JP2000290234A - Production of aromatic carbonate compound and aliphatic carbonate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing in one step and in a high yield an aromatic carbonate compound or aliphatic ester compound from the corresponding aromatic hydroxy compound or aliphatic hydroxy compound, respectively. SOLUTION: This method for producing the subject compound comprises reacting the corresponding aromatic hydroxy compound or aliphatic hydroxy compound with carbon monoxide and oxygen in the presence of a catalyst composed of (a-1) a polynuclear metal complex compound containing a palladium atom and a group VIII transition metal atom other than palladium, (a-2) a polynuclear metal complex compound having plural palladium atoms as the metal center and crosslinked with hetero bidentate ligand or (a-3) a palladium complex compound having as ligand a bipyridyl-based compound with no hydrogen at the α-position carbon of the ring-membered nitrogen atoms, and (b) a redox catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aromatic carbonate compound and an aliphatic carbonate compound, and more particularly, as an intermediate for the synthesis of various organic compounds such as the synthesis of polycarbonate by a transesterification method,
Aromatic carbonate compounds useful as polycarbonate resins and the like, and solvents such as resins and paints, alkylating agents, carbonylating agents or aliphatic carbonate compounds useful as polycarbonate resins, aromatic hydroxy compounds or aliphatic hydroxy compounds And a method for efficiently producing the same.

[0002]

2. Description of the Related Art An aromatic carbonate compound is a useful compound as a raw material for producing a polycarbonate by a transesterification method or as an intermediate raw material for various organic syntheses. In addition, the aliphatic carbonate compound is a compound useful as a solvent for a resin or a paint, an alkylating agent, a carbonylating agent, a polycarbonate resin, or the like.

As a method for producing an aromatic carbonate compound, there is generally a method in which an aromatic hydroxy compound and phosgene are reacted in the presence of an alkali. In this method, toxic phosgene is used, and a stoichiometric amount is used. There are some problems such as by-products of alkali salts. Therefore, many methods for producing aromatic carbonate compounds without using phosgene have been proposed. As a general method for producing an aromatic carbonate compound, a method using an oxidative carbonylation reaction of reacting an aromatic hydroxy compound to be carbonated with carbon monoxide and oxygen in the presence of a catalyst has been proposed. ing. In this method, typical catalysts to be used include a catalyst obtained by combining a palladium compound with a copper compound and a base (JP-B-61-8816, JP-B-61-43338), a palladium compound, and a cocatalyst. And catalysts comprising quinones and tetraalkylammonium halides or alkali metal halides or alkaline earth metal halides (JP-A-54-13574).
No. 3, JP-A-54-135744, JP-A-5-135744
-104564, JP-A-2-142754, JP-A-6-9505, JP-A-6-17226
8, JP-A-6-172269, JP-A-6-172269
271506, JP-A-6-271509,
JP-B-6-57678, JP-A-8-89810, JP-A-8-1930056 and U.S. Pat.
No. 49485), a catalyst comprising a palladium compound, an alkali metal or alkaline earth metal, an iodide or an onium iodide compound, and a zeolite (JP-A-1-16)
5551), a catalyst comprising a palladium compound, an alkali metal halide or an alkaline earth metal halide, and activated carbon (JP-A-8-92168), and the like. In any case, an oxidative carbonylation reaction is performed. The reaction rate is not economically sufficient, and it is necessary to use a large amount of a halogen-containing compound such as an ammonium bromide salt as a base, which results in corrosion of the reactor, loss of raw materials due to halogenation of an aromatic hydroxy compound, etc. There is a problem. In addition, a method using a palladium compound, a copper compound or a lanthanoid compound, 2-hydroxypyridine, and an aprotic polar solvent has been proposed (Japanese Patent Application Laid-Open No. Hei 9-110804). However, it is not economical because an aprotic polar solvent is essential and a solvent recovery step is required.

On the other hand, as a method for producing an aromatic carbonate compound without using an oxidative carbonylation reaction, a production method using a transesterification reaction between dimethyl carbonate and an aromatic hydroxy compound (JP-A-9-176094) However, this method requires a step of producing dimethyl carbonate as a raw material, and is not necessarily an economical method. Further, a production method by a carbon monoxide removal reaction from diphenyl oxalate (JP-A-9-255628) has been proposed. However, in order to produce an aromatic carbonate, carbon monoxide and methanol are used as raw materials. Carbonylation reaction and transesterification reaction between dimethyl oxalate and an aromatic hydroxy compound, which complicates the process and is not economical.

