin-4-one and 0.23 mg of potassium carbonate were dissolved in 10 ml of dimethylformamide 0.73 g of 2-methylsulfonyl-4,6-dimethoxypyridimide were added, and the mixture was stirred at 80 ° C. the completion of the reaction was confirmed by means of TLC, the reaction solution was mixed with 100 ml of diethyl ether and 100 ml of water, and then the organic layer was extracted.The water contained in the extract was removed over sodium sulfate. anhydrous magnesium and then It is extracted under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 4/1, v / v) to obtain 1.0 g (2.52 mmol, yield 75%) of the title compound. 1 H NMR (CDCls, 270 MHz): d 7.48 (t, 1 H), 6.87 (d, 1 H), 6.59 (m, 1 H), 6.4 (m, 1 H), 6.03 (m, 1 H), 5.73 (s, 1 H) ), 3.71 (s, 6H), 3.53 (s, 3H), 1.96 (s, 3H) EXAMPLE 10: Synthesis of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-2- (furan-2-yl) ) -2-methyl) -4H- [1, 3] -benzodioxin-4-one l.Og (4 mmol) of 2- (furan-2-yl) -5-hydroxy-2-methyl-4H- [l , 3] -benzodiozin-4-one prepared in example 2 and 0.89 mg of potassium carbonate were dissolved in 10 ml of dimethylformamide. 0.89 g of 2-methylsulfonyl-4,6-dimethoxypyridimide were added, and the mixture was stirred at 80 ° C. After the completion of the reaction was confirmed by means of TLC, the reaction solution was mixed with 100 ml of diethyl ether and 100 ml of water, and then the organic layer was extracted. The water contained in the extract was removed over anhydrous magnesium sulfate and then extracted under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 4/1, v / v) to obtain 1.1 g (2.86 mmol, yield 75%) of the title compound. AH NMR (CDCls, 270 MHz): d 7.50 (t, 1H), 7.32 (s, 1H), 6.9 (dd, 2H), 6.38 (d, lH), 6.25 (d, 1H), 5.77 (s, lH ), 3.78 (s, 6H), 2.04 (s, 3H) EXAMPLE 11: Synthesis of 2,5-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid acetophenone oxime ester 16 g sodium salt of acetophenone acetophenone oxime prepared in preparation 1 were dissolved in 100 ml of dimethylformamide and this solution was added dropwise to a solution of 37.0 g of 5- (4,6-dimethoxypyridimin-2-yl) oxy-2- (furan-2) -yl) -4H- [1, 3] -benzodioxin-4-one prepared in Example 6 in 100 ml of dimethylformamide at room temperature. The resulting solution was stirred for 30 minutes and added dropwise to a mixture of 21.8 g of 4,6-dimethoxy-2-methylsulfonylpyridimine and 1.38 g of potassium carbonate in 60 ml of dimethylformamide. The reaction solution was stirred for 1 hour maintaining the temperature at 80 to 85 ° C, and then distilled under reduced pressure to remove the solvent. The residue is extracted with water and dichloromethane, and the separated organic layer is dried over anhydrous sodium sulfate, distilled under reduced pressure and recrystallized from acetone to obtain 35 g of the title compound as a white solid. IH NMR (CDCls, 270 MHz): d 7.19-7.62 (m, 8H), 5.73 (s, 2H), 3.78 (s, 12H), 2.26 (s, 3H) MS (FAB) 548 pf: 85-94 ° C EXAMPLE 12: Synthesis of 2,6-di (4,6-dimethoxypyrimin-2-yl) oxybenzoic acid acetophenone oxime ester 16 g of acetophenone oxime sodium salt prepared in preparation 1 were dissolved in 100 ml of dimethylformamide, and this solution was added dropwise to a solution of 37. Og of 5- (4,6-dimethoxypyrimin-2-yl) -oxy-2- (furan-2-yl) -4 H- [1,3] -benzodioxin-4- one prepared in Example 6 in 100 ml of dimethylformide at room temperature. The resulting solution was stirred for 30 minutes and then 21.8 g of 4,6-dimethoxy-2-methylsulfonyl-pyrimidine and 1.3 g of potassium carbonate were added. The temperature of the reaction solution was raised to 80-85 ° C and then the solution was stirred for 3 to 4 hours. The solvent was distilled under reduced pressure and the residue was treated according to the same procedure as in example 11 to obtain 30 g of the title compound. EXAMPLE 13: Synthesis of benzophenone oxime ester of acid, 6-di (4,6-dimethoxy-pyrimidin-2-yl) oxybenzoic acid 50 g of sodium hydride (60%) and 38.4 g of 5- (4,6-dimethoxy-pyrimidine) 2-yl) oxy-2- (furan-2-yl) -2-me-4H- [l, 3] -benzodioxin-4-one prepared in Example 10 were added to 10 ml of dimethylformamide and the temperature of the mixture was maintained at 5 ° C. To this mixture were added dropwise 19.7 g of benzophenone oxime dissolved in 40 ml of dimethylformamide and the resulting solution was stirred for 20 minutes at normal temperature. After the reaction was complete, the entire mixture was added dropwise to a mixture of 21.8 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 1.3 g of potassium carbonate in 100 ml of dimethylformamide. The reaction solution was stirred for 2 hours while maintaining the temperature at 80 ° C, and then distilled under reduced pressure to remove the solvent. The residue is treated according to the procedure of Example 