Catalytic systems and methods for carbonylation

Abstract: A carbonylation catalytic system comprises (A) a combination of (A1) a Group VIII metal source of Periodic Table of the Elements (e.g., palladium, palladium chloride) supported on a carrier, (A2) a ligand such as triphenylphosphine and (A3) an acid such as an alkyl-sulfonic acid, or (B) a combination of (B1) the Group VIII metal source except for palladium (e.g., a platinum compound), (B2) a ligand such as triphenylphosphine and (B3) an electron donative compound having an electron donability ΔνD of not less than 2 (for instance, an amine such as a heterocyclic tertiary amine). The catalytic system (B) may further comprise (B4) an acid such as methanesulfonic acid. In the presence of the catalytic system (A) or (B), an acetylenic or olefinic unsaturated compound is allowed to react with carbon monoxide and a nucleophilic compound having an active hydrogen such as water, an alcohol and a carboxylic acid in a liquid phase to give an unsaturated or saturated carboxylic acid or an ester thereof with high transformation rate and selectivity.

Description: FIELD OF THE INVENTION This invention relates to catalytic systems useful for carbonylation, and to methods for carbonylation of an acetylenic or olefinic unsaturated compound with the use of the catalytic system. BACKGROUND OF THE INVENTION Catalytic systems and technologies for carbonylation of an acetylenic or olefinic unsaturated compound have been proposed. Typical carbonylation reactions include a method which comprises allowing an acetylenic or olefinic unsaturated compound to react with carbon monoxide and a nucleophilic compound. In this method, a carbonylation catalyst comprises a Group VIII metal source of Periodic Table of the Elements and a phosphine which is a typical ligand. EP-A1-106379, EP-A1-235864, EP-A1-274795 and EP-A1-279447 disclose catalytic systems for carbonylation comprising a palladium compound, a triarylphosphine and a proton acid and methods for carbonylation of an acetylenic unsaturated compound and an olefinic compound with the use of such catalytic systems. Japanese Patent Publication No. 29212/1993 (JP-B-5-29212), Japanese Patent Application Laid-open No. 176549/1986 (JP-A-61-176549), Japanese Patent Application Laid-open No. 72649/1987 (JP-A-62-72649) and Japanese Patent Application Laid-open No. 154646/1988 (JP-A-63-154646) disclose carbonylation catalytic systems comprising a bivalent palladium compound, an organic phosphine and a proton acid, and methods for carbonylation of an acetylenic unsaturated compound and an olefinic compound by using the catalytic systems. The Japanese Patent Application Laid-open No. 154646/1988 (JP-A-63-154646) describes that a homogeneous compound is rather preferred as the palladium compound than a heterogeneous compound and that a phosphine having a heterocyclic group is used as the organic phosphine and, as an inert solvent, N-methylpyrrolidone is preferred. Further, Japanese Patent Application Laid-open No. 215851/1992 (JP-A-4-215851) discloses a catalytic system for carbonylation which comprises a Group VIII metal source of Periodic Table of the Elements, a phosphine substituted with an aromatic substitute containing an imino-nitrogen atom, a proton source and an anion source of an alkylsulfonic acid, and a method for carbonylation of an acetylenic unsaturated compound and an olefinic compound using the catalytic system. Moreover, Japanese Patent Application Laid-open No. 215852/1992 (JP-A-4-21852) discloses a catalytic system comprising a Group VIII metal source, a phosphine having an imino-nitrogen atom-containing aromatic substituent, a proton source and an anion source of an alkylsulfonic acid, and a method of carbonylation of an acetylenic or olefinic unsaturated compound with the use of the catalytic system. There is described in these literatures, JP-A-4-215851 and JP-A-4-215852, that as the Group VIII metal source of Periodic Table of the Elements, a compound containing the Group VIII metal, specifically a palladium compound is rather preferred than an element in a metallic state. According to these technologies, a methacrylic acid ester, for example, can be obtained from methylacetylene, carbon monoxide and an alcohol without using sulfuric acid in a large quantity. Therefore, these technologies are superior to the acetone-cyanohydrin method for a production of a methacrylic acid ester in a point that a methacrylic acid ester can be produced without exhausting industrial wastes such as waste sulfuric acid. The catalytic systems used in the methods have, however, a significant disadvantage that they have a short catalyst life although having an initial activity to a certain extent, and thus they are not suitable as a catalyst for commercial use. By way of illustration, in carbonylation of an acetylenic unsaturated compound, use of a heterogeneous catalytic system comprising a catalytic component in a metallic state such as palladium black as the catalytic system results in not so much high catalytic activity and causes a significant decrease of the catalytic activity in a short period. When a homogeneous catalytic system containing a palladium compound such as palladium chloride is used as the catalytic system, the palladium compound is reduced in the course of the reaction to precipitate as a metallic simple substance in the reaction system, and a ligand such as an organic phosphine is oxidized which results in a decreased catalytic activity. In fact, a practical use of a palladium compound as a component of the above-mentioned catalytic system in a carbonylation reaction results in metalation of palladium to rapidly precipitate or dispose in the reaction mixture and thus in decrease of the catalytic activity and reaction rate for carbonylation. Further, as set forth in the Japanese Patent Application Laid-open No. 215852/1992 (JP-A-4-215852), when a catalytic system comprising a Group VIII element and an triarylphosphine as base components is incorporated with a tertiary amine, the catalytic properties of the catalyst is quite decreased in a carbonylation of an olefin. Therefore, in the method using a tertiary amine such as pyridine as described in the Japanese Patent Application Laid-open No. 215852/1992 (JP-A-4-215852), a phosphine having an aromatic substituent containing an imino-nitrogen atom (e.g., bisphenyl-2-pyridylphosphine) is required to be used as the phosphine, and components for the catalytic system are remarkably restricted. Moreover, the catalytic system comprising a palladium compound as the catalytic component shows insufficient catalytic activity. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a carbonylation catalytic system whereby, even though being a heterogeneous catalytic system, a high catalytic activity can be obtained and maintained for a long period, and a method for carbonylation using the catalytic system. Another object of the present invention is to provide a catalytic system whereby, even if containing a palladium source, a decrease of the catalytic activity can be suppressed and thus carbonylation can be conducted with high transformation rate and selectivity and with high stability, and a method for carbonylation with the use of such catalytic system. It is a further object of the invention to provide a catalytic system and a method for carbonylation whereby a carbonylation product such as a carboxylic acid and a carboxylic acid ester can be produced by carbonylation of an acetylenic or olefinic unsaturated compound in a stable liquid phase system with maintaining high transformation rate and selectivity for a long duration. A yet further object of the present invention is to provide a catalytic system and a method for carbonylation which are useful for producing an α,β-ethylenic unsaturated carboxylic acid or a derivative thereof such as methyl methacrylate with high transformation rate and selectivity and with maintaining high stability for a long period. It is another object of the present invention to provide a catalytic system for carbonylation having, regardless of comprising a tertiary amine or not, high stability and high catalytic activity without the use of a special phosphine having an imino-nitrogen atom-containing aromatic substituent, and a method for carbonylation utilizing such catalytic system. It is a further object of the invention to provide a