Process for preparing carbonyl compounds

Abstract: The process for preparing the carbonyl compound involves oxidizing the olefins in the presence of the catalyst composed of the palladium compound and the polyoxoanion compound in a mixture of water with a cyclic ether having at least a dioxane ring or a dioxolan ring or in the presence of the catalyst composed of the palladium compound, the polyoxoanion compound and the quinone and/or the aromatic diol in a solvent. This process yields carbonyl compounds, such as ketones and aldehydes, useful as solvents, raw chemicals and so on, with a high production rate per unit time and unit palladium quantity.

Description: 1. Field of the Invention The present invention relates to a process for preparing carbonyl compounds and, more particularly, to a process for efficiently and stably preparing carbonyl compounds including ketones, particularly such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclopentanone, and aldehydes, such as acetaldehyde, by oxidizing olefins. The carbonyl compounds are useful as solvents, or raw chemical materials, for example. 2. Description of the Related Art Carbonyl compounds including ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetone, and aldehydes such as acetaldehyde, are useful as solvents and raw chemical materials, for example. As the method for the preparation of the carbonyl compounds by the direct oxidation of olefins, there is known the Wacker type oxidation process in which PdCl₂-CuCl₂ is employed as a catalyst. The Wacker type process requires a relatively large quantity of an active chlorinated compound so that it causes the problems with corrosion of equipment, and by-production of chlorinated compounds, for example. Further, the Wacker type oxidation has the defects that a reaction rate is decreased to a remarkable extent as the number of carbons of raw olefin materials increases, and that the reactivity of the internal olefins is low, so that the Wacker type process is industrially applicable only to the production of lower carbonyl compounds such as acetoaldehyde or acetone. In order to solve those problems, various processes have recently been proposed in which catalysts of a new type are employed, in place of a so-called Wacker type catalyst. Those processes, however, are said to be industrially insufficient. For example, Japanese Patent Laid-open Publication (kokai) No. 51-117,189 discloses a process in which there is employed a catalyst composed of a combination of a Pd compound with a heteropolyacid or with an isopolyacid. As this conventional process employs water as a solvent, however, it suffers from the disadvantages that the reaction rate becomes low, and productivity becomes poor, for example. The reason for the low reaction rate is because of the raw olefin material employed is less soluble in a solution containing catalyst (an aqueous solution) and the efficiency in the contact of the raw olefin material with the solution containing catalyst (or a catalyst component) becomes remarkably poor. In addition, this conventional process employs a largely excessive quantity of the heteropolyacid or isopolyacid, relative to the palladium compound, so that a large quantity of the heteropolyacidor the isopolyacid is required in order to ensure the sufficiently high reaction rate. This is disadvantageous in terms of economy and this is further a cause of various problems as will be described hereinafter. It is to be noted that this conventional process can reduce the problem with corrosion of equipment to a considerably low level, as compared with the Wacker type process which requires a large quantity of the active chlorinated compounds, particularly CuCl₂ or hydrochloric acid, however, the problem with corrosion of equipment cannot be said to be solved to a sufficient extent. In fact, this conventional process requires the use of an anti-corrosive agent, such as polyethyl siloxane and so on, and the adjustment of pH of a solution containing catalyst with sulfuric acid to, for example, pH=1. Further, the heteropolyacid and the isopolyacid are remarkably lower than CuCl₂ or hydrochloric acid in terms of the extent to which equipment causes corrosion. However, they are an acidic compound so that this conventional process suffers from the disadvantage that a large quantity of highly concentrated aqueous solution should be employed. This is disadvantageous in terms of complete prevention of corrosion of equipment and further the use of sulfuric acid is disadvantageous in terms of prevention of corrosion of equipment. In addition, the conventional process is likely to cause isomerization of olefins. When the raw material to be employed is an olefin having a long chain, the problems are that the reactivity becomes low and the selectivity to the objective carbonyl compounds becomes low. For instance, when 1-hexene is employed as the raw material, the isomerization to 2-hexene is promoted and, as a result, the reactivity is so lowered that the conversion and the selectivity to 2-hexanone are caused to be lowered, thereby increasing the by-production of 3-hexanone. The cause that the isomerization is likely to occur is considered to result from the fact that only water is employed as the solvent and that a large quantity of the heteropolyacid or the isopolyacid is employed. Further, U. S. Patent No. 4,550,212 discloses a process in which the reaction is carried out in a two-phase solvent composed of decane and water by using a multi-component catalyst, such as a catalyst capable of transferring between phases, obtainable by adding H₃BO₃ or cetyltrimethylammoniumbromide (a surfactant) to a Pd-heteropolyacid system. This process takes advantage of the technology of reaction using a catalyst of such a type as transferring between phases in order to improve the efficiency in the contact of the raw olefin material, concentrated by dissolving it mainly in the decane phase, with the catalyst component that exists mainly on the side of the aqueous solution via the action of the surfactant. It is to be noted, however, that this conventional process basically employs a two-phase type solvent composed of decane and water, which are not incompatible with each other. Hence, this conventional process presents the problems that the efficiency in the contact between the raw olefin material and the catalyst is insufficient and the reaction rate is slow. Further, this process has the defect that the reactivity of 2-butene is lower than that of 1-butene. In addition, this conventional process is of a multi-component system in which the reaction system is complex, so that it presents the drawbacks that the separation and recovery of the product, solvent, and catalyst components, for example, are laborious. In addition, Patent Laid-open Publication (kohyo) No. 63-500,923 proposes a process using a catalyst system in which a redox metal, such as Cu, Fe or Mn, and/or ligand (acetonitrile, for example) are added to a Pd-polyoxoanion system. In this case, however, the