11 to obtain 34g of the title compound. IH NMR (CDCls, 270 MHz): d 7.10-7.48 (m, 13H), 5.72 (s, 2H), 3.72 (s, l 2H), MS (FAB) 610 p.f. 128-130 ° C. EXAMPLE 14: Synthesis of benzophenone oxime ester of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid 50 g of sodium hydride (60%) and 38 g of 5- (4,6-dimethoxypyrimin) 2-yl) oxy-2- (3-methylthiophen-2-yl) -4H- [1,3] -benzodioxin-4-one prepared in Example 8 were added to 150 ml of dimethylformamide and the temperature of the mixture was kept at 5 ° C. To this mixture were added dropwise 19.7 g of benzophenone oxime dissolved in 40 ml of dimethylformamide. The temperature of the resulting solution was raised to room temperature and then the solution was stirred for 20 minutes. 21.8 g of 4,6-dimethoxy-2-ethylsulfonylpyridine and 1.3 g of potassium carbonate were added and the whole mixture was stirred for 3 to 4 hours maintaining the temperature at 80-85 ° C. The solvent was removed by distillation under reduced pressure and then the residue was treated according to the same procedure as in Example 11 to obtain 34g of the title compound. EXAMPLE 15: Synthesis of 2,6-di (4,6-dimethoxypyridin-2-yl) oxybenzoic acid EXAMPLE 18: Synthesis of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-2-benzophenone oxime ester phenyl-4H- [1,3] -benzodioxin-4-one 19.7 g of benzophenone oxime were added to 5.0 g of sodium hydride (60%) dissolved in 300 ml of tetrahydrofuran and the mixture was stirred for 20 minutes at room temperature. normal temperature. To this reaction mixture were added 37.0 g of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-2- (furan-2-yl) -4H- [1,3] -benzodioxin-4-one prepared in Example 6. The whole mixture was stirred for 20 minutes at normal temperature and distilled under reduced pressure to obtain sodium salt of benzophenone oxime ester of 2- (4,6-dimethoxypyrimidin-2-yl) -oxi acid. -6-hydroxybenzoic. Thus the solid salt produced was extracted with water and dichloromethane. The organic layer was separated dried over anhydrous sodium sulfate and distilled under reduced pressure to obtain 30 g of benzophenone oxime ester of 22- (4%) acid., 6-dimethoxypyrimidin-2-yl) oxy-6-hydroxybenzoic acid and benzophenone oxymethyl ester. The resulting compound was dissolved in 100 ml of dimethylformamide without further step of isolation or purification, this solution was added dropwise to a mixture of 1.3 g of potassium carbonate and 21.8 h of 4,6-dimethoxy-2-methylsulfonylpyrimidine in 60 ml. of dimethylformamide at 80 ° C. The entire mixture was stirred for one hour maintaining the temperature at 80-85 ° C and was distilled under reduced pressure to remove the solvent. The residue was treated according to the same procedure as in Example 11 to obtain 30 g of the title compound. EXAMPLE 16: Synthesis of 5- (4,6-dimethoxypyrimidin-2-yl) -oxi-2, 2-dimethyl-4H- [1,3] -benzodioxin-4-one 2.0 G of 2- (4, 5) acid -dimethoxypyridimin-2-yl) oxy-6-hydroxybenzoic acid, 60 mg of dimethylaminopriidine and III of acetone were added to 10 ml of dimethoxyethane. The reaction temperature was reduced to 20 ° C and then 3 g of thionyl chloride dissolved in 1 ml of dimethoxyethane were added slowly by dripping keeping the temperature below 30 ° C. After the addition was complete the mixture was stirred for 2 hours. Then nitrogen gas is blown into the reaction vessel to remove the anhydrous hydrochloride acid or the reaction is then distilled under reduced pressure. The residue was dissolved in 100 ml of a solvent mixture of hexane-dichloromethane (1: 1, v / v), filtered through silica gel and then distilled under reduced pressure. To the residue was added 200 ml of hexane and the resulting solution was allowed to stand at 15 ° C until a white solid was produced. The solid thus produced was filtered to obtain 1.6g of the title compound. J-NMR (270MHz, CDCls): dl.72 (s, 6H), 3.82 (s, 6H), 5.75 (s, 1H), 6.91 (q, 2H), 7.55 (t, 1H) EXAMPLE 17: Synthesis of 5- (4,6-dimethoxypyridimin-2-yl) oxy-2-cyclohexylene-4H- [1,3] -benzodioxin-4-one 3.1g of 2- (4,6-dimethoxypyridimin) 2-yl) -oxi-6-hydroxybenzoic acid, 62 mg of 4-dimethylaminopriidine and 1.32 g of cyclohexanone were added to 10 ml of dimethoxyethane. The reaction temperature was reduced to 20 ° C and then 3 g of thionyl chloride dissolved in 1 ml of dimethoxyethane were added by dripping slowly keeping the temperature below 30 ° C. After the addition was complete, the mixture was stirred for 2 hours. Then, nitrogen gas was blown into the reaction vessel to remove the anhydrous hydrochloric acid and then the reaction solution was distilled under reduced pressure. The residue was treated according to the same procedure as in Example 16 to obtain 1.29 g of the title compound with a white color. NMR JH (270 MHz, CDCl 