stabilized catalytic system whereby carbonylation can be carried out with high transformation rate and selectivity, and a method for carbonylation using the catalytic system. A yet another object of the present invention is to provide a catalytic system and a method for carbonylation whereby a carbonylation product such as a carboxylic acid and a carboxylic acid ester can be produced by carbonylation of an acetylenic or olefinic unsaturated compound in a stable liquid phase system with maintaining high transformation rate and selectivity. A still further object of the present invention is to provide a catalytic system and a method for carbonylation which are useful for producing an α,β-ethylenic unsaturated carboxylic acid or a derivative thereof such as methyl methacrylate with high transformation rate and selectivity. After intensive investigation and research to accomplish the above objects, the inventors of the present invention found that when a Group VIII metal of Periodic Table of the Elements such as palladium is supported on a carrier and is used in a catalytic system in combination with a ligand such as an organic phosphine and an acid such as an alkylsulfonic acid, a high catalytic activity can be obtained in spite of being a heterogeneous catalytic system, and moreover, decrease of such catalytic activity can significantly be suppressed or restrained. They further found that a combination use of a Group VIII element of Periodic Table of the Elements except for palladium, a non-heterocyclic ligand which does not contain a nitrogen atom as a hetero atom, and a specific electron donative compound can suppress or prevent decrease of the catalytic activity, and remarkably improve or enhance the catalytic activity in combination with an amine, and that when using platinum, typically speaking, the catalytic activity can further be enhanced and a carbonylation product can be produced with high selectivity. The present invention has been accomplished based on the above findings. Thus, the present invention provides the use of a carbonylation catalytic system (A) which comprises a combination of (A1) a Group VIII metal source of Periodic Table of the Elements, (A2) a ligand and (A3) an acid in the production of a monomeric carbonyl group containing compound by reacting (a) an acetylenic unsaturated compound or an olefinic unsaturated compound with (b) carbon monoxide. The Group VIII metal source of Periodic Table of the Elements (A1) may be cobalt, nickel, rhodium, palladium or platinum, or a compound of such metal. The carrier may be an activated carbon, an oxide of a metal or nonmetal oxide or a clay mineral. The specific surface area of the carrier may be 10 to 3,000 m 2 /g. The supporting amount of the Group VIII metal source (A1) may frequently be 0.01 to 20% by weight relative to the carrier. The ligand (A2) may be a phosphorus compound such as a tertiary organic phosphine and others; an arsenic compound such as a tertiary organic arsine, for example; or an antimony compound. As the acid, use may be made of a proton acid (a Brönsted acid) such as an arylsulfonic acid, an alkylsulfonic acid, a carboxylic acid, a hydrohalogenic acid, sulfuric acid, nitric acid, a phosphoric acid or a perhalogenic acid, for example. According to the method of the present invention, an acetylenic or olefinic unsaturated compound is allowed to react with carbon monoxide in the presence of the catalytic system (A) to produce a monomeric carbonylation product. Further, the reaction may also be conducted in the presence of a nucleophilic compound having a hydrogen atom which can be left or eliminated (for example, a compound having a hydroxyl group such as water, an alcohol, a carboxylic acid and the like) to give an unsaturated carboxylic acid, a saturated carboxylic acid or a derivative thereof such as an ester or anhydride of the carboxylic acid corresponding to the acetylenic or olefinic unsaturated compound. Furthermore there is provided a catalytic system (A) for carbonylation which comprises a combination of (A1) a palladium source, said palladium source being supported on a carrier having a specific surface area of 100 to 2,000 m 2 /g, (A2) a tertiary organic phosphine or a tertiary organic arsine and (A3) a proton acid. DETAILED DESCRIPTION OF THE INVENTION In this specification, the term "olefinic unsaturated compound" means and includes a compound having an ethylenic unsaturated double bond regardless of the number of such double bond. The catalytic system (A) is now described in detail. The catalytic system (A) comprises (A1) a Group VIII metal source of Periodic Table of the Elements (hereinafter may briefly referred to as Group VIII metal source) which is supported on a carrier or support. The Group VIII metal element includes, for example, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum. On or after the year of 1990, these elements are classified into the Group 8 elements (Fe, Ru, Os), the Group 9 elements (Co, Rh, Ir) and the group 10 elements (Ni, Pd, Pt) of Periodic Table of the Elements. As preferred elements, there may be mentioned cobalt, nickel, rhodium, palladium and platinum, and specifically preferred are cobalt and palladium. Among them, palladium can advantageously be employed. The oxidation number of such element can be selected according to the species thereof and is not critically restricted. The oxidation number may frequently be 0, +2 or +3, for instance. The Group VIII metal source may whichever of a simple substance of the metal, or a compound containing the Group VIII element. The catalytic system (A) of the present invention is characterized in that high catalytic activity can be obtained and maintained for a long time, even though using such simple substance of the metal. Examples of the compound of the Group VIII element include an inorganic acid salt (for instance, a nitrate, a sulfate, a perhalogenate, a hydrohalogenic acid such as hydrochloric acid and hydrobromic acid), an organic acid salt (for example, a sulfonate such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, a phosphonic acid salt, a salt of a carboxylic acid having 20 or less carbon atoms (for example about 12 or less carbon atoms) such as formic acid, acetic acid, propionic acid and others), a halide (a chloride or a bromide, for example), a complex (or a complex salt) and so on. According to the present invention, even when the Group VIII metal source is a hydrohalogenic acid salt of the Group VIII metal such as palladium chloride, a risk of corrosion can be minimized and still more, high catalytic activity can be sustained for a long period of time. As a ligand constructing the complex, there may be mentioned for example OH (hydroxo), an alkoxy group such as methoxy, ethoxy, propoxy and butoxy groups, an acyl group such as acetyl and propionyl groups, an alkoxycarbonyl group such as methoxycarbonyl (acetato) and ethoxycarbonyl group, acetylacetonato, cyclopentadienyl group, benzylidene group, benzylideneacetone, benzylideneacetylacetone, benzylideneacetophenone, a cycloalkadiene such as cyclooctadiene, a halogen atom such as chlorine atom and bromine atom, CO, CN, oxygen atom, H 2 O (aquo), a phosphine (for instance, a triarylphosphine such as triphenylphosphine), a nitrogen-containing compound such as NH 3 (ammine), NO, NO 2 (nitro), NO 3 (nitrato), ethylenediamine, diethylenetriamine, pyridine and phenanthroline. In such complex or complex salt, one or more of ligands of the same or different species may be coordinated. Examples of the complex include a palladium complex such as acetylacetonepalladium, tetrakis(triphenylphosphine)palladium, bis (tri-o-tolylphosphine)palladium acetate, bis(diphenyl-2-pyridylphosphine)palladium acetate, tetrakis(diphenyl-2-pyridylphosphine)palladium, bis (di-o-tolylpyridylphosphine)palladium acetate, bis(diphenylpyridylphosphine)palladium sulfate and others, and corresponding complexes of the above-mentioned Group VIII metals. As the carrier (support), a conventional carrier whereby dispersing property of the catalytic active component can be improved or enhanced and effective surface area can be increased may be used. Examples of such carrier include an activated carbon; a metal or nonmetal oxide (including a compound oxide) such as silica, alumina, silica-alumina, magnesia, silica-magnesia and titania; a clay mineral such as diatomaceous