addition of either of the redox metal or the ligand provides merely the small effect of improvements in the catalyst activity and the improvements in the catalyst activity depends largely upon the synergy between the redox metal and the ligand. Hence, the problems are that the catalyst system becomes complex as a matter of course as well as the separation and recovery of the catalyst components, for example, are as laborious as the other conventional process as described hereinabove. Further, this conventional process presents the severe problem that the sedimentation of the catalyst component is caused to occur as the reaction proceeds, thereby lowering the reaction rate to a remarkably low level, although the reactivity in the initial stage of the reaction is relatively good. Further, Japanese Patent Laid-open Publication (kokai) No. 62-223,145 proposes a process in which the reaction is carried out in a solvent containing a carbamoyl group in the presence of a catalyst system obtainable by adding water to a Pd-redox metal salt-quinone catalyst. This process, however, presents the problems that the reactivity is low and, if the raw olefin material is an internal olefin, the reactivity becomes lower than when the raw olefin material is a terminal olefin. In addition, Jan-E. Backvall et al., J. Am. Chem. Soc., vol. 112, pages 5,160-5,166 (1990) proposes a process using a catalyst composed of a Pd-polycyclic metal-quinone-perchloric acid system. Fe-porphyrin is the most useful as the polycyclic metal to be employed in this process. This conventional process employed, however, is extremely small in scale, although the reaction rate is improved, as compared with the usual Wacker type process. Further, this process causes the isomerization to occur from the terminal olefin to the internal olefin due to the presence of a perchloric acid and these the internal olefin are less inreactivity. In addition, this process presents the drawback that the Pd settles rapidly in the absence of the acid. Moreover, porphyrin compounds, using in this reaction system, are known to be unstable in general. As described hereinabove, those conventional processes, however, have the drawbacks as described hereinabove, so that they are not yet practically applicable on an industrial scale. Demands have been strongly made to develop improvements in technology that can solve those problems and realize industrialization with ease. The present invention has been performed on the basis of the situation as described hereinabove. SUMMARY OF THE INVENTION The object of the present invention is to solve the problems inherently in the conventional processes as described hereinabove and to provide a process for preparing carbonyl compounds, such as aldehydes and ketones, with high efficiency and productivity by oxidizing olefins with the aid of a catalyst system by sufficiently improving the reactivity of the olefins to the carbonyl compounds (the reactivity of ethylene to acetaldehyde and of propylene to acetone as well as the reactivity particularly of a higher olefin such as butene or of internal olefins such as 2-butene to the corresponding ketones) and by maintaining the substantial catalyst activity and the reaction rate at a high and stable level while preventing sedimentation of the catalyst components or deterioration of the activity due to aggregation. The present invention has been completed on the basis of the object as described hereinabove. Accordingly, the present invention provides a process for preparing a carbonyl compound, comprising oxidizing an olefin with the aid of a catalyst composed of a palladium compound and a polyoxoanion compound in the presence of water and a cyclic ether having at least a dioxane ring or a dioxolan ring. The process according to the present invention is remarkably advantageous because it does not require a largely excessive quantity of the polyoxoanion compounds, it does not cause any corrosion of equipment, and it facilitates the separation of the product and soon from the reaction system as well as the separation, recovery and reuse of the solvent, catalyst or their components. Other objects, features and advantages of the present invention will become apparent in the course of the detailed description of the preferred embodiments, which follow. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Catalyst: The catalyst to be employed in the process according to the present invention comprises the palladium compound and the polyoxoanion compounds. As the palladium compounds, there may be used any compound as long as it contains Pd as a metallic components and it includes various known compounds as have been employed commonly in this field. Specifically, as the palladium compounds, there may be mentioned various inorganic palladium compounds or complexes including, for example, palladium sulfate, palladium nitrate, palladium carbonate, palladium-containing polyoxoanion compound such as a palladium salt of a heteropolyacid, a palladium salt of an isopolyacid, a palladium halide such as palladium chloride, palladium bromide, an alkali metal palladate such as sodium tetrachloro-palladate, sodium tetrabromopalladate, potassium tetra-chloropalladate, potassium tetrabromopalladate, an ammine complex compound such as Pd(NH₃)₄Cl₂, palladium hydroxide, palladium oxide, various organic palladium compounds or complexes including, for example, a palladiumu salt of an organic acid such as palladium acetate, a palladiumacetylacetonate, a palladium nitryl complex such as Pd(CH₃CN)₂Cl₂, Pd(PhCN)₂Cl₂ (wherein Ph represents a phenyl group), a palladium phosphine complex such as Pd(PPh₃)₄, a palladium amine complex compound such as Pd₂(dba)₃CHCl₃ (wherein dba represents dibenzylidene acetone), Pd(cod)Cl₂ (wherein cod represents cyclooctadiene), Pd(edta) (wherein edta represents ethylenediaminetetraacetic acid); and an active metallic palladium such as palladium colloid, or highly dispersed palladium metal. Among these palladium compounds, there may preferably be usually employed the palladium compounds containing a divalent palladium (having the oxidation number of +2). Particularly, PdSO₄·2H₂0 is preferably employed. The palladium compounds may be employed in various forms, for example, in the form of an anhydride, in the form containing crystalline water, in the form of a solution such as an aqueous solution, a solution dissolved in an organic solvent, in the form of a suspension or in the form in which the palladium compounds are deposited on a carrier such as active carbon. The palladium compounds may be employed singly, in a mixture of two compounds or more or in the form of a compound material or a composition. The polyoxoanion compounds are not restricted to any particular polyoxoanion compounds as long as they can readily oxidize the reduced-state Pd into the oxidized-state Pd (particularly Pd²⁺) in the catalyst cycle and the resulting polyoxoanion compounds in the reduced state can readily be re-oxidized with the aid of an oxidizing