3): 5 1.39-1.69 (m, 6H), 1.87-2.03 (m, 4H), 3.81 (s, 6H), 5.77 (s, lH), 6.41 (d, lH), 6.56 (d, 1H), 7.35 * t, 1H), 10.29 (s, 1H) EXAMPLE 18: Synthesis of 6- (4,6-dimethoxypyrimin-2-yl) oxy-2-phenyl-4H- [1, 3] -benzodioxin-4-one 0.8g of 5-hydroxy-2-phenyl-4H- [l, 3] 0benzodioxin-4-one, 0.68g of potassium carbonate and 0.72g of 4,6-dimethoxy-2-methylsulfonyl- pyrimidine was added to 50 ml of dimethylformamide. The reaction solution was stirred for 6 hours while heating to 80-85 ° C. The solvent was evaporated from the solution and then water and dichloromethane were added to the residue to extract the organic layer. The separated organic layer was dried over anhydrous sodium sulfate, evaporated and subjected to silica gel column chromatography to obtain l.lg of the title compound. IH NMR (270 MHz, CDCls): d 3.83 (s, 6H), 5.78 (s, 1H), 6.49 (s, lH), 7.04 (d, 2H), 7.41-7.48 (m, 3H), 7.61-7.65 (m, 3H) EXAMPLE 19: Synthesis of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-4H- [1,3] -benzodioxin-4-one 6.0 g of 2- (4,6-dimethoxypyrimidine) -2-yl) -oxi-6-hydroxybenzoic acid, 20 g of dibromomethane and 2 g of potassium hydroxide were dissolved in 30 ml of dimethylformamide, and the mixture was stirred under reflux for 10 hours. The solvent was then distilled under reduced pressure and the residue subjected to silica gel column chromatography to obtain 0.55 g of the title compound. IH NMR (270 MHz, CDCls): d 7.58 (t, lH), 7.01 (d, 1H), 6.97 (d, lH), 5.76 (s, lH), 5.60 (s, 2h), 3.81 (m, 6H EXAMPLE 20: Synthesis of 5- (4,6-dimethoxypyridimin-2-yl) oxy-2-methy1-2- (2-methylpropin-1-yl) -4H- [1,3] -benzodioxin-4-one 2.9 g of 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6-hydroxybenzoic acid, 60 mg of 4-dimethylaminopyridine and 1.0 g of 4-methyl-3-penten-2-one were added to 10 ml of dimethoxyethane. The reaction temperature was reduced to 20 ° C and then 3 g of thionyl chloride dissolved in 1 ml of dimethoxyethane were added by dripping slowly keeping the temperature below 30 ° C. After the addition was complete the mixture was stirred for 2 hours. Then nitrogen gas was blown into the reaction vessel to remove the anhydrous hydrochloric acid and then the reaction solution was distilled under reduced pressure. The residue was dissolved in 100 ml of solvent mixture of hexane-dichloromethane (1: 1, v / v), filtered through silica gel and then distilled under reduced pressure. To the residue was added 200 ml of hexane and the resulting solution was allowed to stand at 15 ° C until a solid was produced. The solid thus produced is filtered to obtain 1.9 g of the title compound. IH NMR (270 MHz, CDCls): d 1.64 (s, 3H), 1.80 (s, 6H), 3.79 (s, 6H), 5.35 (s, lH), 5.74 (s, lH), 6.88 (t, 2H ), 7.51 (t, lH) EXAMPLE 21: Synthesis of acetophenone oxime ester of 2,6-di (4,6-dimethoxypyridimin-2-yl) oxybenzoic acid 13g of acetophenone oxime sodium salt prepared in Preparation 1 was dissolved in 40 ml of dimethylformamide, and this solution was added dropwise at room temperature to 27.0 g of 5- (4,6-dimethoxypyridimin-2-yl) oxy-2,2-dimethyl-4H_ [1, 3]. ] 0benzodioxin-4-one dissolved in 100 ml of dimethylformamide. The resulting solution was stirred for 30 minutes and added dropwise to a mixture of 18.0 g of 4, 6-dimethoxy-2-methylsulfonylpyrimidine and 11.4 g of potassium carbonate in 60 ml of dimethylformamide. The resulting solution was stirred for 30 minutes and added to a mixture of 18.0 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 11.4 g of potassium carbonate in 60 ml of dimethylformamide. The reaction solution was stirred for 1 hour maintaining the temperature at 80 to 85 ° C, and then distilled under reduced pressure to remove the solvent. The residue is extracted with water and dichloromethane, and the separated organic layer is dried over anhydrous sodium sulfate, distilled under reduced pressure and recrystallized from acetone to obtain 24 g of the title compound as a white solid. EXAMPLE 22: Synthesis of benzophenone oxime ester of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid 5.0 g of sodium hydride (60%) and 38 g of 5- (4,6- dimethoxypyridimin-2-yl) oxy-2-phenyl-4H- [1,3] -benzodioxin-4-one were added to 100 ml of dimethylformamide and the temperature of the mixture was maintained at 5 ° C. To this mixture were added dropwise 19.7 g of benzophenone oxime dissolved in 40 ml of dimethylformamine and the resulting solution was stirred for 20 minutes at normal temperature. Upon completion of the reaction, the entire mixture was added dropwise to a mixture of 21.8 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 1.3 g of potassium carbonate in 100 ml of dimethylformamide. The reaction solution was stirred for 2 hours while maintaining the temperature at 80 ° C, and then distilled under