earth, kaolin, bentonite, pumice, asbestos, alundum and corundum; or silicon carbide, for example. As examples of the activated carbon, there may be mentioned, regardless of its origin, an activated carbon obtainable from whichever of a raw material including a carbonizable vegetable (plant) raw material such as wood, charcoal, coconut shell and carbonized products of these materials; a carbonizable mineral raw material such as lignite, coal, coal tar and petroleum pitch; a carbonizable polymer raw material such as phenol resin, furan resin, epoxy resin, acrylic resin and polyacrylonitrile, vinylidene chloride resin. The activated carbon may be a product obtainable by any activating process or treatment such as chemical activation, or steam (aqueous vapor) activation, for example. Preferred examples of the carrier include an activated carbon; a metal or nonmetal oxide such as silica, alumina (including γ-alumina), silica-alumina and titania, and in particular, an activated carbon. Form (shape) of the carrier may be selected according to the reaction type such as suspension type and fixed-bed type, and is for instance powdery, granular, fibrous structure, pellet structure or honeycomb structure, for example. The specific surface area of the carrier may be selected from a range as far as the catalytic activity is not adversely affected, and is, for example, 0.1 to 3,000 m 2 /g, usually about 10 to 3,000 m 2 /g, preferably 10 to 2,500 m 2 /g, and more preferably 50 to 2,000 m 2 /g (for instance 50 to 1,500 m 2 /g). The carrier having a specific surface area of 100 to 2,000 m 2 /g may frequently be used. When the specific surface area of the carrier is too small, high catalytic activity can hardly be obtained. The pore volume and mean pore size (diameter) can be any volume and size within a range wherein the activity and stability of the catalyst are not sacrificed. As such, the mean pore size of the carrier may, for example in case of the activated carbon, usually 0.5 to 20 nm (5 to 200 Å), and preferably 1 to 15 nm (10 to 150 Å). The pore volume of the carrier is for example 0.05 to 7 ml/g, preferably 0.05 to 3 ml/g, and more preferably 0.1 to 2 ml/g. Exceedingly small mean pore size or pore volume of the carrier tends to decrease the catalytic activity. Conversely, the catalyst life has a tendency to be shortened because of an excess amount of the mean pore size or pore volume. Supporting amount of the Group VIII metal source may be chosen within a range insofar as the catalytic activity and the stability of the catalyst, and is, for instance, 0.01 to 40% by weight, usually 0.01 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight and frequently 0.5 to 5% by weight relative to the amount of the carrier. When too much small amount of the catalyst is supported on the carrier, sufficiently high catalytic activity may hardly be obtained. On the contrary, too much large amount of the supported catalyst may occasionally result in sacrificing the activity and stability of the catalyst as well as economical performance. Supporting of the Group VIII metal source (A1) on the carrier can be conducted according to a conventional supporting process such as impregnation, coating, spraying, adsorption or precipitation process. By oxidizing or reducing the metal source supported on the carrier, the oxidation number of the metal element can be converted to a desired value. By way of illustration, by supporting a compound of the Group VIII metal having an oxidation number of +2 such as palladium chloride on the carrier and subjecting the supported compound to a treatment with a reducing agent such as formalin, a simple substrate of the Group VIII metal having a oxidation number of 0 such as palladium metal supported on the carrier can be obtained. The catalytic system (A) contains a ligand (A2). This ligand (A2) may frequently be different from the ligand which constitute the metallic compound (complex) of the Group VIII metal as mentioned above. Usually, the ligand (A2) comprises at least one phosphorus atom, arsenic atom, nitrogen atom or antimony atom, and can be coordinated to the Group VIII element. These ligand can be used singly or in combination. Examples of the ligand (A2) include a ligand shown by the following formula (Ia): wherein A represents a phosphorus atom, an arsenic atom or an antimony atom; and R 1 , R 2 and R 3 independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group, or R 2 and R 3 may together form an optionally substituted alkylene group, with a proviso that R 1 to R 3 are not concurrently hydrogen atoms. In the formula (Ia), the alkyl group includes, for example, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups. Preferred alkyl group includes, for instance, a lower alkyl group having 1 to 6 carbon atoms, specifically 1 to 4 carbon atoms. As examples of the alkenyl group, there may be mentioned a straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms such as vinyl, allyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl and 1-decenyl groups. Preferred examples of the alkenyl group include an alkenyl group having 2 to 6 carbon atoms, and in particular 2 to 4 carbon atoms. The alkynyl group includes, for example, an alkynyl group having 2 to 10 carbon atoms such as ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, 1-nonynyl and 1-decynyl groups. Example of the cycloalkyl group includes a cycloalkyl group having 4 to 10 carbon atoms such as cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups. The aryl group includes, for instance, phenyl group and naphthyl group. The heterocyclic group includes a heterocyclic group containing a nitrogen atom as a hetero atom, specifically an aromatic heterocyclic group. As such heterocyclic group, there may be mentioned, for example, a pyridyl group such as 2-pyridyl group, a pyrazinyl group such as 2-pyrazinyl group, a quinolyl group such as 2-quinolyl group, an isoquinolyl group such as 1-isoquinolyl group, a pyrimidinyl group such as 2-pyrimidinyl group, a pyridazinyl group such as 3-pyridazinyl group, cinnolinyl group, triazinyl group, quinoxalinyl group or quinazolinyl group, for example. Preferred example of the heterocyclic group includes pyridyl group or pyrimidinyl group, for example. These alkyl group, cycloalkyl group, aryl group and heterocyclic group may have a various substitute which does not affects on the catalytic activity adversely such as a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group or a cyano group. The halogen atom includes fluorine, chlorine, bromine and iodine atoms. As the alkyl group, there may be mentioned for instance an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl and other groups, preferably an alkyl group having 1 to 6 carbon atoms and typically 1 to 4 carbon atoms. Example of the alkoxy group includes an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy and hexyloxy groups. Typically preferred alkoxy group includes a lower alkoxy group having 1 to 4 carbon atoms. As the alkoxycarbonyl group, there may be mentioned for instance an alkoxycarbonyl group having, in the alkoxy moiety, 1 to 10 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl and hexyloxycarbonyl groups. Preferred example of the alkoxycarbonyl group includes a lower alkoxycarbonyl group having, in the alkoxy moiety, 1 to 6 carbon atoms, and typically 1 to 4 carbon atoms. The acyl group includes, for example, an acyl group having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl and pivaloyl groups. R 2 and R 3 may together form an alkylene group having 1 to 10 carbon atoms such as methylene, ethylene, propylene, isopropylene, isopropylidene and tetramethylene groups, to form a cyclic group containing A. By way of illustration, R 2 and R 3 may together form a phosphacycloalkylene group having 3 to 10 carbon atoms together with a phosphorus atom. Preferred example of the ligand includes an organic phosphorus compound, an organic arsenic compound and an organic antimony compound, typically an organic phosphine and an organic arsine, and specifically an organic phosphine. The organic phosphine may be whichever of a primary phosphine (for example, methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, isoamylphosphine, phenylphosphine or cyclohexylphosphine), a secondary phosphine (for instance, dimethylphosphine, diethylphosphine, diisopropylphosphine, di-n-butylphosphine, diisoamylphosphine, diphenylphosphine, dicyclohexylphosphine) or