As a method for producing an aliphatic carbonate compound, there is generally a method in which an aliphatic hydroxy compound and phosgene are reacted in the presence of an alkali. In this method, toxic phosgene is used, and a stoichiometric amount is used. There are some problems such as by-products of alkali salts. Accordingly, many methods for producing an aliphatic carbonate compound without using phosgene have been proposed. As a method for producing an aliphatic carbonate compound, for example, a method of reacting a nitrite of an aliphatic hydroxy compound with carbon monoxide,
However, since nitrites are corrosive gases and are also explosive, there is a problem in safety, and there is a need for cost for countermeasures. There is also a problem. Further, a method of reacting an aliphatic hydroxy compound with an alkylene carbonate (Japanese Patent Publication No. 60-27658) has been proposed, but the alkylene carbonate is expensive and requires the use of glycol as a by-product. Problem. Alternatively, a method of reacting an aliphatic hydroxy compound with a carbamic acid ester of an aliphatic hydroxy compound (Japanese Patent Publication No. 1-49698) has been proposed, but a carbamic acid ester of an aliphatic hydroxy compound is expensive, and There is a problem that the reaction rate is extremely slow. Furthermore, a method of reacting an aliphatic hydroxy compound with urea has been proposed (Japanese Patent Publication No. 62-54297). In this method, toxic ammonia is produced as a by-product and an economically sufficient reaction rate is obtained. There are problems such as that a high reaction temperature of 200 ° C. or more is required to obtain.

On the other hand, a method has been reported in which an aliphatic hydroxy compound is reacted with carbon monoxide in the presence of a catalyst. Examples of the catalyst used in this method include a paper (ACSSymposium Series, No. 6).
26, p. 70, American Chemical Society), a palladium compound catalyst, a copper compound catalyst, a cobalt compound catalyst, etc. using a copper compound as a co-catalyst have been proposed. There is a problem that the catalyst life is not sufficient in terms of economy.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the conventional methods for producing an aromatic carbonate compound and an aliphatic carbonate compound, and solves the problem by using an aromatic hydroxy compound or an aliphatic hydroxy compound. It is an object of the present invention to provide a method for efficiently producing an aromatic carbonate compound or an aliphatic carbonate compound in one step and at a high yield.

[0008]

DISCLOSURE OF THE INVENTION In view of the above situation, the present inventors have solved the problems of the prior art, and obtained a high yield of aromatic carbonate from an aromatic hydroxy compound or an aliphatic carbonate compound in one step. Intensive research was conducted to develop a method for efficiently producing an ester compound or an aliphatic carbonate compound. As a result, (a-1) a polynuclear metal complex compound comprising a palladium atom and a transition metal atom other than palladium belonging to Group VIII of the Periodic Table, and (a-2) a heteronuclear metal compound having a plurality of palladium atoms as metal centers, Polynuclear metal complex compound bridged by a coordinating ligand or (a-3) a palladium complex compound having as a ligand a bipyridyl-based compound having no hydrogen at the α-position carbon of a ring member nitrogen atom, and (b) a redox catalyst It has been found that the above object of the present invention can be achieved by using these as a catalyst. The present invention has been completed based on such findings. That is, the present invention provides an aromatic hydroxy compound or an aliphatic hydroxy compound, carbon monoxide and oxygen, (a-1) a polynuclear metal comprising a palladium atom and a transition metal atom other than palladium belonging to Group VIII of the periodic table. A method for producing an aromatic carbonate compound or an aliphatic carbonate compound, characterized by reacting in the presence of a catalyst comprising the complex compound and (b) a redox catalyst; (A-
2) An aromatic compound having a plurality of palladium atoms as a metal center and reacting in the presence of a catalyst comprising a polynuclear metal complex compound crosslinked by a heterobidentate ligand and (b) a redox catalyst. A method for producing a carbonate compound or an aliphatic carbonate compound; and an aromatic hydroxy compound or an aliphatic hydroxy compound, carbon monoxide and oxygen, and (a-3) hydrogen at the α-position carbon of the ring member nitrogen atom. A method of producing an aromatic carbonate compound or an aliphatic carbonate compound, characterized by reacting a palladium complex compound having no bipyridyl compound as a ligand with a catalyst comprising (b) a redox catalyst. Is what you do.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention, various conventionally known aromatic hydroxy compounds can be used and can be appropriately selected depending on the kind of a desired aromatic carbonate compound. And aromatic hydroxy compounds selected from aromatic monohydroxy compounds and aromatic dihydroxy compounds. As the aromatic monohydroxy compound, a compound represented by the general formula (I)

[0010]

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[Wherein, n represents an integer of 1 to 3;
Represents a hydrogen atom, a halogen atom (eg, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, a cyano group or an ester group, and o
It may be in any of the-, m- and p-positions. And an aromatic monohydroxy compound having 6 to 18 carbon atoms (monohydric phenol). Specific examples include phenols such as phenol, cresol, p-methylphenol, t-butylphenol (pt-butylphenol, etc.), 4-cumylphenol, methoxyphenol, chlorophenol, cyanophenol and the like.