reduced pressure to remove the solvent. The treatment residue according to the same procedure as in example 21 to obtain 38 g of the title compound. EXAMPLE 23: Synthesis of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid benzaldoxime ester 5.0 g of sodium hydride (60%) and 33.2 g of 5- (4,6-dimethoxypyrimidine) 2-yl) oxy-2,2-dimethyl-4H- [l, 3] -benzodoxin-4-one were added to 10 ml of dimethylformamide and the temperature was maintained at 5 ° C. To this mixture were added dropwise 12.1 g of benzaldehyde oxime dissolved in 40 ml of dimethylformamide and the resulting solution was stirred for 20 minutes at normal temperature. After the reaction was complete, the entire mixture was added dropwise to a mixture of 21.8 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 1.3 g of potassium carbonate in 100 ml of dimethylformamide. The reaction solution was stirred for 2 hours while maintaining the temperature at 80 ° C and then distilled under reduced pressure to remove the solvent. The residue was treated according to the same procedure as in Example 21 to obtain 42.1 g of the title compound. IH NMR (CDCls, 270 MHz): d 8.09 (s, 1H), 7.20-7.61 (, 8H), 5.73 (s, 2H), 3.78 (s, 12H) EXAMPLE 24: Synthesis of 4-nitrobenzaldoxime ester of acid 2,6-di (4,6-dimethoxypyrimidin-2-yl) -oxybenzoic acid 5.0 g of sodium hydride (60%) and 38 g of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-2, 2 Dimethyl-4H- [1, 3] 0-benzodioxin-4-one were added to 150 ml of dimethylformamide and the temperature was maintained at 5 ° C. To this mixture was added dropwise 16.6 g of 4-nitrobenzaldoxime dissolved in 40 ml of dimethylformamide and the resulting solution was stirred for 20 minutes at room temperature. 21.8 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 1.3 g of potassium carbonate were added to this reaction mixture and the temperature was raised to 80-85 ° C. The solution was then stirred for 3 to 4 hours at that temperature and distilled under reduced pressure to remove the solvent. The residue was treated according to the same procedure as in Example 21 to obtain 39.9 g of the title compound. IH NMR (CDCls, 270 MHz): d 7.21-8.27 (, 8H), 5.74 (s, 2H), 3.79 (s, 12H) EXAMPLE 25: Synthesis of 2,6-di (4-methoxybenzaldoxime 2,6-di-4-methoxy ester) , 6-dimethoxy-pyridin-2-yl) oxybenzoic acid 15.1 g of 4-methoxybenzaldoxime were added to 5.0 g of sodium hydride (60%) dissolved in 300 ml of tetrahydrofuran and the mixture was stirred for 20 minutes at normal temperature. To this reaction mixture was added 38.Og of 5- (4, 6-dimethoxypyrimidin-2-yl) oxy-2-phenyl-4H- [1,3] -benzodioxin-4-one. The whole mixture was stirred for another 20 minutes at normal temperature and was distilled under reduced pressure to obtain the sodium salt of 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6-hydroxybenzoic acid 4-methoxybenzaldoxime ester. . The solid salt thus produced is extracted with water and dichloromethane. The separated organic layer was extracted with water and dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate and stripped under reduced pressure to obtain 30 g of 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6-hydroxybenzoic acid 4-methoxybenzaldoxime ester. The resulting compound was dissolved in 100 ml of dimethylformamide without isolation step or subsequent purification, and the solution thus obtained was added dropwise to a mixture of 1.3 g of potassium carbonate and 21.8 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine. dissolved in 60 ml of dimethylformamide at 80 ° C. The entire mixture was stirred for one hour maintaining the temperature at 80-85 ° C and was distilled under reduced pressure to remove the solvent. The residue was treated according to the same procedure as in Example 21 to obtain 35g of the title compound. Preparation 2: Synthesis of 5-hydroxy-2-methyl-2- (2-oxo-propyl) -benzo [1,3] dioxin-4-one 15.4 g of 2,6-dihydroxybenzoic acid, 13. Og of 2, 4-pentanedione and 7.3 g of dimethylformamide were dissolved in 150 ml of toluene and the resulting mixture was stirred keeping the temperature at 10 ° C. To this mixture was added dropwise 15.3 g of phosphorus oxychloride maintaining the temperature in a range of 10 to 20 ° C and the resulting solution was stirred for 6 hours at normal temperature to complete the reaction. After the completion of the reaction was confirmed by means of TLC, sodium carbonate solution and aqueous sodium bicarbonate solution were sequentially used to neutralize the organic layer. The separated organic layer was washed with brine and water (once each), dried over anhydrous sodium sulfate and filtered. The filtrate was distilled under reduced pressure and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 10/1) to obtain 20.2 g (yield 85.5%) of