a tertiary phosphine. The organic arsine may also be whichever of a primary arsine, a secondary arsine or a tertiary arsine. Preferred example of such organic phosphine and organic arsine includes a tertiary phosphine and a tertiary arsine shown by the formula (Ia). Preferable organic phosphine may be an organic phosphine of the formula (Ia) wherein at least one of R 1 to R 3 is an aryl group such as phenyl group or a substituted phenyl group. The heterocyclic group and the alkylene group formed by a combination of R 2 and R 3 are also preferred as an alternative for the aryl group or as in combination with the aryl group. As practical examples of the organic phosphine, there may be mentioned (i) an optionally substituted triarylphosphine such as triphenylphosphine, tri(4-methylphenyl)phosphine, tri(3,5-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri (4-methoxyphenyl)phosphine, tri (3,5-dimethoxyphenyl)phosphine, tri(4-chlorophenyl)phosphine and tri(3,5-dichlorophenyl)phosphine; (ii) a mono-C 1-10 alkyl-diarylphosphine such as methyldiphenylphosphine, ethyldiphenylphosphine, propyldiphenylphosphine and butyldiphenylphosphine; (iii) a di-C 1-10 alkyl-monoarylphosphine such as dimethylphenylphosphine, diethylphenylphosphine, dipropylphenylphosphine and dibutylphenylphosphine; (iv) a tri-C 1-10 alkyl-phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, triamylphosphine or trihexylphosphine, for example; (v) a mono-C 4-10 cycloalkyl-diarylphosphine such as cyclopentyldiphenylphosphine and cyclohexyldiphenylphosphine; (vi) a di-C 4-10 cycloalkyl-monoarylphosphine such as dicyclopentylphenylphosphine and dicyclohexylphenylphosphine; (vii) a tri-C 4-10 cycloalkylphosphine such as tricyclopentylphosphine and tricyclohexylphosphine; (viii) a phosphine having a heterocyclic group such as 2-pyridylbisphenylphosphine, bis(2-pyridyl)phenylphosphine, tris(2-pyridyl)phosphine, 2-pyridylbismethylphosphine, bis(2-pyridyl)methylphosphine, 2-pyridylbisethylphosphine, bis(2-pyridyl)ethylphosphine, 2-pyridylbisbutylphosphine, bis(2-pyridyl)butylphosphine, 6-methyl-2-pyridylbisphenylphosphine, bis(6-methyl-2-pyridyl)phenylphosphine, tris(6-methyl-2-pyridyl)phosphine, 6-ethyl-2-pyridylbisphenylphosphine, bis(6-ethyl-2-pyridyl)phenylphosphine, tris (6-ethyl-2-pyridyl)phosphine, 6-butyl-2-pyridylbisphenylphosphine, bis(6-butyl-2-pyridyl)phenylphosphine, tris(6-butyl-2-pyridyl)phosphine, 4,6-dimethyl-2-pyridylbisphenyl-phosphine, 6-methoxy-2-pyridylbisphenylphosphine, bis(6-methoxy-2-pyridyl)phenylphosphine, tris(6-methoxy-2-pyridyl)phosphine, 6-chloro-2-pyridylbisphenylphosphine, bis(6-chloro-2-pyridyl)phenylphosphine, tris (6-chloro-2-pyridyl)phosphine, 4,6-dichloro-2-pyridylbisphenylphosphine, 6-bromo-2-pyridylbisphenylphosphine, bis(6-bromo-2-pyridyl)phenylphosphine, 2,6-bis(diphenylphosphino)pyridine, 2,6-bis(di-p-tolylphosphino)pyridine and so on; (ix) other phosphine such as ethane-1,2-diylbisdiphenylphosphine, ethane-1,2-diylbis[bis(trifluoromethyl)phosphine], ethene-1,2-diylbisdiphenylphosphine, ethyne-1,2-diylbisdiphenylphosphine, 1,2-phenylenebisdiphenylphosphine, hexafluorocyclopentene-1,2-diylbisdiphenylphosphine, tetrafluorocyclobutene-1,2-diylbisdiphenylphosphine, octafluorocyclohexene-1,2-diylbisdiphenylphosphine, 1,4-diphenyl-1,4-diphosphacyclohexane or bis(1,2-diphenyl)phosphinomethylcyclobutane, for example. As preferred organic arsine, there may be mentioned an organic arsine corresponding to the preferred organic phosphine as mentioned above, including an optionally substituted triarylarsine such as triphenylarsine; a mono-C 1-10 alkyl-diarylarsine such as ethyldiphenylarsine; a di-C 1-10 alkyl-monoarylarsine such as diethylphenylarsine and others. An antimony compound (typically, a tertiary organic stibine) corresponding to the above-exemplified phosphorus compound may also preferably be employed as the ligand. The ligand (A2) may be supported on the carrier together with the Group VIII metal source. Supporting of such ligand can be conducted according to a conventional technology, for example, the process as mentioned above. As the acid (A3) constituting the catalytic system (A), a variety of proton acids (inorganic acids and organic acids) and Lewis acids can be used. The proton acid includes, for example, sulfuric acid, a hydrohalogenic acid, nitric acid, phosphoric acid, a sulfonic acid (for instance, an arylsulfonic acid or an alkylsulfonic acid), phosphonic acid, a carboxylic acid, perhalogenic acid and a heteropolyacid. These acid may be used singly or in combination. The acid may probably act or function as a proton source (proton donor). Therefore, when employing a Lewis acid, such Lewis acid may frequently be used in combination with other proton source. As the inorganic compound among the proton acids, there may be exemplified with sulfuric acid; a hydrohalogenic acid such as hydrochloric acid and hydrobromic acid; a phosphoric acid (for example, orthophosphoric acid or pyrophosphoric acid); perhalogenic acid such as perchloric acid; a heteropolyacid containing V, W or Mo such as phosphomolybdic acid, tungstosilicic acid and vanadomolybdic acid. Among such proton acids, the organic compound includes, for instance, an optionally substituted arylsulfonic acid such as benzenesulfonic acid, p-toluenesulfonic acid and naphthalenesulfonic acid; an optionally substituted alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, t-butylsulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid and trichloromethanesulfonic acid; a phosphonic acid such as benzenephosphonic acid; a carboxylic acid including an optionally substituted saturated aliphatic carboxylic acid such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and oxalic acid, an alicyclic acid such as cyclohexanecarboxylic acid, an aromatic carboxylic acid such as benzoic acid, phthalic acid, isophthalic acid and terephthalic acid, an unsaturated aliphatic carboxylic acid such as acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and oleic acid; an amino acid such as aspartic acid or glutamic acid. The acid may be an acidic ion exchange resin such as an ion exchange resin having a sulfonic acid group, a phosphonic acid group or a phosphinic acid group, for example. Example of the Lewis acid includes a halide of an element belonging to the Group VIIIB, the Group IVA, the Group IVB, th Group VA or the Group VB of Periodic Table of the Elements, or a complex compound thereof such as BF 3 , BF 3 •O(C 2 H 5 ) 2 , AlCl 3 , TiCl 4 , Ti[OCH(CH 3 ) 2 ] 4 , SnCl 4 , SnCl 2 , NbF 5 , TaF 5 , PF 5 , AsF 5 and SbF 5 ; or an alkoxide (for example, a C 1-5 alkoxide). The acid may usually have an anion capable of coordinating. As preferred example of the acid, there may be mentioned a proton acid (Brönsted acid) including an arylsulfonic acid such as p-toluenesulfonic acid; an alkylsulfonic acid having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably an alkylsulfonic acid having 1 to 4 carbon atoms such as methanesulfonic acid; an aliphatic carboxylic acid, preferably an aliphatic unsaturated carboxylic acid having 2 to 10 carbon atoms; an inorganic acid (for instance, sulfuric acid, a hydrohalogenic acid or a phosphoric acid). The acid may be supported on the carrier with the Group VIII metal source. Such acid can be supported according to a conventional method such as a technology as mentioned above. The catalytic system (A) may further comprises an electron donative (electron repelling) compound. As the electron donative compound, a compound having an electron donability ΔνD of not less than 2 may be used, for example. The electron donability means a sift value of wave number of O-D non-conjunctive stretching vibration of a deuterated (deuterium-containing) methanol (0.4 mol per liter) in a liquid compound when benzene is used as a primary standard, and is defined as "an electron donability ΔνD relative to methanol D". Such electron donative compound may probably have coordinating properties to the Group VIII element. As such electron donative compound, there may be exemplified with an amine, an imine, an amide, a sulfoxide, an aldehyde, an ether, a ketone, a lactone, an ester, a nitrile, a nitro compound, an aromatic hydrocarbon, an aliphatic hydrocarbon and so on. These compounds may be used singly or in combination. With respect to the electron donability ΔνD, there can be referred to, for