agent, such as oxygen. The polyoxoanion compounds contain a metal having at least two different valency state upon dissociation into ions on the anion. There may be employed various known compounds which are employed commonly in this field. As the polyoxoanion of the polyoxoanion compounds, there may be mentioned ones containing one or more than one metal component selected from V, Mo, W, Nb, and Ta, for example. Further, the polyoxoanions may be heteropolyoxoanions or isopolyoxoanions. In addition, when the polyoxoanion has one kind of the metal component, the one containing Mo or V is preferred. When the polyoxoanion is composed of two or more than two kinds of the metal components, the one containing two kinds of Mo and V, Mo and W or V and W is preferred or the one containing three kinds of Mo, W and V is preferred. The above mentioned heteropolyoxoanion is of such a structure that a hetero atom selected from various hetero atoms, such as P, Si, As, Ge, B, Se, and Te, for example, is contained in the structure of the polyoxoanion. In the process according to the present invention, there may be employed the heteropolyoxoanion containing those various hetero atoms as described hereinabove. Particularly, the heteropolyoxoanion containing P as the hetero atom is preferred. Specifically, preferred examples of the polyoxo anions may include heteropolyoxoanions, such as [PV₂Mo₁₀O₄₀]⁵⁻, [PV₃Mo₉O₄₀]⁶⁻, [PV₄Mo₈O₄₀]⁷⁻, [PV₆Mo₆O₄₀]⁹⁻, [PV₈Mo₄O₄₀]¹¹⁻, [PMo₆W₆O₄₀]³⁻, [P₂VMo₂W₁₅O₆₂]⁷⁻, [PV₃W₇O₄₀]⁶⁻, [P₂VMo₅W₁₂O₆₂]⁷⁻, [PMo₁₂O₄₀]³⁻, and isopolyoxoanions, such as [Mo₃V₃O₁₉]⁵⁻, [V₂Mo₆O₂₆]⁶⁻, [V₄Mo₈O₃₆]⁴⁻, [V₆Mo₆O₃₆]⁶⁻, [V₈Mo₄O₃₆]⁸⁻, or [V₂Mo₃W₇O₃₆]²⁻. As the polyoxoanion compounds, there may be mentioned compounds composed of the aforesaid heteropolyoxoanion or isopolyoxoanion and one or more than one positive ion component (a counter cation). In other words, the polyoxoanion compounds may be a heteropolyacid, a isopolyacid or a salt thereof. The polyoxoanion compounds may contain crystalline water. As the positive ion component (the counter cation), there may be mentioned H⁺, NH⁴⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Pd²⁺, and Rh³⁺, for example. Among these ions, H⁺ is particularly preferred. The polyoxoanion compounds may include various ones in accordance with the kind of and combination of the polyoxoanions and the positive ion components, and any one of those polyoxoanion compounds may be employed. Among these polyoxoanion compounds, the heteropolyacid consisting of the aforesaid heteropolyoxoanion and H⁺ is preferred in terms of the catalyst activity. As particularly preferred examples of the heteropolyacids, there may be mentioned H₃[PMo₂O₄₀], H₆[PV₂Mo₁₈O₄₀], H₆[PV₃Mo₉O₄₀], H₇[PV₄Mo₈O₄₀], H₉[PV₆W₆O₄₀], H₉[PMo₆W₈O₄₀], H₁₁[PMo₄V₈O₄₀], H₃[PMo₆W₈O₄₀], H₇[PMo₆V₆O₄₀], H₆[PV₃W₉O₄₀], H₇[P₂VMo₂W₁₅O₆₂] and H₇[P₂VMo₅W₁₂O₆₂]. The polyoxoanion compounds, such as those aforesaid heteropolyacids, may be employed in various forms, for example, in the form of an anhydride, in the form containing crystalline water, in the form of a solution such as an aqueous solution, a solution dissolved in an organic solvent, in the form of a suspension or in the form in which the polyoxoanion compounds are deposited on a carrier such as active carbon, The polyoxoanion compounds may be employed singly, in a mixture of two compounds or more or in the form of a compound material or a composition. The catalyst to be employed for the process according to the present invention comprises at least one or more than one aforesaid palladium compound and at least one or more than one aforesaid polyoxoanion compound. These catalyst components may be supplied to the reaction system separately or in the form of a mixture. It is to be noted herein that a palladium salt of the heteropolyacid or a palladium salt of the isopolyacid may be employed as in the aforesaid palladium compound or the aforesaid polyoxoanion compound or both of thereof. The rates of the polyoxoanion compound and the palladium compound to be employed for forming the catalyst may be chosen in accordance with the kind of and the combination of those compounds. The polyoxoanion may range usually from 0.5 mole to 100 moles, preferably from 1 mole to 20 moles, 1 per mole of the palladium component in the palladiumu compound. When the rate of the polyoxoanion is smaller than 0.5 mole per 1 mole of the palladium component, on the one hand, the re-oxidation of the reduced type palladium component into the oxidized type palladium component in the catalyst cycle cannot be performed to a sufficient extent, thereby failing to maintain the catalyst activity at a high level. When the rate of the polyoxoanion is larger than 100 moles per 1 mole of the palladium component, on the other hand, undesirable by-products are likely to be formed and such a large amount of the polyoxoanion is economically disadvantageous. It is further to be noted that the catalyst may contain other co-catalyst component (including a ligand component), if desired, within the range that does not adversely affect the objects of the present invention. In the process according to the present invention, the catalyst may be employed in a homogeneous state, in a heterogeneous state or in a state which is composed homogeneous state and heterogeneous state, when it is employed in the presence of the cyclic ether and water. For instance, the catalyst may be employed in the form of a homogeneous solution in which the catalyst components are dissolved in a mixture solvent composed of the cyclic ether and water or in the form in which a portion of the catalyst components are dissolved in the mixture solvent and the other portion thereofis dispersed in the mixture solvent. Further, a portion or a whole of the catalyst components may be employed in the form in which it is deposited or fixed on an appropriate carrier such as active carbon, silica or a polymer. Materials existing together with the catalyst (cyclic ethers and water or solvents thereof): In accordance with the present invention, it is of significance that the oxidation of the olefins is carried out with the aid of the catalyst in the presence of at least a mixture of the cyclic ether having a dioxane ring and/or a dioxolan ring with water. It is to be noted herein that the process according to the present invention usually employs a catalyst solution, preferably a homogeneous solution containing catalyst, composed of a mixture of the solvents consisting of the cyclic ether and water with the catalyst when the process is carried out in a liquid phase, although the conventional processes are carried out in a catalyst solution (an aqueous solution) using water as a solvent. However, the process according to the present invention can be carried out in a gaseous phase, particularly in a vapor phase passage system, in which the catalyst is employed in the state, for example, in which the catalyst is deposited or fixed on the carrier such as active carbon or the polymer. Hence, in this case, each of the