the title compound with a white color. IH NMR (270 MHz, CDCls): d 10.24 (s, lH), 7.45 (t, 1H), 6.67 (s, lH), 6.48 (d, lH), 3.14 (q, 2H), 2.27 (s, 3H ), 1.83 (s, 3H) Preparation 3: Synthesis of 5-hydroxy-2-methyl-2- (2-methyl- [1,3] -dioxaran-2-ylmethyl) benzo [l, 3] dioxin-4- Method A: 11.8 g of 5-hydroxy-2-methyl-2- (2-oxo-propyl) -benzo [1,3] -dioxin-4-one prepared in Preparation 2 and 12.4 g of ethylene glycol were dissolved in 100 ml of toluene and to this solution 0.95 g of p-toluenesulfonic acid and 0.4 g of pyridine were added. The resulting solution was refluxed for 2 hours by continuously removing the water. After the completion of the reaction was confirmed by TLC, the organic layer was separated, washed three times with aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate and filtered. The filtrate was styled under reduced pressure and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 10 / L) to obtain 12.9 g (yield 92.1%) of the title compound. IH NMR (CDCls 270 MHz): d 10.24 (S, 1H), 7.33 (t, 1H), 6.56 (d, 1H), 6.35 (d, 1H), 3.88 (m, 4H), 2.30 (s, 2H) , 1.77 (s, 3H), 1.34 (s, 3H) Method B: 15.4 f of 2,6-dihydroxybenzoic acid, 13.0 g of 2,4-pentadione and 7.3g of dimethylformamide were dissolved in 150 ml of toluene and stirred keeping the temperature at 10 ° C. To this mixture, 15.3 g of phosphorus oxychloride were added dropwise maintaining the temperature in a range of 10 to 20 ° C and the resulting solution was stirred for 6 hours at normal temperature to complete the reaction. After the reaction was complete, sodium carbonate solution and aqueous sodium bicarbonate solution were sequentially used to neutralize the reaction solution from which the toluene layer was separated. The separated toluene layer is dried over anhydrous sodium sulfate and filtered. Then 21.0 g of ethylene glycol was added to this filtrate, 1.6 g of p-toluenesulfonic acid and 0.7 g of pyridine and the resulting solution was reacted for 2 hours by removing the water under azotropic distillation. After the reaction was complete, the organic layer was separated, washed with aqueous sodium bicarbonate aqueous solution and then washed twice with water. The organic layer was dried over anhydrous sodium sulfate and distilled under reduced pressure to obtain 22.6 g (Yield 80.7%) of the title compound in the form of a syrup. The NMR data of the compound thus obtained were identical to those mentioned in method A. Preparation 4: Synthesis of 5-hydroxy-2-methyl-2- (2-methyl- [1, 3] -dithioran-2-ylmethyl) benzo [1,3] dioxin-4-one 11.8 g of 5-hydroxy-2-methyl-2- (2-oxo-propyl) -benzo [1,3] -dioxin-4-one prepared in preparation 2, 18.8 g of 1,2-ethanethiol, 0.95 g of p-toluenesulfonic acid and 0.4 g of pyridine were dissolved in 100 ml of toluene and this solution was refluxed for 4 hours by completely removing the water. After the end of the reaction was confirmed by TLC, the organic layer was separated, washed three times with aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate and filtered. The filtrate was distilled under reduced pressure and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane 10/1) to obtain 13.7 g (87.8% yield) of the title compound.

Preparation 5: Synthesis of 5-hydroxy-2-methyl-2- (2,5,5-trimethyl- [1, 3] dioxan-2-ylmethyl) benzo [1,3] dioxin-4-one 11.8 g of 5 -hydroxy-2-methyl-2- (2-oxo-propyl) -benzo [1,3] -dioxin-4-one prepared in Preparation 2, 20.8 g of 2,2-dimethyl-1,3-propanediol, 0.95 g of p-toluenesulfonic acid and 0.4 g of pyridine were dissolved in 100 ml of toluene and this solution was refluxed for 4 hours by continuously removing the water. After the completion of the reaction was confirmed by TLC, the organic layer was separated, washed three times with aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate and filtered. The filtrate was distilled under reduced pressure and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 10/1) to obtain 12.9 g (yield 80.0%) of the title compound. Preparation 6: Synthesis of 5-hydroxy-2-methyl-2- (2, 4,5-trimethyl- [1, 3] dioxaran-2-ylmethyl) benzo [1, 3] dioxin-4-one 11.8 g of 5 -hydroxy-2-methyl-2- (2-oxo-propyl) benzo [1,3] dioxin-4-one prepared in that prepared in preparation 2, 18.0 g of 2,3-butanediol, 0.95 g of p-acid toluenesulfonic acid and 0.4 g of pyridine were dissolved in 100 ml of toluene and this solution was refluxed for 4 hours while the water was completely removed. Upon confirmation of the reaction by means of TLC, the organic layer was separated, washed three times with aqueous sodium bicarbonate solution, dried over sodium sulfate and filtered. The filtrate was distilled under reduced pressure and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 10/1) to obtain 12.7 g (yield 82.4%) of the title compound.