instance, "Solvent Effect on Organic Chemical Reaction" written by Senoo and Arai, published by Sangyo Tosho Co., Ltd., Japan on April 25, 1976. For the following electron donative compounds as examples, the value of the electron donability ΔνD is indicated in a parenthesis, for reference. The amine includes, for instance, an aliphatic amine such as methylamine, ethylamine (233), n-propylamine (230), n-butylamine, diethylamine, di-n-propylamine (242), dibutylamine and triethylamine (238); an alicyclic amine such as cyclohexylamine; an aromatic amine such as aniline (158), N-methylaniline (151) and N,N-dimethylaniline (148); an alkanolamine such as dimethanolamine, trimethanolamine, ethanolamine, diethanolamine, triethanolamine, dipropanolamine, tripropanolamine, butanolamine, dibutanolamine, tributanolamine, dimethylaminoethanol and diethylaminoethanol; a heterocyclic amine such as morpholine, N-methylpyrrolidone, pyrrole, imidazole, 1-methylimidazole, pyridine (168), α-picoline (183), β-picoline, γ-picoline (160), 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine (179), 2,3,4-trimethylpyridine, 2,4,6-trimethylpyridine, dipyridine, o-toluidine (145), piperidine (240), 4-vinylpyridine (193), pyrazine, pyrimidine, quinoline or isoquinoline. The amine also includes a resin and an ion exchange resin having a basic group such as amino group, a substituted amino group including, for instance, a monoalkylamino group or a dialkylamino group and quaternary ammonium group (e.g. an amine resin such as a pyridine resin obtainable from a reaction of pyridine and formaldehyde). Typical example of the amine includes a secondary amine and a tertiary amine, and specifically a heterocyclic amine containing a nitrogen atom as a hetero atom (for example, pyridine, imidazole, etc.) or a derivative thereof and an alkanolamine. The derivative of such heterocyclic amine includes, for instance, a compound substituted with an alkyl group having 1 to 4 carbon atoms and others (e.g. picoline, lutidine, dipyridine or 1-methylimidazole). The heterocyclic amine such as pyridine and its derivative may frequently have aromaticity. Example of the imine includes ethyleneimine (237), or N-phenylethyleneimine (186), for example. The amide includes, for instance, formamide, acetamide, N,N-dimethylformamide (107), N,N-dimethylacetamide (113), tetramethylurea and hexamethylphosphamide. As the sulfoxide, there may be mentioned dimethylsulfoxide (141), diisopropylsulfoxide, sulfolane, 2-methylsulfolane and 3-methylsulfolane, for instance. The aldehyde includes, for example, an aliphatic aldehyde such as acetaldehyde (79), propionaldehyde (85), n-butylaldehyde (83), acrolein (122), metacrolein and crotonaldehyde (75); and an aromatic aldehyde such as benzaldehyde (53) . Example of the ether includes a chain ether such as diethyl ether (78), di-n-propyl ether (73), di-isopropyl ether (75), ethyl n-butyl ether (77), ethyl vinyl ether (31), n-butyl vinyl ether (33), isobutyl vinyl ether (33), diallyl ether (66), 1,2-dimethoxyethane (71), cellosolve (ethylene glycol monoethyl ether), carbitol (diethylene glycol ethyl ether), diglyme [bis(2-methoxyethyl) ether], diethylene glycol dimethyl ether and diethylene glycol diethyl ether; an aromatic ether such as anisole (26), phenetole (25), 1,2-dimethoxybenzene and diphenyl ether; and a cyclic ether such as propylene oxide (59), styrene oxide (51), 3,3-bischloromethyloxetane (78), furan (4), tetrahydrofuran (90), 1,3-dioxolan (58), 2-methyl-1,3-dioxolan (61), 4-methyl-1,3-dioxolan (56), 2-phenyl-1,3-dioxolan (56), 4-chloromethyl-1,3-dioxolan (43), tetrahydropyran (93) and 1,4-dioxane (77). Typical use is made of an aromatic ether having an optionally substituted aryl group (for instance, anisole) or a chain ether (e.g. diethylene glycol dimethyl ether) among these ethers. As the ketone, there may be mentioned for example an aliphatic ketone such as acetone (64), methyl ethyl ketone (57), diethyl ketone (56), diisopropyl ketone, methyl vinyl ketone (89) and methyl isobutyl ketone; an alicyclic ketone such as cyclohexanone(66); an aromatic ketone such as acetophenone (56), for example. Example of the lactone includes β-propiolactone (34), γ-butyrolactone (66), ε-caprolactone (82) and so on. The ester includes, for instance, an organic carboxylic acid alkyl ester such as methyl acetate (36), ethyl acetate (39), methyl chloroacetate (27), butyl acetate, methyl dichloroacetate (23), methyl propionate (33), ethyl propionate (32) and methyl isobutyrate (32); a vinyl ester such as vinyl acetate (21); an unsaturated carboxylic acid alkyl ester such as methyl acrylate (30), ethyl acrylate (33), methyl methacrylate (37), methyl crotonate and ethyl crotonate. Even when an unsaturated carboxylic acid alkyl ester (e.g. methyl methacrylate or methyl crotonate) is used as the ester, the reaction may proceed smoothly. As example of the nitrile, there may be mentioned acetonitrile (49), propionitrile (52), butyronitrile, acrylonitrile (37), benzonitrile (38) and others. Example of the nitro compound includes an aliphatic nitro compound such as nitromethane (6) and nitroethane (8), an aromatic nitro compound such as nitrobenzene (21). The aromatic hydrocarbon includes, for example, toluene (2), xylene (4), ethylbenzene (4), styrene (2), α-methylstyrene (4) and p-methylstyrene (2). Example of the aliphatic hydrocarbon includes ethylene chloride (2). Practically, an electron donative compound having an electron donability ΔνD of 4 to 250, preferably 10 to 230 (for instance, about 20 to 200) may be used among these compounds. A compound having an electron donability ΔνD of 30 to 250, preferably 50 to 250 (e.g. 100 to 250) may also be included in such preferred electron donative compounds. The electron donative compound may frequently be used as a reaction solvent in order to simplify the preparing process of the catalytic system. From the standpoint of operating properties of the reaction or others, a compound which is other than a vinyl compound (that is, a non-polymerizable compound) and does not adversely affects on the carbonylation is typically employed. As such compound, there may be mentioned, for instance, the amine such as a tertiary amine, the amide, the sulfoxide, the ether, the ketone, the ester, the nitrile, the nitro compound and the aromatic hydrocarbon (specifically, the amine, the ether, the ester and the aromatic hydrocarbon). Preferred example of the electron donative compound includes a basic compound such as the amine, the imide and the amide. Typically, when use is made of such basic compound (especially, a secondary amine and a tertiary amine) in combination with the Group VIII metal source (typically, a palladium source), the catalytic activity can significantly be improved or enhanced in many cases. Therefore, the catalytic system (A) may preferably comprise a basic compound selected from the group consisting of the amine, the imide and the amide. Further, combination use of these basic compounds with the ether and/or the ester may occasionally increase or enhance the transformation rate and the selectivity of the reaction. In the catalytic system (A), the ligand and the electron donative compound can be used in a suitable combination according to species of the metal source. By way of illustration, a combination use of the Group VIII metal source (A1) (for example, a palladium source) and an organic phosphine as the ligand may not sacrifice the stability or activity of the catalyst, regardless of species of the organic phosphine. Therefore, the organic phosphine can be used in a suitable combination with the compound having an electron donability ΔνD of not less than 2. When a triarylphosphine is employed as the organic phosphine, for example, the nitrogen-containing compound pound or the basic compound, including an amine such as pyridine or its derivative as mentioned above, is frequently employed for significant increase or improvement of not only the stability but also the activity of the catalyst. Proportions of each components of the catalytic system may be selected from a range according to species of each of the catalytic components, where the catalytic activity due to an interaction or correlation of the Group VIII metal source supported on the carrier, the ligand and the acid is not sacrificed and the stability can be maintained. Proportion of the ligand (A2) such as the organic