cyclic ether and water may be supplied to the reaction system in a gaseous state or in any state that can comply with the catalyst in a solid state. In other words, the cyclic ether and water are not restricted to the case that they are supplied as solvents for the catalyst components, when they are employed as materials existing together with the catalyst, and they may be supplied in various forms and in various supply systems, neither in restricted states nor in restricted supply systems. As described hereinabove, the catalyst is used in the presence of the materials existing together with the catalyst, such as solvents composed of at least water and the cyclic ether having the dioxane ring and/or the dioxolan ring, not with water alone, thereby improving the velocity of producing the carbonyl compounds from the various olefins with a remarkable extent. Further, the high production velocity can be maintained in a stable manner, thereby achieving the objects of the present invention. In other words, by using the catalyst together with the materials existing with the catalyst, such as the solvents containing the particular cyclic ether as well as water, the process according to the present invention can suppress the sedimentation or aggregation of the catalyst components as the reaction proceeds, which is the problem in the conventional processes. Further, the process according to the present invention can maintain the catalyst performance, i.e. the catalyst activity and selectivity, at a high level and in a stable manner and further improve the efficiency in the contact between the olefin and the catalyst with a remarkable extent. As the dioxane ring of the cyclic ethers, there may be mentioned a 1,4-dioxane ring and a 1,3-dioxane ring. These dioxane rings may be unsubstituted or substituted at least with one substituent such as an alkyl group. As the dioxolan ring, a 1,3-dioxolan ring is preferred, and it may be unsubstituted or likewise substituted. As the cyclic ethers, there may be usually employed a cyclic ether composed of one dioxane ring or one dioxolan ring. It is to be noted herein that there also may be employed a cyclic ether composed of two or more than two dioxane rings or two or more than two dioxolan rings or a cyclic ether composed at least of one dioxane ring and one dioxolan ring. Typical examples of the cyclic ethers may include 1,4-dioxane, an alkyl-substituted 1,4-dioxane, 1,3-dioxane, an alkyl-substituted 1,3-dioxane, 1,3-dioxolan, or an alkyl-substituted 1,3-dioxolan. The alkyl substituent of each of the alkyl-substitued dioxanes and the alkyl-substituted dioxolans is not restricted to a particular one and it may be linear or branched or of a cyclic structure such as a cycloalkyl group or a cycloalkylalkyl group or a araklyl group. Usually, the alkyl substituent may preferably include, for example, a lower alkyl group having from one to about four carbon atoms; such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, when the compatibility and affinity of the cyclic ethers with water are taken into account. Among the alkyl substituents, methyl and ethyl are particularly preferred. The number of the alkyl substituents of the alkyl-substituted dioxanes and the alkyl-substituted dioxolans and the position of the alkyl substituents thereof are not restricted to particular ones, however, the number of the alkyl substituents thereof is preferably one or two, particularly preferably one, in terms of the compatibility and affinity with water. Representative examples of the dioxanes and dioxolans substituted with one alkyl substituent may include 2-alkyl-1,4-dioxane, 2-alkyl-1,3-dioxane, 4-alkyl-1,3-dioxane, 5-alkyl-1,3-dioxane, 2-alkyl-1,3-dioxolan or 4-alkyl-1,3-dioxolan. It is to be noted herein that the cyclic ethers have the compatibility and have the affinity with water, because they have the dioxane ring and/or the dioxolan ring. This property plays a significant role in achieving the objects of the present invention to a sufficient extent, particularly when the cyclic ether and water are employed as liquid solvents. The extent of the compatibility and affinity with water may vary with the presence or absence of the substituent on the dioxane ring or the dioxolan ring and the kind of the substituent, i.e. the size of the alkyl substituent, for example. In the process according to the present invention, there may favorably employed the cyclic ethers having a higher affinity with water, preferably having a higher compatibility with water. As it is commonly known that the cyclic ethers are generally superior in solubility in a hydrocarbon, such as an olefin, or an organic compound, this property is of significance in achieving the objects of the present invention to a sufficient extent, when the cyclic ethers and water are employed as liquid solvents. Preferable examples of the specific cyclic ethers include 1,4-dioxane, 1,3-dioxane, 2-methyl-1,4-dioxane, 2-ethyl-1,4-dioxene, 2-methyl-1,3-dioxane, 2-ethyl-1,3-dioxane, 4-methyl-1,3-dioxane, 4-ethyl-1,3-dioxane, 5-ethyl-1,3-dioxane, 1,3- dioxolan, 2-methyl-1,3-dioxolan, 2-ethyl-1,3-dioxolan, 4-methyl-1,3-dioxolan, and 4-ethyl-1,3-dioxolan. Among these examples, 1,4-dioxane, 1,3-dioxane, 1,3-dioxolan, 2-methyl-1,3-dioxolan, for example, are preferred. The various cyclic ethers may be employed singly or in combination with two or more as the component for the material existing together with the catalyst or as the component for the solvent. The rate of the cyclic ether with respect to water in the material existing together with the catalyst, such as the solvents, is not restricted to a particular one and it may arbitrarily be chosen with the following taken into account. In other words, the appropriate rate of the cyclic ether with respect to water may be determined on the basis of the kind of the catalysts or their ingredients, i.e. the palladium compounds or the polyoxoanions, the kinds of the raw olefins and the cyclic ethers, reaction systems, and reaction conditions, for example, although it may vary with these elements and it cannot be determined in a uniform way. Further, it should be taken into account that an extremely low quantity of water reduces solubility of the catalyst components or the reaction rate becomes low due to the reason for reaction mechanism. On the other hand, if the water content becomes extremely large, the Pd component settles as a metallic palladium (Pd o ) or aggregates, thereby causing the likelihood to reduce the catalyst activity. In addition, as the solubility of the raw olefins into water is so low, the problem may arise that the efficiency in contact between the raw olefins and the catalyst (the solution containing catalyst) is so lowered, particularly in the liquid-phase reaction, that the sufficient reaction rate cannot be achieved. From these reasons, the material existing together with the catalyst, particularly water, is employed at the rate ranging usually from 5% to 70% by weight, preferably from 10% to 50% by weight, in