EXAMPLE 26: Synthesis of 5- (6,6-dimethoxypyrimidin-2-yl) oxy-2-methyl-2- (2-methyl- [1,3] dioxaran-2-ylmethyl) -benzo [1,3] dioxin -4-one 14. Og of 5-hydroxy-2-methyl-2- (2-methyl- [1,3] -dioxaran-2-ylmethyl) -benzo- [1,3] dioxin-4-one prepared in Preparation 3 and 12. Og of 2-methylsulfonyl-4,6-dimethoxypyrimidine were dissolved in 150 ml of toluene, and to this solution were added 10.4 g of potassium carbonate as base. The resulting solution was stirred for 3 hours under reflux. Upon confirmation of the reaction by means of TLC, the organic layer was separated, washed with 100 ml of water three times to remove the potassium carbonate, dried over anhydrous sodium sulfate and filtered. The filtrate was distilled under reduced pressure and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 10/1) to obtain 20.lg (yield 96.0%) of the title compound with a white color. . IH NMR (CDCls 270MHz): d 7.56 (t, 1H), 6.94 (d.1H), 6.88 (d, 1H), 5.75 (s, 1H), 391-3.95 (m, 4H), 3.82 (s, 6H) ), 2.38 (q, 2H), 1.82 (s, 3H), 1.40 (s, 3H) EXAMPLE 27: Synthesis of 4- (4,6-dimethoxypyrimidin-2-yl) oxy-2-methyl-2- (2 -methyl- [1,3] titioran-2-ylmethyl) -benzo [1,3] dioxin-4-one 15.6 g of 5-hydroxy-2-methyl-2- (2-methyl- [1,3] - dithioran-2-ylmethyl) benzo- [1,3] dioxin-4-one prepared in preparation 4 and 12.0 g of 2-methylsulfonyl-4,6-dimethoxypyrimidine were dissolved in 150 ml of toluene, and to this solution 10.4 were added. g of potassium carbonate as a base. The resulting solution was stirred for 3 hours under reflux. Upon confirmation of the reaction by means of TLC, the organic layer was separated, washed with 100 ml of water three times to remove the potassium carbonate, dried over anhydrous sodium sulfate and filtered. The filtrate was distilled under reduced pressure and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 10/1) to obtain 18.8g (yield 83.4%) of the title compound with a white color. EXAMPLE 28: Synthesis of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-2-methyl-2- (2,5,5-trimethyl- [1,3] dioxan-2-ylmethyl) -benzo [1.3 ] dioxin-4-one 16.1 g of 5-hydroxy-2-methyl-2- (2,5,5-trimethyl- [l, 3] -dioxan-2-ylmethyl) benzo- [1,3] dioxin-4 -one prepared in preparation 5 and 12.0 g of 2-methylsulfonyl-4, 6-dimethoxypyrimidine were dissolved in 150 ml of toluene, and to this solution were added 10.4 g of potassium carbonate as base. The resulting solution was stirred for 3 hours under reflux. Upon confirmation of the reaction by means of TLC, the organic layer was separated, washed with 100 ml of water three times to remove the potassium carbonate, dried over anhydrous sodium sulfate and filtered. The filtrate was distilled under reduced pressure and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 10/1) to obtain 22.4 g (yield 91.0%) of the title compound with a white color. EXAMPLE 29: Synthesis of acetophenone oxime ester of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid 0.75 g of acetophenone oxime sodium salt prepared in Preparation 1 was dissolved in 5 ml. of dimethylformamide and this solution was added dropwise to 4.2 g of 5- (4,6-dimethoxypyridin-2-yl) oxy-2-methyl-2- (2-methyl- [1,3] -dioxaran-2-ylmethyl ) benzo [1,3] dioxin-4-one prepared in Example 26 dissolved in 20 ml of dimethylformamide at room temperature. The resulting solution was stirred for 30 minutes and 2.3 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 0.15 g of potassium carbonate in 10 ml of dimethylformamide were added dropwise to the mixture. The reaction solution was stirred for 2 hours maintaining the temperature at 80-85 ° C and then distilled under reduced pressure to remove the solvent. The residue was extracted with water and dichloromethane, and the separated organic layer was dried over anhydrous sodium sulfate, distilled under reduced pressure and recrystallized from acetone to obtain 4.1 g (yield 85.0%) of the title compound as a white solid. . EXAMPLE 30: Synthesis of benzophenone oxime ester of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid 4.4g of sodium hydride (60%) and 41.8 g of 5- (4,6- dimethoxypyrimidin-2-yl) oxy-2-methy1-2- (2-methyl- [1,3] dioxaran-2-ylmethyl) -benzo [1,3] dioxin-4-one prepared in Example 26 were added to 200 ml of dimethylformamide and the temperature was kept at 5 ° CA this mixture were dripped 19.8 g of benzophenone oxime dissolved in 100 ml of dimethylformamide and the resulting solution was stirred for 20 minutes at normal temperature. After the reaction was complete, the entire mixture was added dropwise to a mixture of 24.0 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 1.4 g of potassium carbonate in 150 ml of dimethylformamide. Then the solution was stirred for 2 hours maintaining the temperature at 80 ° C, and then distilled under reduced pressure to remove the solvent. The residue is treated according to the procedure of Example 29 to obtain 52g (yield 85.4%) of the title compound. EXAMPLE 31: Synthesis of benzophenone oxime ester of 2,6-di (4,6-dimethoxypyrimidin-2-yl) -oxybenzoic acid 0.44g of sodium hydride (60%) and 4.5 g of 5- (4,6-dimethoxypyrimidine) -2-yl) oxy-2-methy1-2- (2-methyl- [1,3] dithioran-2-ylmethyl) -benzo [1,3] dioxin-4-one prepared in Example 27 were added to 20 of dimethylformamide and the temperature was maintained at 5 ° C. To this mixture were added dropwise 2. Og of benzophenone oxime dissolved in 10 ml of dimethylformamide and the resulting solution was stirred for 20 minutes at normal temperature. After the reaction was complete, the entire mixture was added dropwise to a mixture of 2.4 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 0.15 g of potassium carbonate in 15 ml of dimethylformamide. The solution was then stirred for 2 hours maintaining the temperature at 80 ° C, and distilled under reduced pressure to remove the solvent. The waste was treated according to e? procedure of Example 29 to obtain 4.4g (yield 72.0%) of the title compound. EXAMPLE 32: Synthesis of benzophenone oxime ester of 2,6-di (4,6-dimethoxypyrimidin-2-yl) -oxybenzoic acid 0.44g of sodium hydride (60%) and 4.9 g of 5- (4,6-dimethoxypyrimidine) -2-yl) oxy-2-methyl-2- (2, 5,5-trimethyl- [1, 3] dioxan-2-ylmethyl) -benzo [1,3] dioxin-4-one prepared in Example 28 were added to 20 ml of dimethylformamide and the temperature was maintained at 5 °. C. To this mixture was added dropwise 2.0 g of benzophenone oxime dissolved in 10 ml of dimethylformamide and the resulting solution was stirred for 20 minutes at normal temperature. After the reaction was complete, the entire mixture was added dropwise to a mixture of 2.4 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 0.15 g of potassium carbonate in 15 ml of dimethylformamide. The solution was then stirred for 2 hours maintaining the temperature at 80 ° C, and distilled under reduced pressure to remove the solvent. The residue was treated according to the procedure of Example 29 to obtain 4.6g (yield 76.1%) of the title compound. EXAMPLE 33: Synthesis of benzaldoxime oxime ester of 2,6-di (4,6-dimethoxypyrimidin-2-yl) -oxybenzoic acid 0.44g of sodium hydride (60%) and 4.2 g of 5- (4,6-dimethoxypyrimidine) -2-yl) oxy-2-methyl-2- (2-methyl- [1, 3] dioxan-2-ylmethyl) -benzo [1,3] dioxin-4-one prepared in Example 26 were added to 20 of dimethylformamide and the temperature was maintained at 5 ° C. To this mixture was added dropwise 1.2 g of benzaldehyde oxime dissolved in 10 ml of dimethylformamide and the resulting solution was stirred for 20 minutes at normal temperature. After the reaction was complete, the entire mixture was added dropwise to a mixture of 2.4 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 0.15 g of potassium carbonate in 20 ml of dimethylformamide. The solution was then stirred for 2 hours maintaining the temperature at 80 ° C, and distilled under reduced pressure to remove the solvent. The residue was treated according to the procedure of Example 29 to obtain 4.6 g (86% yield) of the title compound. EXAMPLE 34: Synthesis of 2,4-nitrobenzaldoxime ester of 2, d-di (4,6-dimethoxypyrimidin-2-yl) -oxybenzoic acid 0.44g of sodium hydride (60%) and 4.2 g of 5- (4,6-dimethoxypyrimidine) -2-yl) oxy-2-methy1-2- (2-methyl- [1,3] dioxaran-2-ylmethyl) -benzo [1,3] dioxin-4-one prepared in Example 26 were added to 20 dimethylformamide and the temperature was kept at 5 ° C. To this mixture 1.7g of 4-nitrobenzaldoxime dissolved in 10 ml of dimethylformamide was added dropwise and the resulting solution was warmed to room temperature and then stirred for 20 minutes. To this reaction mixture were added 2.4 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 0.3 g of potassium carbonate.The reaction mixture was heated to 80-85 ° C., stirred for 3 to 4 hours and distilled under reduced pressure to remove the solvent The residue was treated according to the same procedure as in Example 29 to obtain 4.5g (yield 78.0%) of the title compound.

Claims (11)

1. Having described the present invention, the content of the following is claimed as property: RF.TVTNDTCATIONS 1.- Process for preparing a 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime ester derivative represented by the following formula (I): wherein Ri represents hydrogen, halogen, cyano, nitro, alkylene: n of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyloxy of 2 to 6 carbon atoms, alkylthio having 1 to 4 carbon atoms, amino which may be substituted with alkyl having 1 to 4 carbon atoms, aryl, aryloxy, acyl with 1 to 4 carbon atoms or acyloxy with 1 to 4 carbon atoms, n means an integer between 1 to 5, Rs represents hydrogen, halogen, cyano, nitro, alkylene with 1 to 4 carbon atoms, aleoxi with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkoxycarbonyl, alkenyloxycarbonyl having from 2 to 4 carbon atoms, alkylaminocarbonyl having from 1 to 4 carbon atoms, di (alkylCy-) aminocarbonyl, arylmethylaminocarbonyl, heteroarylmethylaminocarbonium, or phenyl which may be substituted with Ri, characterized because a compound that has the following formula (V), wherein R represents hydrogen or an alkali metal cation, and Ri, R2 and n are as defined above, are reacted with a pyrimidine derivative having the following formula (VI) wherein Z represents halogen, alkylsulfonyl or arylsulfonyl with 1 to 4 carbon atoms. 2. The process according to claim 1, wherein the compound of the formula (V) is prepared by reacting a derivative of 5- (4,6-dimethoxy-pyrimidin-2-yl) oxy-4H- ( l, 3) -benzodioxin-4-one having the following formula (IV) in which R3 and R4 independently represent hydrogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms with from 1 to 6 halogen atoms, benzyl, or phenyl which may be substituted with one or two groups selected from 1 to 5 halogen atoms and / or alkyl having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 atoms of carbon, haloalkyl with 1 to 2 carbon atoms and nitro, or Rs and R4 together represent an alkylene chain cor. r.? 1 = 6 carbon atoms which can be substituted with 1 to 5 halogen atoms and / or alkyl with 1 to 4 carbon atoms, R4 also represents in which Q represents sulfur, oxygen or NRs (re represents hydrogen or alkyl with 1 to 4 carbon atoms), Re, Re and RT independently represent hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or haloalkyl with 1 to 2 carbon atoms which may be substituted with 1 to 5 halogen atoms, or Re and Re together represent a benzo benzene ring = molten, in which the ring of benzene can be substituted with one or two groups selected from 1 to 5 halogen atoms and / or alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, haloalkyl with 1 to 2 carbon atoms , cyano and nitro, RT represents hydrogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms with 1 to 5 halogen atoms or an alkylbenzene ring,
2. X and Y independently represent oxygen or sulfur,
3. Rio, Rn, R12 and Ris independently represent hydrogen, alkyl with 1 to 4 carbon atoms or haloalkyl with 1 to 4 carbon atoms with 1 to 5 halogen atoms, and m means 0 or 1, with an oxime or its metal salt having the following formula (III) wherein R, Ri, R2 and n are as defined in claim 1. 3. The process according to claim 1 or 2, wherein the reaction is carried out in one or more solvents selected from a group consisting of tetrahydrofuran, diethyl ether, dimethylformamide, dimethyl sulfoxide, dichloromethane, carbon tetraeloride, benzene and toluene.