The aromatic dihydroxy compound is represented by the general formula (II) HO-Ar-OH (II) wherein Ar represents an arylene group. Aromatic dihydroxy compounds (dihydric phenols) represented by the formula: Specific examples include catechol, hydroquinone, resorcin and phenols which are substituted derivatives thereof. The aromatic dihydroxy compound is represented by the general formula (III)

[0013]

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[Wherein, R is a hydrogen atom, a halogen atom (eg, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms. A and b may each be an integer of 1 to 4. And Y is a single bond, an alkylene group having 1 to 8 carbon atoms, and 2 to 2 carbon atoms.
8 alkylidene group, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or -S
—, —SO—, —SO ₂ —, —O—, —CO— bond or general formula (IV)

[0015]

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The bond represented by ] It is a C12-C27 aromatic dihydroxy compound (dihydric phenol) represented by these.

Here, there are various dihydric phenols represented by the above general formula (III).
-Bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. The dihydric phenols other than bisphenol A include 1,1-bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; hydroquinone; 4,4′-dihydroxydiphenyl; (Hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide;
Bis (4-hydroxyphenyl) sulfone; bis (4-
Bis (4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) compound other than bisphenol A such as bis (4-hydroxyphenyl) ketone, or bis (3,5-dibromo-)
4-hydroxyphenyl) propane; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane and the like. When these phenols have an alkyl group as a substituent, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms.

As the aliphatic hydroxy compound, conventionally known various compounds can be used and can be appropriately selected depending on the kind of the desired aliphatic carbonate compound. For example, selected from aliphatic monohydroxy compounds and aliphatic dihydroxy compounds. Aliphatic hydroxy compounds.
As the aliphatic monohydroxy compound, a compound represented by the general formula ROH
(However, R represents an aliphatic alkyl group having 1 to 20 carbon atoms. The structure of R may be any of primary, secondary, and tertiary, and may appropriately include a branched structure, a cyclic structure, a halogen atom, and the like. .)). Specifically, methanol, ethanol, 1-propanol, 2-propanol, 2-chloro-1-propanol, 1-chloro-2-propanol,
1-butanol, 2-butanol, isobutanol, t
ert-butanol, 1-pentanol, 2-methyl-
1-butanol, 3-methyl-1-butanol, 2,2
-Dimethyl-1-propanol, cyclopentanol,
1-hexanol, 2-methyl-1-pentanol, 3
-Methyl-1-pentanol, 4-methyl-1-pentanol, 2,2-dimethyl-1-butanol, 2,3-
Dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 2-ethyl-1-butanol, 3-ethyl-
1-butanol, cyclohexanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-decanol, 2-decanol, 1-dodecanol, 2-dodecanol, 1-tetradecanol, 2-tetradecanol , 1-hexadecanol, 2-hexadecanol, 1-octadecanol, 2-octadecanol, benzyl alcohol and the like.

The aliphatic dihydroxy compound is represented by the general formula HOR'OH (where R 'represents an aliphatic alkylene group having 2 to 20 carbon atoms. The structure of R' may be a branched structure or a cyclic structure at any position. , A halogen atom or the like.). Specifically, ethylene glycol, 1,2
-Dihydroxypropane, 1,3-dihydroxypropane, 1,2-dihydroxybutane, 1,4-dihydroxybutane, 1,2-dihydroxyhexane, 1,6-dihydroxyhexane, 1,2-dihydroxyoctane,
1,8-dihydroxyoctane, 1,2-dihydroxydecane, 1,10-dihydroxydecane, 1,2-dihydroxydodecane, 1,10-dihydroxydodecane,
Cyclohexanediol, cyclohexanedimethanol, 1,2-dihydroxy-1-phenylethane, p-
(Hydroxymethyl) benzyl alcohol and the like.

The carbon monoxide to be reacted with the aromatic hydroxy compound or the aliphatic hydroxy compound may be a simple substance, may be diluted with an inert gas, or may be a mixed gas with hydrogen. The oxygen to be reacted with the aromatic hydroxy compound or the aliphatic hydroxy compound may be pure oxygen, but may be generally diluted with an inert gas, for example, an oxygen-containing gas such as air. .