the solvent mixture. It is further noted that the materials existing together with the catalyst, such as the solvents, may contain other solvent components much as, for example, an alcohol, a hydrocarbon, an ether, an ester, a ketone or a nitrile, unless improving the objects of the present invention. In the process according to the present invention, the solvents may be employed in any form as long as they are employed as the materials existing together with the catalyst. For example, the solvents may be employed as solvents for making the catalyst a homogeneous solution or as dispersing the catalyst or in such a state that they are contained in the catalyst or in the catalyst components. When the catalyst or the catalyst component is dissolved or dispersed in the solvent mixture consisting of the cyclic ether and water, the rate of the solvent mixture may be in the range usually from approximately 1 liter to 10,000 liters per 1 mole of the palladium component to be employed. Raw Olefins: The olefins to be employed for the process according to the present invention are not restricted to particular ones as long as they contain at least one olefinic double bond (C=C), and they may include, for example, an olefin having a plurality of olefinic double bonds, such as a diene, or a triene, in addition to a mono-olefin. Further, the olefins may contain a terminal olefin having the olefinic double bond (C=C) at its terminal position, an internal olefin having the olefinic double bond (C=C) at its internal position, and an olefin having the olefinic double bonds at both of its terminal and internal positions. In addition, the olefins may be a linear olefin such as a linear alkene, or a linear alkadiene or a cyclic olefin having a cyclic substituent, such as a cyclic olefin, e.g. a cycloalkene, or a cycloalkadiene, a cycloalkyl group or an aromatic group. The number of carbon atoms of the olefins is not restricted to a particular one as long as the number of carbon atoms is two or more. The number of the carbon atoms thereof usually ranges from 2 to 20, preferably from 2 to approximately 10. The linear olefins may be a straight-chain olefin or a branched-chain olefin. As the linear olefins, there may specifically mentioned, for example, a monoolefin including ethylene, propylene, 1-butene, trans-2-butene, cis-2-butene, isobutene, 1-pentene, 2-pentene, 3-methyl-1-butene, an isopentene such as 2-methyl-2-butene or the like, 1-hexene, 2-hexene, 3-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, an isohexene such as 4-methyl-2-pentene, neohexene, 1-heptene, 2-heptene, 3-heptene, 4-methyl-1-hexene, an isoheptene such as 5-methyl-2-hexene, 1-octene, 2-octene, 3-octene, 4-octene, isooctene, 1-nonene, 2-nonene, isononene, 1-decene, 2-decene, 3-decene, 4-decene, 5-decene, isodecene, undecene, dodecene, tridecene, tetradecene, hexadecene, and a diene including a pentadiene, a hexadiene, a heptadiene, an octadiene, or a decadiene. Specific examples of the cyclic olefins may include a cycloalkene such as cyclopentene, cyclohexene, cyclooctene, or cyclodecene, a cycloalkadiene such as cyclooctadiene. Further, the cycloalkenes and the cycloalkadienes may be substituted with a substituent such as an alkyl substituent. The olefins having the aromatic group may include, for example, various compounds in which an aryl group such as a phenyl group or an alkyl phenyl group is substituted on the various linear olefins or the cyclic olefins. As typical examples of the olefins having the aromatic substituent, there may be mentioned, for example, a styrene type hydrocarbon such as styrene, p-methylstyrene, or β-methylstyrene. As the olefins having other cyclic structure, there may be mentioned, for example, vinylcyclohexane, vinylcyclohexene, or allylcyclohexane. As the specific examples of the olefins that can be employed particularly favorably, there may be mentioned, for example, ethylene, propylene, 1-butene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, isopentene, 1-hexene, 2-hexene, 3-hexene, 4-methyl-1-pentene, isohexene, neohexene, 1-heptene, 2-heptene, 1-octene, 2-octene, isooctene, cyclopentene, cyclohexene, cyclooctene or styrene. As described hereinabove, the process according to the present invention can realize the high reactivity for the internal olefins such as 2-butene and the cyclic olefins such as cyclopentene, as well as the α-olefins( terminal α-olefins). In the process according to the present invention, the olefins as the hydrocarbons are usually employed as the raw materials, however, the olefins containing a hetero atom may also be employed as the raw materials unless improving the objects of the present invention. Further, the various olefins may be employed singly or in combination with two or more than two olefins. In addition, the raw olefins may contain other components that do not adversely affect the objects of the present invention. The olefins may be supplied to the reaction system, as needed, in a mixture with water or other solvents. Oxidizing Agents: In the process according to the present invention, the oxidizing agents to be employed for the oxidation of the olefins may usually include, for example, oxygen gases and mixed gases of oxygen gases and a dilute gas, such as oxygen-enriched air, or air. As the dilute gas, there may be usually employed, for example, nitrogen gas, although the dilute gas is not restricted to a particular one, and it may further include, for example, helium, argon, or carbon dioxide. In addition, the oxygen and oxygen-containing gases may contain other ingredients as long as they do not adversely affect the objects of the present invention. The gases to be employed as the oxidizing agents may be supplied to the reaction system, as desired, in such a system as containing other ingredients such as moisture or solvent components. Oxidation: The process according to the present invention synthesises the carbonyl compounds, i.e. the ketones and/or aldehydes, by oxiding the corresponding olefins with the aid of the catalyst in the presence of the materials existing together with the catalyst. The reaction system is not restricted to a particular one as long as the olefins can be treated with the aid of the catalyst in the presence of the material existing together with the catalyst. The reaction system in the vapor phase reaction and/or in the liquid phase reaction may include, for example, a batch system, a semi-batch system, a semi-continuous system, a continuous system or a system in which the aforesaid systems are combined. As described hereinabove, the catalyst can be employed in the various states, that is, in a homogeneous state (in a homogeneous solution contaioning catalyst) in which the catalyst is dissolved in the solvent, in a heterogeneous state (in a heterogeneous solution containing catalyst) in which only a portion of the catalyst is dissolved in the solvent while the rest of the catalyst is dispersed therein or in a heterogeneous state (in a solid state) in which the catalyst is