4. 4. The process according to claim 1 or 2, wherein the reaction is carried out in the presence of one or more bases selected from a group consisting of potassium carbonate, sodium carbonate, sodium hydride, sodium hydrocarbonate , lithium hydroxide, sodium hydroxide and potassium hydroxide.
5. 5. A derivative of 5- (4,6-dimethoxypyrimidin-2-yl) oxy-4H- (1, 3) -benzodioxin-4-one having the following formula (IV): wherein 3 and A are as defined in claim 2.
6. 6.- A process for preparing a compound having the following formula (IVa), wherein Rs * and R a_ independently from each other represent hydrogen, alkyl having from 1 to 4 carbon atoms, haloalkyl having from 1 to 4 carbon atoms having 1 to 5 halogen, benzyl or phenyl atoms which can be substituted with one or two groups selected from 1 to 5 halogen atoms and / or alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 to 2 carbon atoms or nitro or, R3? and R_j »together represent an alkylene chain with from 2 to 6 carbon atoms which can be substituted with 1 to 5 halogen atoms and / or alkyl with 1 to 4 carbon atoms, by reacting a compound having the following formula ( VII) and a compound having the following formula (VIII) in which R3 *. and R4 & they are defined above, with thionyl chloride in a solvent in the presence of a catalytic amount of dimethylaminopyridine.
7. 7. A process for preparing the compound of the formula (IVa) is defined in claim 6 by reacting the compound of the formula (VID as defined in claim 6 with a compound of the formula (VIII) as defined in claim 6 or a compound having the following formula (IX), wherein R3 * and R4 * are defined as in claim 6 and R14 represents alkyl with 1 to 4 carbon atoms, corresponding to compound (VIII) er. the presence? n acid catalyst and a dehydrating agent.
8. 8. A process for preparing the compound of the formula (IVa) as defined in claim 6 by reacting a compound having the following formula (X) wherein R3 * and R4"are defined in claim 6, with the pyrimidine derivative of the formula (VI) as defined in claim 1.
9. 9. - A process for preparing the compound of the formula (IVa) as defined in claim 6 wherein R3 and R4 represent hydrogen by reacting the compound of the formula (VII) as defined in claim 6 with dihalomethane having the following formula (XI) P? p (XI) in which P represents bromine or iodine, in a solvent in the presence of a base.
10. 10. A process for preparing a compound having the following formula (IVb) wherein R3, Re, Re, RT and Q are defined as in claim 2, by reacting a compound having the following formula (XII) wherein R3, Re, Re, RT and Q are as defined in claim 2, with a pyrimidine derivative of the following formula (XIII), in a solvent in the presence of a base.
11. 11. A process for preparing a compound having the following formula (IVc), wherein R3 to RT are as defined in claim 2, is introduced into a 2,6-dihydroxybenzoic acid having the following formula (XIV), using a halogenating agent to produce a cyclic acrylate compound having the following formula (XVII), (XVII in which R3 and RT are as defined in claim 2, in the first reaction step, the compound (XVII) thus obtained is reacted with a compound having the following formula (XVIII), (XVIII wherein R3, RT to R13, m, X and Y are as defined in claim 2, in the second step and finally the compound (XIX) thus obtained is reacted with the pyrimidine derivative of the formula (VI) as is defined in claim 1 in the third reaction. SUMMARY OF THE TNVENCTON The present invention relates to a process for preparing a 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime ester derivative represented by the following formula (I): wherein Ri represents hydrogen, halogen, cyano, nitro, alkyl with «Of 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyloxy with 2 to 6 carbon atoms, alkylthio with 1 to 4 carbon atoms, amino which can be substituted with alkyl having 1 to 4 carbon atoms, aryl, aryloxy, acyl with 1 to 4 carbon atoms or acyloxy with 1 to 4 carbon atoms, n means an integer between 1 to 5, R2 represents hydrogen, halogen, cyano, nitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkoxycarbonyl, alkenyloxycarbonyl with 2 to 4 carbon atoms. carbon, alkylaminocarbonyl with 1 to 4 carbon atoms, di (C 1 -4) alkylaminocarbonyl, arylmethylaminocarbonyl, heteroarylmethylaminocarbonyl, or phenyl which may be substituted with Ri, characterized in that a compound having the following formula (V), wherein R represents hydrogen or an alkali metal cation, and Ri, R2 and n are as defined above, is reacted with a pyrimidine derivative having the following formula (VI) wherein Z represents halogen, alkylsulfonyl or arylsulphonyl having 1 to 4 carbon atoms.