On the other hand, as described above, the catalyst used in the method of the present invention comprises component (a-1), component (a-2) or component (a-3) [these components are collectively referred to as component (a). And the component (b). Here, the component (a-1) of the catalyst includes a palladium atom and a transition metal other than palladium belonging to Group VIII of the periodic table (Groups 8 to 10 in the new periodic table) in one polynuclear metal complex compound. Any compound having an atom may be used. Transition metal atoms other than palladium belonging to Group VIII of the periodic table include iridium, rhodium,
Ruthenium, platinum, nickel and the like can be mentioned. The content of the palladium atom and the transition metal atom other than palladium belonging to Group VIII of the periodic table in such a polynuclear metal complex compound may be any number as long as at least one is contained in the structure. Specific examples of such polynuclear metal complex compounds include dichlorocarbonyliridium bis (2-diphenylphosphinopyridine) palladium chloride, dichlorocarbonyliridium bis (diphenylphosphinomethane) palladium chloride, and carbonyliridium bis (diphenylphosphinomethane). Palladium chloride, dichlorocarbonylrhodium bis (2-diphenylphosphinopyridine) palladium chloride, dichlorocarbonylrhodiumbis (diphenylphosphinomethane) palladium chloride, carbonylrhodiumbis (diphenylphosphinomethane) palladium chloride, trichlorodicarbonylruthenium bis (2 −
Diphenylphosphinopyridine) palladium chloride,
Trichlorodicarbonyl ruthenium bis (diphenylphosphinomethane) palladium chloride, chlorodicarbonyl ruthenium bis (diphenylphosphinomethane) palladium chloride, chloroplatinum bis (2-diphenylphosphinopyridine) palladium chloride, chloroplatinum bis (diphenylphosphinomethane) ) Palladium chloride, chloronickel bis (2-diphenylphosphinopyridine) palladium chloride, chloronickel bis (diphenylphosphinomethane) palladium chloride and the like.

As the component (a-2) of the catalyst, any compound may be used as long as it has a plurality of palladium atoms as a metal center in one polynuclear metal compound and is crosslinked by a heterobidentate ligand. It may be. Heterodidentate ligands include phosphine structure, phosphite structure, phosphate structure, pyridine structure, imine structure, amine structure, nitrile structure, arsine structure, carbonyl structure, etc., which are common ligands for palladium complexes. Any structure may be used as long as it includes two or more different structures selected from the group consisting of at least one structure. In the present invention, among these heterobidentate ligands, a compound having a phosphine structure and a pyridine structure and a compound having an arsine structure and a pyridine structure are preferable. Specific examples of the compound having a phosphine structure and a pyridine structure include 2-diphenylphosphinopyridine, di-2-pyridylphenylphosphine, tri-2-pyridylphosphine, 2-diphenylphosphinoquinoline, and the like. Specific examples of the compound having a pyridine structure include 2-diphenylarsinopyridine. Specific examples of the polynuclear metal complex compound having a plurality of such palladium atoms as a metal center and crosslinked by a heterobidentate ligand include difluorobis (2-diphenylphosphinopyridine) dipalladium and dichlorobis (2 -Diphenylphosphinopyridine) dipalladium, dibromobis (2
-Diphenylphosphinopyridine) dipalladium, diiodobis (2-diphenylphosphinopyridine) dipalladium, dinitrite bis (2-diphenylphosphinopyridine) dipalladium, diazidobis (2-diphenylphosphinopyridine) dipalladium, diisothi Ocyanatobis (2-diphenylphosphinopyridine) dipalladium, dithiocyanatobis (2-diphenylphosphinopyridine) dipalladium, dicyanatobis (2-diphenylphosphinopyridine) dipalladium, diisocyanatobis (2-diphenylphospho) Finopyridine) dipalladium, difluorobis (2-diphenylphosphinoquinoline) dipalladium, dichlorobis (2-diphenylphosphinoquinoline) dipalladium, dibromobis (2-diphenylphosphine) Fino quinoline) dipalladium,
Diiodobis (2-diphenylphosphinoquinoline) dipalladium, dinitritebis (2-diphenylphosphinoquinoline) dipalladium, diazidobis (2-diphenylphosphinoquinoline) dipalladium, diisothiocyanatobis (2-diphenylphosphino) Quinoline)
Dipalladium, dithiocyanatobis (2-diphenylphosphinoquinoline) dipalladium, dicyanatobis (2
-Diphenylphosphinoquinoline) dipalladium, diisocyanatobis (2-diphenylphosphinoquinoline)
Dipalladium, difluorobis (di-2-pyridylphenylphosphine) dipalladium, dichlorobis (di-2
-Pyridylphenylphosphine) dipalladium, dibromobis (di-2-pyridylphenylphosphine) dipalladium, diiodobis (di-2-pyridylphenylphosphine) dipalladium, dinitrite bis (di-2-
Pyridylphenylphosphine) dipalladium, diazidobis (di-2-pyridylphenylphosphine) dipalladium, diisothiocyanatobis (di-2-pyridylphenylphosphine) dipalladium, dithiocyanatobis (di-2-pyridylphenylphosphine) Dipalladium, dicyanatobis (di-2-pyridylphenylphosphine) dipalladium, diisocyanatobis (di-2-pyridylphenylphosphine) dipalladium, difluorobis (tri-2-pyridylphosphine) dipalladium,
Dichlorobis (tri-2-pyridylphosphine) dipalladium, dibromobis (tri-2-pyridylphosphine) dipalladium, diiodobis (tri-2-pyridylphosphine) dipalladium, dinitrite bis (tri-2-pyridylphosphine) dipalladium , Diazidobis (tri-2-pyridylphosphine) dipalladium, diisothiocyanatobis (tri-2-pyridylphosphine) dipalladium, dithiocyanatobis (tri-2-pyridylphosphine) dipalladium, dicyanatobis (tri-2-pyridin) Pyridylphosphine) dipalladium, diisocyanatobis (tri-2-pyridylphosphine) dipalladium, dichlorobis (2-diphenylarsinopyridine) dipalladium, dibromobis (2-diphenylarsinopyridine) dipradi Arm, diiodobis (2-diphenyl al Shino pyridine) dipalladium, di-nitrite-bis (2-diphenyl al Shino pyridine) dipalladium, Jiajidobisu (2-diphenyl al Shino pyridine)
Dipalladium, diisothiocyanatobis (2-diphenylarsinopyridine) dipalladium, dithiocyanatobis (2-diphenylarsinopyridine) dipalladium,
Dicyanatobis (2-diphenylarsinopyridine) dipalladium, dichlorobis (2-diphenylphosphinopyridine) (μ-dimethylacetylenedicarboxylate) dipalladium, dichlorobis (di-2-pyridylphenylphosphine) (μ-dimethylacetylenedicarboxylate) ) Dipalladium, dichlorobis (tri-2-
Pyridylphosphine) (μ-dimethylacetylenedicarboxylate) dipalladium, tetrachlorobis (2-
Diphenylphosphinopyridine) tripalladium and the like. Further, a compound having a hetero-bidentate ligand and a compound having a palladium atom, which are precursors for synthesizing these polynuclear metal complex compounds, may be used alone and physically mixed.