phosphine is, for example, 0.1 to 1,000 mol, usually 5 to 500 mol, preferably 10 to 200 mol and more preferably 15 to 100 mol, relative to 1 mol of the Group VIII metal source (A1). The ligand may typically be used in a proportion of 10 to 100 mol, and preferably 20 to 60 mol per mol of the metal source. When such ligand is used in a too much small proportion, the catalytic activity tends to be decreased. On the contrary, use of the ligand in an excess amount is apt to result in an economical disadvantage. In regard to the acid (for instance, a proton acid as a proton source), the amount of such acid is, per mol of the Group VIII metal source, for example 0.1 to 1,000 mol, usually 5 to 500 mol, preferably 10 to 200 mol and more preferably 15 to 100 mol. Typical use is made of the acid in an amount of 10 to 100 mol, specifically 20 to 60 mol per mol of the metal source. Proportion of the ligand such as the organic phosphine relative to 1 mol of the acid is, for instance, 0.01 to 50 mol, usually 0.1 to 50 mol, preferably 0.2 to 20 mol and more preferably 0.5 to 5 mol. The amount of the electron donative compound is, for example, 1 to 100,000 mol, preferably 5 to 50,000 mol and more preferably 10 to 10,000 mol, relative to 1 mol of the Group VIII metal source. Such electron donative compound may frequently be used in a proportion of 10 to 10,000 mol (for example 50 to 7,000 mol), and particularly 100 to 5,000 mol per mol of the Group VIII metal source. The electron donative compound may be used as a reaction solvent, and in such a case, an excess amount of the electron donative compound relative to 1 mol of the Group VIII metal source may be sufficient. When the electron donative compound is not used as the reaction solvent, the proportion of the compound is typically 2 to 200 mol, preferably 5 to 100 mol and more preferably 10 to 50 mol per mol of the Group VIII metal source. The electron donative compound may practically be used as the reaction solvent. In a catalytic system where a Group VIII metal source as a catalytic active component is not supported on a carrier, use of a heterogeneous catalytic system containing the catalytic active component in a metal form (state) may sometimes result in an insufficient catalytic activity with decreasing the catalytic activity in a short period. When using a heterogeneous catalytic system containing a Group VIII metal compound, in some cases, the catalytic activity may gradually be decreased or sacrificed in the course of the use for some period or some times. Typically, such catalytic system containing a palladium source tends to result in significant deactivation of the catalyst, as mentioned above, although having comparatively high initial activity. To the contrary, the catalytic system (A) has, in spite of being a heterogeneous catalytic system, a high catalytic activity in carbonylation of an unsaturated hydrocarbon. Further, according to such catalytic system, high catalytic activity and long catalyst life can be obtained even when the Group VIII metal source is in a metallic form (a simple substance). Moreover, even if containing a palladium source as the Group VIII metal source, the catalytic system has meritoriously high stability, and high catalytic activity can be maintained or sustained for a long period of time. Thus, the catalyst can be used for a long time or repeatedly without activating treatment. Accordingly, the catalytic system (A) is useful for carbonylation of an acetylenic or olefinic (or ethylenic) unsaturated compound. According to the method of the present invention, an acetylenic or olefinic unsaturated compound is allowed to react with carbon monoxide in the presence of the catalytic system (A) to give a carbonylation reaction product. The acetylenic or olefinic unsaturated compound may preferably be an asymmetric acetylenic or olefinic compound, and more preferably be an α-acetylenic compound, an α-olefinic compound or an allene compound. The acetylenic compound (acetylene series compound) has usually 2 to 30, preferably 2 to 20, and particularly 2 to 10 carbon atoms. The olefinic compound and the allene compound may have, for example, 2 to 30, preferably 2 to 20, and typically 2 to 10 carbon atoms. These unsaturated compounds include an alkyne, an alkene (olefin), a cycloalkene, a cycloalkadiene and a bridged unsaturated hydrocarbon, each of which may have a substituent. The unsaturated hydrocarbon may have both of a double bond and a triple bond, or two or more of double bonds in a molecule. The unsaturated compound may have a various substituent. Example of such substituent includes a halogen atom such as fluorine, chlorine or bromine, for example; a C 1-10 cycloalkyl group such as cycloheptyl, cyclohexyl and cyclooctyl groups; an aryl group such as phenyl and naphthyl groups; an aralkyl group such as benzyl and phenethyl groups; a cyano group; an acyl group having 1 to 7 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl and pivaloyl groups; an acyloxy group having, in the alkyl moiety, 1 to 6 carbon atoms such as acetoxy group; a hydroxyl group; an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, butoxy and t-butoxy groups; a haloalkyl group such as trifluoromethyl and trichloromethyl groups; a haloalkoxy group such as trifluoromethoxy and trichloromethoxy groups; a carboxyl group; an alkoxycarbonyl group having, in the alkoxy moiety, 1 to 6 carbon atoms; an amino group and an N-substituted amino group such as a monoalkylamino group and a dialkylamino group; an amide group and an N-substituted amide group such as acetamide group, for example. As example of the alkyne, there may be mentioned acetylene, propyne, 1-butyne, 2-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 2-octyne, 4-octyne, 1,7-octadiyne, 5-methyl-3-heptyne, 4-propyl-2-pentyne, 1-nonyne, phenylacetyne, benzylethyne and cyclohexylethyne. The alkene includes, for example, ethylene, propylene, phenylethylene, 1-butene, 2-butene, 1-pentene, 3-methylpentene-1, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 2-octene, 4-octene, allene, cyclohexene and norbornadiene. As carbon monoxide, whichever of pure carbon monoxide or a carbon monoxide diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide and others may be employed. The unsaturated compound may be carbonylated individually, or in the presence of another reactant such as a nucleophilic compound having a hydrogen or a hydrogen atom which can be left in the reaction (active hydrogen). Example of the nucleophilic compound having a hydrogen atom capable of releasing includes a compound having a hydroxyl group such as an alcohol, water and a carboxylic acid. The alcohol may also include a silanol. The alcohol may be whichever of an aliphatic, alicyclic, aromatic alcohol or a phenol, and of a monohydric or polyhydric alcohol. Such alcohol may have one or more of substituents other than a hydroxyl group among the substituents as exemplified in the explanation of the unsaturated compound. As the monohydric alcohol, there may be mentioned, for instance, an aliphatic alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-methylpropan-1-ol, 2-methylpropan-1-ol, 2-methylpropan-2-ol, 1-hexanol, 1-octanol, 2-ethylhexanol, stearyl alcohol, allyl alcohol, crotyl alcohol and propargyl alcohol; an alicyclic alcohol such as cyclopentanol, cyclohexanol 4-methylcyclohexanol, cyclohexen-1-ol, cycloheptanol, cyclooctanol and borneol; and an aromatic alcohol such as benzyl alcohol, salicyl alcohol, benzhydrol and phenethyl alcohol. The phenol includes, for example, phenol, an alkylphenol, resorcinol, catechol and 2,2-bis(4-hydroxyphenyl)propane. Example of the polyhydric alcohol includes ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, trimethylene glycol, tetramethylene glycol, 1,6-hexanediol, glycerol, trimethylolpropane(2,2-bishydroxymethyl-1-butanol), pentaerythritol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, a carbohydrate (a monosaccharide, an oigosaccharide, a polysaccharide) such as glucose, fructose, mannose, galactose, saccharose, aldohexose, aldopentose, altrose, allose, talose, gulose, idose, ribose, arabonose, xylose, lyxose, erythrose, threose and cellulose. Preferred example of the alcohol includes a monohydric alcohol having 1 to 20, particularly 1 to 10, and among them 1 to 5 carbon atoms. An aliphatic saturated alcohol may typically used as the alcohol. As example of the