deposited or fixed on a carrier or a polymer. The raw olefins, the catalysts and the solvents or the materials existing together with the catalysts may be supplied each in a liquid state or in a gaseous state. In other words, they can be supplied in a system, for example, in which a solution having catalyst obtainable by admixing the catalyst with the solvent or a mixture of the resulting solution having catalyst with the olefin is used in a liquid phase and the reactions carried out in a batch system, in which the olefin in a gaseous state and the gases (oxygen gases or oxygen-containing gases) as the oxidizing agent are introduced into the solution having catalyst or the gases as the oxidizing agent are introduced into a mixed solution composed of the catalyst solution and the olefin, in which the catalyst solution, the olefins and the oxidizing gases are introduced simultaneusly into a reaction region, or in which the catalyst component is deposited or fixed to the carrier or the polymer in a heterogenous state (in a solid state) and the gaseous olefin, the oxidizing gases and solvent vapors (gaseous materials existing together with the catalyst) are exposed in gaseous state to the catalyst component in the solid state. When the reaction is carried out in a batch system, the rate of the raw olefins with respect to the catalyst may appropriately range usually from 1 mole to 10,000 moles, preferably from 10 moles to 5,000 moles, per 1 mole of the palladium component to be employed, although it cannot be determined in a constant manner because it depends upon the activity of the catalyst and other reaction conditions. If the rate is too small, on the one hand, the productivity with respect to the catalyst unit becomes too low and it is economically disadvantageous. If the rate becomes too large, on the other hand, no sufficient rate of selectivity may be achieved or the reaction may take a longer time. When the reaction is carried out in such a liquid or gaseous phase system that the olefin and the oxidizing gases are continuously supplied to the solution having the catalyst or to the solid catalyst layer, the rate of the raw olefin to be supplied per 1 mole of the palladium component may appropriately range usually from approximately 10 moles to 5,000 moles per hour. The reaction temperature may appropriately be set within the range usually from 0 °C to 200 °C, preferably from 20°C to 100 °C, when the reaction is carried out in the liquid phase system. If the reaction temperature is below 0°C, the reaction rate may become too low. When the reaction temperature exceeds 200°C, by-products are likely to occur. When the reaction is carried out in the gaseous phase system, the reaction temperature may appropriately range usually from 50 °C to 700 °C, preferably from 100 °C to 500°C. If the reaction temperature is below 50 °C, on the one hand, the reaction rate may become too low. If the reaction temperature is above 700 °C, on the other hand, by-products are likely to be formed. The reaction pressure may economically range usually from ambient pressure to approximately 9.8 MPa (100 kg/cm²) although it may be chosen within a wide scope in the range from ambient to high pressure. Reaction Product: As described hereinabove, the carbonyl compounds, such as the ketones, the aldehydes or mixtures thereof, can be produced from the corresponding olefins in a stable manner with high efficiency. For example, when ethylene is employed as a raw material, acetaldehyde is yielded as a reaction product. Further, when propylene is employed as a raw material, acetone is yielded as a reaction product. In addition, 1-butene, 2-butene or a mixture thereof yields methyl ethyl ketone, and 4-methyl-1-pentene yields methyl isobutyl ketone. The carbonyl compounds as the reaction products yielded in the manner as described hereinabove may be separated, isolated and purified in conventional manner, thereby yielding a single compound or a mixture having a desired purity or a desired composition. When the unreacted raw materials are left, they are recovered for recirculation to the reaction system. The catalyst employed are then reproduced or separated, as desired, for recirculation. Further, the solvents or the materials employed together with the catalyst, particularly the cyclic ethers and so on constituting the components therefor, can be readily separated and recovered in conventional manner and recirculated as desired. The carbonyl compounds yielded in the process according to the present invention in the manner as described hereinabove can be employed appropriately in various fields including a synthetic chemistry field, for example, as solvents, or chemicals. In accordance with the process according to the present invention, the carbonyl compounds, such as the aldehydes and the ketones, can be produced stably with high reactivity and high yield in a remarkably mild condition by oxiding the corresponding olefins because the catalyst is employed in the presence of the particular materials existing together with the catalyst, ice, the solvents, for example, consisting of a mixture of water and the particular cyclic ether, not in the presence of water alone, in oxidizing the olefins with the aid of the catalyst system composed of the palladium compound and the polyoxoanion compounds such as the heteropolyacids or the isopolyacids. For example, ethylene yields acetaldehyde and propylene yields acetone. Further, methyl ethyl ketone is prepared from 1-butene or 2-butene, and cyclopentanone is prepared from cyclopentene. In addition, a higher olefin, an internal olefin or a cyclic olefin can be converted into the corresponding carbonyl compounds such as ketones or aldehydes. Further, the process according to the present invention can remarkably improve the efficiency in the contact between the olefins as the raw materials and the catalyst components (the catalyst solution) when the oxidation is carried out in the liquid phase in which the the materials existing together with the catalyst, composed of the cyclic ethers and water, are employed as the solvents. Additionally, this process can effectively prevent the activity of the compounds employed as the catalyst from deteriorating due to sedimentation or conversion into an insoluble form or for other reasons. Furthermore, the process according to the present invention can maintain the high reaction rate in a stable manner. In other words, the present invention can provide the process for preparing the carbonyl compounds, which is remarkably advantageous over the conventional processes. Hence, the process according to the present invention can sufficiently realize the industrial process that can produce the carbonyl compounds from the corresponding olefins as well as it achieves improvements in the conventional processes for preparing acetaldehyde from ethylene, acetone from propylene, and so on. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described more in detail by way of working examples with reference to comparative examples. It is to be noted herein, however, that the present invention should not be interpreted in any respect as being restricted to the following examples and it should be construed as encompassing various modifications and changes within the scope and spirit of the present invention as defined by the claims. Example 1: An autoclave was charged with a solution of 0.4 mmol (0.0955 gram) of PdSO₄ · 2H₂0 and 1.8 mmol (3.52 grams; water content, 13.3% by weight) of H₆PV₃Mo₉O₄₀ in 25 ml of 1,4-dioxane and 5 ml of water, and 216 mmol of trans-2-butene was oxidized with oxygen at 97 °C for 35 minutes while the total pressure was held at 0.98 MPa (10 kg/cm²) (gauge pressure) by supplying oxygen, thereby yielding methyl ethyl ketone (MEK) in the quantity of 100.5 mmol. In this case, the quantity (in mol) of the MEK produced per mol of palladium, i.e. the TON of the MEK, was 431 mol/(mol.hour). No undissolved materials, such as sediment, were found in the reaction solution after completion of the reaction. Example 2: The procedures of Example 1 were followed in substantially the same manner, except for using o.2 mmol(o.o478g) Of PdSO₄ · 2H₂O and setting the reaction temperature to 79 °C, the reaction time to 70 minutes and the reaction pressure (total pressure) to 0.784 MPa (8 kg/cm²) (gauge pressure). This example gave MEK in the quantity of 92.3 mmol. This yield corresponds to the TON of the MEK at 396 mol/(mol.hour). In this case, no undissolved materials, such as precipitats (sedments), were found in the reaction solution after the reaction had been finished. Comparative Example 1: The procedures were followed in substantially the same manner as in Example 2, except for using 10 ml of acetonitrile and 30 ml of water, in place of 25 ml of 1,4-dioxane and 5 ml of water, additionally using 2 mmol (0.501 gram) of CuSO₄ · 5H₂O as a metal component, and setting the reaction pressure (total pressure) to 0.882 MPa (9 kg/cm²) (gauge pressure). This example yielded MEK in the quantity as low as 39.7 mmol, and this yield corresponds to the TON of the MEK at 85 mol/(mol.hour). Further, black precipitates, presumably Pd black, were recovered in the quantity of 44.0 mg from the reaction mixture after completion of the reaction. Example 3: The procedures were performed in substantially the same manner as in Example 1, except for setting the reaction temperature to 58°C, the reaction time to 120 minutes and the reaction pressure (total pressure) to 0.588 MPa (6 kg/cm²) (gauge pressure). As a result, MEK was yielded in the quantity of 88.8 mmol. This yield corresponds to the TON of the MEK at 111 mol/(mol.hour). In this example, no undissolved materials, such as precipitates, were found in the reaction mixture after the reaction has been finished. Example 4: The procedures were followed in substantially the same manner as in Example 3, except for using 1.8 mmol (3.88 grams; water content, 23.7% by weight) of H₇PV₄Mo₈O₄₀, in place of H₆PV₃Mo₉O₄₀. This example yielded MEK in the quantity of 79.2 mmol, and this yield corresponds to the TON of the MEK at 99 mol/(mol.hour), No undissolved materials, such as precipitates, were found in the reaction mixture after the completion of the reaction. Comparative Example 2: The procedures were followed in substantially the same manner as in Example 4, except for using 10 ml of tetrahydrofuran (THF) and 20 ml of water, in place of 25 ml of 1,4-dioxane and 5 ml of water. This example yielded MEK in the quantity as low as 40 mmol, and this yield corresponds to the TON of the MEK at 51 mol/(mol.hour). Further, black precipitates, presumably Pd black, were recovered in the quantity of 5 mg from the reaction mixture after completion of the reaction. Comparative Example 3: The procedures were followed in substantially the same manner as in Example 4, except for using 30 ml of water, in place of 25 ml of 1,4-dioxane and 5 ml of water. This example yielded MEK in the quantity as remarkably low as 3 mmol, and this yield corresponds to the TON of the MEK at 4 mol/(mol.hour). Further, black precipitates, presumably Pd black, were recovered in the quantity of 87.2 mg from the reaction mixture after completion of the reaction. Example 5: An autoclave was charged with a solution of 0.21 mmol (0.0499 gram) of PdSO₄ · 2H₂0 and 1.8 mmol (3.52 grams; water content, 13.3% by weight) of H₆PV₃Mo₉O₄₀ in 15 ml of 1,4-dioxane and 15 ml of water, and 225 mmol of trans-2-butene was oxidized with oxygen at 76 °C for 70 minutes while the total pressure was held at 0.882 MPa (9 kg/cm²) (gauge pressure) by supplying oxygen, thereby yielding methyl ethyl ketone (MEK) in the quantity of 100.5 mmol, This yield corresponds to the TON of the MEK at 293 mol/(mol.hour). No undissolved materials, such as sediment, were found in the reaction solution after completion of the reaction. Example 6: The procedures were followed in substantially the same manner as in Example 5, except for using 10 ml of 1,4-dioxane and 20 ml of water, in place of 15 ml of 1,4-dioxane and 15 ml of water. This example gave MEK in the quantity of 55.7 mmol. This yield corresponds to the TON of the MEK at 223 mol/(mol.hour). In this case, no undissolved materials, such as precipitats, were found in the reaction solution after the reaction had been finished. Example 7: A Pyrex reactor was charged with a solution of 0.80 mmol (0.1907 gram) of PdSO₄ · 2H₂0 and 4.2 mmol (9.08 grams; water content, 23.7% by weight) of H₇PV₄Mo₈O₄₀ in 50 ml of 1,4-dioxane and 10 ml of water, and the mixture was heated in an oil bath of 50 °C. In this state, propylene and oxygen were supplied to the solution within the reactor at normal pressure at the rates of 40 cm³ per minute and 20 cm³ per minute, respectively, and the oxidation was continued for 1 hour. As a result, acetone was yielded in the quantity of 58.4 mmol. In this case, the quantity (in mol) of acetone produced per mol of palladium for the reaction time of 1 hour corresponds to the TON of the acetone at 78 mol/(mol.hour). No undissolved materials, such as sediment, were found in the reaction solution after completion of the reaction. This continuous system has the advantages that costs of equipment can be lowered and the period of time required for production can be shortened. Example 8: A Pyrex reactor was charged with a solution of 0.20 mmol (0.0477 gram) of PdSO₄ · 2H₂0 and 4.2 mmol (9.08 grams; water content, 23.7% by weight) of H₇PV₄Mo₈O₄₀ in 50 ml of 1,4-dioxane and 10 ml of water, and the mixture was heated in an oil bath of 50 °C. In this state, 1-octene was suppled in the quantity of 100 mmol (11.2 grams) and oxygen was then supplied to the solution within the reactor at normal pressure at the rate of 60 cm³ per minute. The oxidation was carried out in this state for 1 hour. As a result, 2-octanone was yielded in the quantity of 22.0 mmol. In this case, the quantity (in mol) of 2-octanone produced per mol of palladium for the reaction time of 1 hour corresponds to the TON of the octanone at 110 mol/(mol.hour). No undissolved