As the component (a-3) of the catalyst, any compound may be used as long as it is a palladium complex compound having as a ligand a bipyridyl compound having no hydrogen at the α-position carbon of the ring member nitrogen atom. . Specifically, such a palladium complex compound has the general formula (V)

[0024]

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Wherein R ¹ and R ⁸ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a total of 6 to 20 carbon atoms.
Represents an aromatic group having a hydrocarbon group on the ring of, R ¹ and R ² including R ¹ or R ⁸ , substituents adjacent to each other such as R ⁷ and R ⁸ are respectively bonded to form an aromatic ring, Alternatively, an aromatic ring or an unsaturated aliphatic ring containing a hetero atom such as a nitrogen atom, an oxygen atom, and a phosphorus atom may be formed. R ^{2 to} R
⁷ independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group having a hydrocarbon group on a ring having 6 to 20 carbon atoms or a hydrogen atom, and R ¹ , R ² and R ² And R ³ , R
³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷
And the substituents adjacent to each other as in R ⁸ may be bonded to each other to form an aromatic ring, or an aromatic ring containing a hetero atom such as a nitrogen atom, an oxygen atom, a phosphorus atom or an unsaturated aliphatic ring. Good. A and B each independently represent a halogen atom, a hydroxy group, an aromatic alkoxy group, an aliphatic alkoxy group, or a hydrocarbon group having 1 to 20 carbon atoms. )).

In the above formula (V), the aliphatic hydrocarbon group having 1 to 20 carbon atoms out of R ^{1 to} R ⁸ includes a linear or branched alkyl group having 1 to 20 carbon atoms or a carbon atom having 1 to 20 carbon atoms. Cycloalkyl groups of the formulas 3 to 20 are exemplified. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl,
Octyl, decyl, dodecyl, tetradecyl,
Hexadecyl group, octadecyl group, cyclopentyl group,
Examples include a cyclohexyl group and a cyclooctyl group. An appropriate substituent such as a lower alkyl group may be introduced on the ring of the cycloalkyl group. Examples of the aromatic group having a hydrocarbon group on a ring having 6 to 20 carbon atoms include an aromatic group such as a phenyl group and a naphthyl group, and an aromatic group such as a phenyl group and a naphthyl group. 1 to 10 linear, branched or cyclic alkyl groups
And groups introduced more than once.