carboxylic acid, an aliphatic carboxylic acid such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid; an alicyclic carboxylic acid such as cyclohexanecarboxylic acid; an aromatic carboxylic acid such as benzoic acid, phthalic acid, isophthalic acid and terephthalic acid; and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and oleic acid. An aliphatic carboxylic acid, preferably that having 2 to 20, and more preferably 2 to 18 carbon atoms, and in particular an aliphatic carboxylic acid having 2 to 10 carbon atoms may be used as the carboxylic acid. An alcohol or water may frequently be used as the nucleophilic compound having a hydrogen atom which can be left in the reaction. In the carbonylation reaction, a compound corresponding to the olefinic unsaturated compound and the acetylenic unsaturated compound can be produced according to species of the reactant. By way of illustration, when water is employed as the reactant, a corresponding carboxylic acid and an unsaturated carboxylic acid such as an α,β-unsaturated carboxylic acid are produced by carbonylation of the olefinic unsaturated compound and the acetylenic unsaturated compound. The use of an alcohol results in production of an ester corresponding to the carboxylic acid and the unsaturated carboxylic acid. Further, in the case of using a carboxylic acid, an acid anhydride corresponding to the carboxylic acid and the unsaturated carboxylic acid is produced. For example, when use is made of ethylene as the olefinic unsaturated compound, and methanol or water as the reactant (nucleophilic compound), methyl propionate or propionic acid can be produced by reacting with carbon monoxide. By allowing allene as the olefinic unsaturated compound and methanol or water as the reactant (nucleophilic compound) to react with carbon monoxide, methyl methacrylate or methacrylic acid may be obtained. Methyl methacrylate or methacrylic acid may also be produced by using propyne as the acetylenic compound and methanol or water as the reactant (nucleophilic compound) to react with carbon monoxide. Thus, according to the method of the present invention, species of the reactant may be selected depending on the objective compound, and is frequently water, an alcohol or an organic carboxylic acid. Proportions of each components in the carbonylation may be selected within a wide range. By way of exemplification, the amount of the catalytic system is, in terms of atomic metal of the Group VIII metal source, 1 x 10 -6 to 2 x 10 -1 mol, preferably 1 x 10 -5 to 1 x 10 -1 mol and frequently 1 x 10 -4 to 1 x 10 -2 mol, relative to 1 mol of the acetylenic or olefinic unsaturated compound. The proportion of the catalytic system (A) may also selected from within the range 0.01 to 15% by weight, preferably 0.1 to 10% by weight, and frequently 0.5 to 8% by weight relative to the acetylenic or olefinic unsaturated compound. When the catalytic system (A) is employed, the proportion of carbon monoxide is, for example per mol of the acetylenic or olefinic unsaturated compound, 0.1 to 100 mol, preferably 1 to 80 mol, and more preferably 1.5 to 50 mol (for instance, 1.5 to 5 mol). The reactant (nucleophilic compound) may be used, for instance, in an amount of about 0.1 to 100 mol, preferably 0.1 to 80 mol, and more preferably 1 to 50 mol (for example, about 1.5 to 5 mol), relative to 1 mol of the acetylenic or olefinic unsaturated compound. When water is employed as the reactant, the amount thereof may be 0.5 to 10 mol per mol of the unsaturated compound. Meanwhile, the reactant may also be used as a reaction solvent. The reaction (carbonylation) may be carried out in an inert organic solvent. As example of such organic solvent, there may be mentioned an aliphatic hydrocarbon such as hexane and octane; an aromatic hydrocarbon such as benzene; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride and chlorobenzene; and a mixture of these solvents. Where the electron donative compound or the reactant is used as a solvent, the above-mentioned organic solvent is not necessarily employed. The carbonylation reaction may typically be conducted at a temperature of, for instance, 10 to 250°C (e.g. 10 to 200°C) and preferably 25 to 200°C, and under a pressure of 1.01 - 152 bars (1 (atmospheric) to 150 atm) and preferably 1.01 - 101.3 bars (1 to 100 atm). The reaction may be carried out in accordance with a conventional method such as a batch method, semi-batch method or continuous method, and in a liquid phase or in a gas (gaseous) phase. Since the catalytic system (A) has high stability, the reaction is practically conducted in a liquid phase. Meanwhile, the above mentioned catalytic system (A) may be used singly or in a suitable combination. After completion of the reaction, the reaction product(s) can easily be separated and purified according to a conventional technology such as a separating means including filtration, concentration, distillation, extraction, crystallization, recrystallization and column chromatography, or a combination of these technologies. Since comprising the Group VIII metal source supported on the carrier as the catalytic component, the catalytic system (A) of the present invention has high catalytic activity and excellent stability even thought being a heterogeneous catalytic system, and thus can maintain high catalytic activity in a carbonylation reaction. Therefore, when use is made of the catalytic system (A) for carbonylation of an acetylenic or olefinic unsaturated compound, a carbonylation product such as a carboxylic acid or an ester of a carboxylic acid can stably be produced in a stable liquid phase with high transformation rate and selectivity for a long period. Such carbonylation can be conducted without activation of the catalyst. Further, an α,β-ethylenic unsaturated carboxylic acid or a derivative thereof can be produced with high transformation rate and selectivity as well as high stability. The following examples are merely intended to illustrate the present invention in further detail and should not be construed as defining the scope of the invention. EXAMPLES In the following examples, the term "part" means "part by weight". Example 1 To 100 parts of acetone and 0.03 part of concentrated hydrochloric acid (an aqueous solution containing about 35% or more of hydrogen chloride) was added 1.77 part of palladium chloride for dissolving. A granular activated carbon [trade name: Shirasagi C, manufactured by Takeda Chemical Industries Co., Ltd.; specific surface area of 1,200 m 2 /g; pore volume of 0.53 ml/g; mean pore size of 17 nm (1.7 Å)] (100 parts) was dipped in the resultant solution to adsorb palladium chloride on the activated carbon. A nitrogen-substituted stainless-steel autoclave (inner volume of 30 ml) was charged with palladium chloride-supporting activated carbon prepared above in an amount of 5 x 10 -6 mol in terms of palladium chloride, and with 2 x 10 -4 mol of triphenylphosphine, 2 x 10 -4 mol of methanesulfonic acid, 4 ml of methanol and 0.1 g of methylacetylene, in turn. The autoclave was introduced with carbon monoxide up to a pressure of 60 Kg/cm 2 , and was sealed. The reaction was conducted under heating and stirring at 60°C for 2 hours. The reaction product was analyzed by gas chromatography. As a result, the mean transformation rate of methylacetylene was 142 mol/hr per gram atom of palladium, and the methylacetylene-based selectivity for the product methyl methacrylate was 80%. Example 2 The reaction solution obtained in Example 1 was concentrated under reduced pressure to remove the produced methyl methacrylate and unreacted methanol and methylacetylene. To the residual concentrate, were added methanol and methylacetylene in the same proportions as Example 1. Carbon monoxide was introduced into the autoclave and the reaction was conducted in the same manner as Example 1. A series of procedures of such concentration of the reaction mixture, charging of the raw materials, and the reaction was repeated five (5) times. The results are set forth in Table 1. In the following Tables, the term "Transformation rate" means the mean transformation rate (mol per hour) of methylacetylene per gram atom of palladium. The term "Selectivity" shows the methylacetylene-based selectivity (%) for the product methyl methacrylate. As apparent from Table 1, although the catalyst was used repeatedly, the transformation rate of