materials, such as precipitates, were found in the reaction solution after completion of the reaction. Example 9: An autoclave was charged with a solution of 0.2 mmol (0.0482 gram) of PdSO₄ · 2H₂0 and 1.8 mmol (3.52 grams; water content, 13.3% by weight) of H₆PV₃Mo₉O₄₀ in 25 ml of 2-methyl-1,3-dioxolan and 5 ml of water, and 225 mmol of trans-2-butene was oxidized with oxygen at 76 °C for 60 minutes at the pressure of 0.882 MPa (9 kg/cm²) (gauge pressure) by supplying oxygen, thereby yielding MEK in the quantity of 71.4 mmol. This yield corresponds to the TON of the MEK at 357 mol/(mol.hour). No undissolved materials, such as sediment, were found in the reaction solution after completion of the reaction. Example 10: An autoclave was charged with a solution of 0.20 mmol (0.0482 gram) of PdSO₄ · 2H₂0 and 1.8 mmol (3.52 grams; water content, 13.3% by weight) of H₆PV₃Mo₉O₄₀ in 25 ml of 1,4-dioxane and 5 ml of water, and 147 mmol (10.0 grams) of cyclopentene was added to the solution. Thereafter, the pressure within the autoclave was elevated to 0.833 MPa (8.5 kg/cm²) (gauge pressure) by supplying nitrogen at 60°C and then to the total pressure of 0.98 MPa (10 kg/cm²) (gauge pressure) by supplying oxygen. The reaction was carried out in this state for 120 minutes at the pressure of 0.98 MPa (10kg/cm²) (Gauge pressure) by supplying oxygen. As a result, cyclopentanone and 2-cyclopenten-1-one were yielded in the quantities of 11.2 mmol and 8.7 mmol, respectively. No undissolved materials, such as sediment, were found in the reaction solution after completion of the reaction. Example 11: An autoclave was charged with a mixture (dispersion solution) of 1.001 grams of 5% by weight Pd/carbon and 1.8 mmol (3.52 grams; water content, 13.3% by weight) of H₆PV₃Mo₉O₄₀ in 25 ml of 1,4-dioxane and 5 ml of water, and 225 mmol of 1-butene was oxidized with oxygen at 79°C for 120 minutes at the pressure of 0.784 MPa (8 kg/cm²) (gauge pressure) by supplying oxygen, thereby yielding MEK in the quantity of 54.1 mmol. This yield corresponds to the TON of the MEK at 78 mol/(mol.hour). This heterogeneous system has the advantage that separation operations are simple. Example 12: The procedures of Example 2 were followed in substantially the same manner, except for using 1-butene as raw olefin. This example yielded MEK in the quantity of 90.4 mmol, and this yield corresponds to the TON of the MEK at 387 mol/(mol.hour). No undissolved materials such as precipitate were found in the reaction mixture after the completion of the reaction. Example 13: The procedures of Example 1 were followed in substantially the same manner, except for using 0.2 mmol(0.0608g) of Pd(acac)₂ instead of using 0.4 mmol(0.0955g) of PdSO₄ · 2H₂O, setting the reaction temperature to 77 °C and setting the reaction time to 90 minutes. This example yielded MEK in the quantity of 102.4 mmol, and this yield corresponds to the TON of the MEK at 512 mol/(mol.hour). No undissolved materials such as precipitate were found in the reaction mixture after the completion of the reaction. Example 14: The procedures of Example 1 were followed in substantially the same manner, except for using 0.2 mmol(0.0453g) of Pd(NO₃)₂ instead of using 0.4 mmol(O.0955g) of PdSO₄ · 2H₂O, setting the reaction temperature to 77 °C and setting the reaction time to 90 minutes. This example yielded MEK in the quantity of 66.9 mmol, and this yield corresponds to the TON of the MEK at 223 mol/(mol.hour). No undissolved materials such as precipitate were found in the reaction mixture after the completion of the reaction. Example 15: A solution containing 0.7 mmol of [V₈Mo₄O₃₆]⁻⁸ was obtained by mixing water solution composed 10 ml of water and 20 ml of 1,4-dioxane with 0.68g of NaVO₃ and 0.67g of Na₂MoO₄ · 2H₂O and adding sulfuric acid in order to adjusting pH of the solution to 1.6. An autoclave was charged with a mixture of said solution and 0.1 mmol (0.0239g) of PdSO₄ · 2H₂O. In the autoclave 226 mmol of trans-2-butene was oxidized with oxygen at 79 °C for 120 minutes while the total pressure was held at 0.784 MPa (8 kg/cm²) (gauge pressure) by supplying oxygen. Thereby MEK was yielded in the quantity of 21.3 mmol, and this yield corresponds to the TON of the MEK at 107 mol/(mol.hour). No undissolved materials such as precipitate were found in the reaction mixture after the completion of the reaction. Example 16: The procedures of Example 2 were followed in substantially the same manner, except for using 1.8 mmol(4.421g, content of water;11.2% by weight) of H₆PV₃W₉O₄₀ in place of H₆PV₃Mo₉O₄₀ and setting the reaction temperature to 90 minutes. This example yielded MEK in the quantity of 50.1 mmol, and this yield corresponds to the TON of the MEK at 167 mol/(mol.hour). No undissolved materials such as precipitate were found in the reaction mixture after the completion of the reaction.

Claims: A process for preparing a carbonyl compound, comprising: oxidizing an olefin with the aid of a catalyst composed of a palladium compound and a polyoxoanion compound in the presence of water and a cyclic ether having at least a dioxane ring or a dioxolan ring. A process for preparing a carbonyl compound as claimed in claim 1, wherein the palladium compound is at least a member selected from a group consisting of palladium sulfate, palladium acetylacetonate, Pd(NO₃)₂ and active metallic palladium. A process for preparing a carbonyl compound as claimed in claim 1, wherein the polyoxoanion compound is at least a member selected from a group consisting of a heteropolyoxoanion and a isopolyoxoanion. A process for preparing a carbonyl compound as claimed in claim 1, wherein the polyoxoanion compound is at least a member selected from a group consisting of H₆[PV₃Mo₉O₄₀] and H₇[PV₄Mo₈O₄₀]. A process for preparing a carbonyl compound as claimed in claim 1, wherein the cyclic ether is at least a member selected from a group consisting of an unsubstituted 1,4-dioxane, an alkyl-substituted 1,4-dioxane, an unsubstituted 1,3-dioxolan and an alkyl-substituted 1,3-dioxolan. A process for preparing a carbonyl compound as claimed in claim 1, wherein the cyclic ether is at least a member selected from a group consisting of 1,4-dioxane and 2-methyl-1,3-dioxolan. A process for preparing a carbonyl compound as claimed in claim 1, wherein the olefin is at least a member selected from a group consisting of a cyclic olefin and a linear olefin having from 2 to 20 carbon atoms. A process for preparing a carbonyl compound as claimed in claim 1, wherein the olefin is at least a member selected from a group consisting of a cycloalken and a linear olefin having from 2 to 10 carbon atoms.

Inventors: ISHII HIROTOSHI IDEMITSU KOSAN, SAITO YOSHINORI IDEMITSU KOSAN, TSUZUKI MASANORI IDEMITSU KOSA, ISHII, HIROTOSHI, IDEMITSU KOSAN COMPANY LIMITED, SAITO, YOSHINORI, IDEMITSU KOSAN COMPANY LIMITED, TSUZUKI, MASANORI, IDEMITSU KOSAN COMPANY LIMITED
Applicants: IDEMITSU KOSAN CO, IDEMITSU KOSAN COMPANY LIMITED
Application year: 1992
Main classification: C07C45
IPC codes: C07C45