Further, this R¹~ R⁸Are identical to each other
Or may be different. R ¹~ R⁸Each other in
Are bonded to each other to form an aromatic ring or
It may form an unsaturated aliphatic ring. On the other hand, A and B
Of which are chlorine, bromine and iodine
Atoms and the like. Aromatic alkoxy of A and B
The di- and aliphatic alkoxy groups are represented by the above general formula
Aroma described in (I), (II), (III) and (IV)
Group hydroxy compounds or the general formulas ROH and HOR'O
H derived from the aliphatic hydroxy compound described in
Aromatic and aliphatic alkoxy groups
Can be A and B hydrocarbon groups having 1 to 20 carbon atoms
Is the above R¹~ R⁸Having 1 to 20 carbon atoms
As described for the group. As A and B
Is particularly preferably a chlorine atom, a bromine atom and an iodine atom.
A and B may be the same or different from each other.
You may. Further, in the bipyridyl structure, aromatic
Ring, unsaturated aliphatic ring, alkyl group, alkylcarbonyl
Group, alkoxycarbonyl group, etc. adversely affect the reaction of the present invention
May suitably have a substituent within a range not giving
No.

Examples of the complex compound represented by the general formula (V) include (2,2′-biquinoline) palladium dichloride, (4,4′-dimethyl-2,2′-biquinoline) palladium dichloride, 2,2'-biquinoline-
4,4'-dicarboxylic acid dipotassium salt) palladium dichloride, (dimethyl-2,2 '
-Biquinoline-4,4'-dicarboxylate) palladium dichloride, (6,7-dihydro-5,8-dibenzo [b, j] [1,10] phenanthroline) palladium dichloride, (2,9-dimethyl-1) , 10-phenanthroline) palladium dichloride, (2,9-diphenyl-1,10-phenanthroline) palladium dichloride, (2,9-di-t-butyl-1,10-phenanthroline) palladium dichloride, (6,6′- Dimethyl-2,2'-bipyridyl) palladium dichloride,
(6,6′-diphenyl-2,2′-bipyridyl) palladium dichloride, (6,6′-di-t-butyl-2,
2'-bipyridyl) palladium dichloride, (2,2 '
-Biquinoline) palladium dibromide, (4,4'-dimethyl-2,2'-biquinoline) palladium dibromide, (2,2'-biquinoline-4,4'-dicarboxic acid dipotassium salt) palladium dibromide , (Dimethyl-2,2'-biquinoline-4,4 '
-Dicarboxylate) palladium dibromide, (6,
7-dihydro-5,8-dibenzo [b, j] [1,1
0] phenanthroline) palladium dibromide, (2
9-dimethyl-1,10-phenanthroline) palladium dibromide, (2,9-diphenyl-1,10-phenanthroline) palladium dibromide, (2,9-di-
t-butyl-1,10-phenanthroline) palladium dibromide, (6,6′-dimethyl-2,2′-bipyridyl) palladium dibromide, (6,6′-diphenyl-2,2′-bipyridyl) palladium dibromide Bromide,
(6,6'-di-t-butyl-2,2'-bipyridyl)
Palladium dibromide, (2,2'-biquinoline) palladium diiodide, (4,4'-dimethyl-2,2 '
-Biquinoline) palladium diiodide, (2,2'-
Biquinoline-4,4'-dicarboxylic acid
(Dipotassium salt) palladium diiodide, (dimethyl-2,2'-biquinoline-4,4'-dicarboxylate) palladium diiodide, (6,7-dihydro-5,8-dibenzo [b, j] [1,10] phenanthroline) palladium diiodide, (2,9-dimethyl-1,10-phenanthroline) palladium diiodide, (2,9-diphenyl-1,10-phenanthroline) palladium diiodide, (2 , 9-Di-t-butyl-1,10-phenanthroline) palladium diiodide, (6,6'-dimethyl-2,2'-bipyridyl)
Palladium diiodide, (6,6′-diphenyl-
2,2′-bipyridyl) palladium diiodide,
(6,6'-di-t-butyl-2,2'-bipyridyl)
Palladium diiodide and the like can be mentioned. Further, a bipyridyl-based compound having no hydrogen at the α-position carbon of the ring member nitrogen atom and a compound having a palladium atom, which are precursors for the synthesis of these palladium complex compounds, respectively,
It may be in a physically mixed form.

In the present invention, the polynuclear metal complex compound or palladium complex compound as the component (a) may be used alone or in combination of two or more. Compounds that can be precursors of these polynuclear metal complex compounds or palladium complex compounds may be used alone and in a physically mixed form. Component (a) of these catalysts may be appropriately combined with a ligand such as alkyl phosphine or aromatic phosphine, a phosphite, a phosphate, or a nitrile ligand such as acetonitrile, as long as the reaction is not hindered. You may.

In the production method of the present invention, a redox catalyst is used as the component (b). Examples of the redox catalyst include a lanthanoid compound, a transition metal of Group V of the periodic table (Group 5 in the new periodic table), a compound of a transition metal of Group VI (Group 6 in the new periodic table), and a transition metal of Group VII. At least one selected from the group consisting of a metal (Group 7 in the new periodic table) compound, an iron compound, a cobalt compound, a nickel compound and a copper compound is used, and these are any of organic complexes, organic salts, and inorganic salts. It may be in the form. Specific examples include a cerium compound, a vanadium compound, a chromium compound, a manganese compound, an iron compound, a cobalt compound, a copper compound and the like, and preferably a cerium compound and a manganese compound. Particularly preferred redox catalysts include Ce (TMHD) ₄ , Mn (TMHD) ₃ , Ce
(Trop) ₄ , Mn (Trop) ₃ [here, TM
HD represents a 2,2,6,6-tetramethyl-3,5-heptane dionate ion, and Trop represents a tropolonate ion. And the like.