methylacetylene and the selectivity for methyl methacrylate were scarcely changed or sifted. Repeating times Transformation rate (mol/hr) Selectivity (%) 1 141 81 2 139 82 3 140 81 4 138 82 5 139 80 Comparative Example 1 The procedure of Example 1 was repeated except that palladium chloride which was not supported on a carrier was used instead of palladium chloride supported on the activated carbon. Resultantly, the fed methylacetylene was transformed to methyl methacrylate at an average transformation rate of 145 mol/hr per gram atom of palladium, and the methylacetylene-based selectivity for methyl methacrylate was 81%. By analyzing the reaction mixture after completion of the reaction, it was found that a part of palladium chloride was reduced to cause a precipitate of metallic palladium. Comparative Example 2 The series of procedures described in Example 2 were repeated five times in the same manner as Example 2, except for using the reaction mixture obtained in Comparative Example 1 instead of the reaction mixture obtained in Example 1. The results are shown in Table 2. As clearly shown in Table 2, when the catalyst was utilized repeatedly, the transformation rate of the methylacetylene was significantly decreased. Repeating times Transformation rate (mol/hr) Selectivity (%) 1 112 79 2 98 80 3 83 78 4 61 78 5 53 76 Example 3 To a diluted aqueous solution of hydrochloric acid containing 1.77 part of palladium chloride was added 100 parts of γ-alumina [trade name: Neospeed, manufactured by Mizusawa Chemical Co., Ltd., Japan; specific surface area of 200 m 2 /g; pore volume of 0.40 ml/g; mean pore size of 80 Å], and γ-alumina was dipped in palladium chloride with stirring. To the dipped γ-alumina, were added 5 parts of an aqueous solution of formalin and 100 parts of a 1N aqueous solution of sodium hydroxide to reduce palladium chloride. The resultant mixture was filtrated, and the residue was washed with water and dried to give a metallic palladium-supported catalyst. The reaction was conducted in the same manner as Example 1 except that, instead of the palladium chloride supported on the activated carbon, the metallic palladium supported on γ-alumina was used in an amount of 5 x 10 -6 mol in terms of metallic palladium, and that 2 x 10 -4 mol of 2,6-bis(diphenylphosphino)pyridine was employed in lieu of triphenylphosphine. As a result, the mean transformation rate of methylacetylene was 245 mol/hr per gram atom of palladium, and methyl methacrylate was produced with a methylacetylene-based selectivity of 87%. Thus, the series of the procedures, that is, the concentration of the reaction mixture, charging of the raw materials and the reaction, was repeated 10 times in the same manner as Example 2. Resultantly, even after the procedure was repeated 10 times, methylacetylene was transformed to methyl methacrylate at a mean transformation rate of 239 mol/hr per gram atom of palladium, and the catalytic activity was scarcely decreased. Comparative Example 3 The reaction was conducted in the similar manner as Example 3 except for using palladium black which was not supported on a carrier in lieu of the metallic palladium supported on γ-alumina. As a result, the mean transformation rate for methylacetylene was 112 mol/hr per gram atom of palladium and the methylacetylene-based selectivity for methyl methacrylate was 83%. Then, the series of the procedures as in Example 2, namely, concentration of the reaction mixture, the charging of the raw materials and the reaction, was repeated 10 times. After ten-time repetition of the procedures, the mean transformation rate of methylacetylene was remarkably decreased to 18 mol/hr per gram atom of palladium, and the selectivity for methyl methacrylate was decreased to 43%. Example 4 The procedure of Example 1 was followed except that triphenylarsine was employed instead of triphenylphosphine. Methylacetylene was transformed to methyl methacrylate at a mean transformation rate of 23 mol/hr per gram atom of palladium, and the methylacetylene-based selectivity for the product methyl methacrylate was 53%. After repeating the series of procedures of concentration of the reaction mixture, charging of the raw material and the reaction five times in the same manner as Example 2, the mean transformation rate of methylacetylene and the methylacetylene-based selectivity for methyl methacrylate changed scarcely.

Claims: Use of a catalytic system (A) comprising (A1) a Group VIII metal source of Periodic Table of the Elements, said metal source being supported on a carrier, (A2) a ligand and (A3) an acid in the production of a monomeric carbonyl group containing compound by reacting (a) an acetylenic unsaturated compound or an olefinic unsaturated compound with (b) carbon monoxide. Use as claimed in claim 1, wherein the Group VIII metal source (A1) is at least one metal selected from cobalt, nickel, rhodium, palladium and platinum, or a compound of said metal. Use as claimed in claim 1, wherein the carrier in the catalytic system (A) is at least one member selected from an activated carbon, a metal oxide, a nonmetal oxide and a clay material. Use as claimed in claim 1, wherein the carrier in the catalytic system (A) has a specific surface area of 10 to 3,000 m 2 /g. Use as claimed in claim 1, wherein the supporting amount of the Group VIII metal source (A1) is 0.01 to 20% by weight relative to the carrier. Use as claimed in claim 1, wherein the ligand (A2) is at least one member selected from a phosphorus compound, an arsenic compound and an antimony compound. Use as claimed in claim 1, wherein the ligand (A2) is a tertiary organic phosphine or a tertiary organic arsine. Use as claimed in claim 7, wherein the tertiary organic phosphine or tertiary organic arsine has an aryl group, a substituted aryl group or an aromatic heterocyclic group containing a nitrogen atom as a hetero atom. Use as claimed in claim 1 wherein the acid (A3) is a proton acid or a Lewis acid. Use as claimed in claim 9, wherein the proton acid is at least one member selected from an arylsulfonic acid, an alkysulfonic acid, a carboxylic acid, a hydrohalogenic acid, sulfuric acid, nitric acid, a phosphoric acid and a perhalogenic acid. A catalytic system (A) for carbonylation which comprises a combination of (A1) a palladium source, said palladium source being supported on a carrier having a specific surface area of 100 to 2,000 m 2 /g, (A2) a tertiary organic phosphine or a tertiary organic arsine and (A3) a proton acid. Method for the production of a monomeric carbonyl group containing compound by carbonylation which comprises allowing (a) an acetylenic unsaturated compound or an olefinic unsaturated compound to react with (b) carbon monoxide in the presence of a catalytic system (A) comprising (A1) a Group VIII metal course of Periodic Table of the Elements, said metal source being supported on a carrier, (A2) a ligand and (A3) an acid. Method as claimed in claim 12, wherein the unsaturated compound is an α-acetylenic compound or an α-olefinic compound. Method as claimed in claim 12, wherein the acetylenic unsaturated compound or olefinic unsaturated compound is allowed to react with carbon monoxide and (c) a nucleophilic compound having a hydrogen atom which can be left in the reaction. Method for carbonylation as claimed in claim 14, wherein the nucleophilic compound (c) is at least one member selected from water, a compound having a hydroxyl group and a carboxylic acid. Method as claimed in claim 15, wherein the compound having a hydroxyl group is an alcohol. Method as claimed in claim 14, wherein the compound (a) is an asymmetric acetylenic or olefinic unsaturated compound, and the compound (c) is at least one compound selected from water, an alcohol having 1 to 20 carbon atoms and a carboxylic acid having 1 to 20 carbon atoms. Method as claimed in claim 15, wherein the compound (a) is an α-acetylenic hydrocarbon, and the catalytic system (A) comprises a combination of (A1) a Group VIII metal source of Periodic Table of the Elemements, said metal source being supported on a carrier, (A2) a tertiary organic phosphine or a tertiary organic arsine and (A3) a proton acid.

Inventors: INA TOMOHIDE, MATSUOKA KAZUYUKI, PAN LI RUI, INA, TOMOHIDE, MATSUOKA, KAZUYUKI, PAN, LI RUI
Applicants: DAICEL CHEM, DAICEL CHEMICAL INDUSTRIES, LTD.
Application year: 1995
Main classification: B01J31
IPC codes: C07C67, B01J31