In the catalyst used in the method of the present invention, an appropriate amount of a co-catalyst such as an onium halide compound can be added, if necessary, in addition to the components (a) and (b). Examples of the onium halide compound include a compound represented by the following formula (VI). R ⁹ R ¹⁰ R ¹¹ R ¹² CD ・ ・ ・ (VI)

Wherein C is a nitrogen atom or a phosphorus atom, and D is
Halogen atoms such as fluorine, chlorine, bromine and iodine, hydro
It represents a xy group, an alkoxy group or an aryloxy group. R
⁹~ R ¹²Is an alkyl group having 1 to 8 carbon atoms or carbon
An aryl group having a prime number of 6 to 12, specifically, methyl
Group, ethyl group, propyl group, butyl group, pentyl group,
Xyl group, octyl group, cyclohexyl group, phenyl
Group, tolyl group, xylyl group, naphthyl group, etc.
You. R⁹~ R¹²May be the same or different.
Also, R⁹And R^Ten, R¹¹And R¹²Are together
Tte-(CH_Two)_nA divalent group represented by-
Is an integer of 2 to 7. )
In addition, the above-mentioned formula (V
Bis (triphenylphosphophosphonate other than the compound represented by I)
(Ranylidene) ammonium halides can also be used. So
As a specific example, tetra-n-butylammonium bromide
Amide, tetraphenylphosphonium bromide, bis (
Triphenylphosphoranylidene) ammonium bromide,
Bis (triphenylphosphoranylidene) ammonium hydrogen
Droxide, bis (triphenylphosphoranylidene) a
And ammonium phenoxide.

In the production method of the present invention, the amount of the catalyst used is not particularly limited and may be an ordinary amount. For example, for the component (a), the amount used may be the aromatic hydroxy compound or the raw material. Aliphatic hydroxy compound 1
The amount of palladium is 1 × 10 ^{-8 to} 0.5 mol, preferably 1 × 10 ^{-6 to} 0.1 mol, per mol. If the amount is less than 1 × 10 ⁻⁸ , the reaction rate may be too low to be practical. On the other hand, if it exceeds 0.5 mol, the effect corresponding thereto is not recognized and it is economically disadvantageous. (B)
The amount of the component to be used is generally 0.1 to 100 mol, preferably 0.5 to 50 mol, per 1 mol of palladium of the component (a). If the amount is less than 0.1 mol, the reaction rate may be low, which is not practical. If the amount exceeds 100 mol, the oxidative decomposition reaction of the aromatic carbonate compound or aliphatic carbonate compound produced by the component (b) may occur. Progresses and is economically disadvantageous.

In the production method of the present invention, the reaction proceeds in the absence of a solvent or in a solvent. In general, it is economically advantageous to carry out the method of the present invention in the absence of a solvent.However, if necessary for the production process of an aromatic carbonate compound or an aliphatic carbonate compound, it is preferable to carry out the method in a solvent. Is also good. Here, examples of the solvent that can be used include an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon, a halogenated hydrocarbon, an ether, an ester, a nitrogen-containing solvent, a sulfur-containing solvent, and the like, and a catalyst used in the production method of the present invention. Can be selected as appropriate depending on the type and combination of.

In the present invention, the reaction temperature is not particularly limited, but is usually 50 to 200 ° C., preferably 70 to 1 ° C.
It is in the range of 50 ° C. If the temperature is higher than the above range, side reactions such as a decomposition reaction increase, and if the temperature is lower than the above range, the reaction rate is reduced and is not practical. Further, the reaction pressure is generally set to a pressurized state because a gaseous raw material such as carbon monoxide or oxygen is used.
× 10 ^{-2 to} 20 MPa, preferably 1 × 10 ^{-2 to} 10 M
Within the range of Pa, the oxygen partial pressure is 1 × 10 ^{−2 to} 10 MPa,
Preferably, it should be in the range of 1 × 10 ^{−2 to 5} MPa. In particular, the oxygen partial pressure is desirably adjusted so that the gas composition in the reaction system is out of the explosion range. When the reaction pressure is too low, the reaction speed is reduced. Expensive and economically disadvantageous. When using an inert gas, hydrogen, or the like, the partial pressure is not particularly limited, but may be appropriately used within a practical pressure range.

The reaction system may be batch, semi-continuous or continuous. Here, the state of the reaction system is one of a liquid phase state, a mixed state of a liquid phase and a gas phase, and a mixed state of a liquid phase, a gas phase and a solid phase. The state of the catalyst in the reaction system may be homogeneous or non-uniform, and can be selected by appropriately selecting the catalyst. The catalyst may be used in a state where it is supported on an appropriate carrier, if necessary. The raw material components and the catalyst may be diluted as necessary. As a diluent, an inert solvent such as a saturated hydrocarbon is used in a liquid phase, and an inert solvent such as nitrogen, argon, ethane, and propane is used in a gas phase. An active gas is used.

The production method of the present invention comprises reacting an aromatic hydroxy compound or an aliphatic hydroxy compound with carbon monoxide and oxygen in the presence of the above-mentioned specific catalyst to obtain an aromatic carbonate compound or This is for producing an aliphatic carbonate compound. There are various aromatic carbonate compounds (that is, carbonates of aromatic hydroxy compounds) or aliphatic carbonate compounds (that is, carbonates of aliphatic hydroxy compounds) that are the target products obtained by this reaction. . For example, when an aromatic monohydroxy compound is used as a raw material, the compound represented by the general formula (VII)

[0038]

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[In the formula, X and n are the same as those in the general formula (I). ] The aromatic carbonate represented by the formula: When an aromatic dihydroxy compound is used as a raw material, the compound represented by the general formula (VIII)

[0040]

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[Wherein, R, a, b, and Y are the same as those of the general formula (II)
Same as I). m depends on the molecular weight of the product and is an integer of 1 or more. In addition, the terminal structure of the molecule is not particularly defined. ] The aromatic carbonate represented by the formula: Further, when an aliphatic monohydroxy compound is used as a raw material, the compound represented by the general formula (IX)

[0042]

Embedded image

(In the formula, R represents an aliphatic alkyl group having 1 to 20 carbon atoms. The structure of R may be any of primary, secondary and tertiary, and may have a branched structure, a cyclic structure, a halogen atom or the like. May be included.). When an aliphatic dihydroxy compound is used as a raw material, the compound represented by the general formula (X)

[0044]

Embedded image

(Wherein, R ′ represents an aliphatic alkylene group having 2 to 20 carbon atoms. The structure of R ′ may be any position,
It may contain a branched structure, a cyclic structure, an aromatic ring, a halogen atom and the like. In addition, the terminal structure of the molecule is not particularly defined. )).

[0046]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples.
As will be described in more detail, the present invention is not limited by these examples. The catalysts and reagents used in the following examples are commercially available products or those prepared according to the method described in the literature.

Example 1 In a 30 ml autoclave, 3.02 g (32 mmol) of phenol and 4.9 mg of dichlorobis (2-diphenylphosphinopyridine) dipalladium were added.
(6 micromol, 12 micromol as Pd), M
n (2,2,6,6-tetramethyl-3,5-heptanedionate) ₃ was 14.5 mg (24 μmol), and bis (triphenylphosphoranylidene) ammonium bromide was 0.15 g (0.24 g). Mmol). By pressurizing and depressurizing with carbon monoxide, the inside of the autoclave was replaced with carbon monoxide. Then, 0.50 in 25 ° C conversion
Carbon monoxide was pressurized so as to be MPa, and air was further pressurized so that the whole pressure was 0.75 MPa.

This was heated to 100 ° C. and reacted for 3 hours. After cooling and depressurizing, 20 ml of methylene chloride was added to obtain a dark brown homogeneous reaction solution. As a result of analyzing the reaction solutions by gas chromatography, 0.38 mmol of diphenyl carbonate (DPC) was produced. (2.33% yield). Table 1 shows the reaction conditions of Example 1, and Table 2 shows the amount, yield, and production rate of the product obtained in Example 1. In addition, the yield of DPC is shown by% on the basis of phenol, and the DPC generation rate is expressed by TOF (m
ol-DPC / mol-Pd.hour).

Example 2 In Example 1, dibromobis (2-diphenylphosphinopyridine) dipalladium was used instead of dichlorobis (2-diphenylphosphinopyridine) dipalladium.
The same operation as in Example 1 was carried out except that 9 mg (6 μmol, 12 μmol as Pd) was added. Table 1 shows the reaction conditions of Example 2 and the DP obtained in Example 2
Table 2 shows the production amount, yield, and production rate of C.

Example 3 In Example 1, dicyanatobis (2-diphenylphosphinopyridine) dipalladium was used instead of dichlorobis (2-diphenylphosphinopyridine) dipalladium.
The same operation as in Example 1 was carried out except that 9 mg (6 μmol, 12 μmol as Pd) was added. Table 1 shows the reaction conditions of Example 3 and the DP obtained in Example 3
Table 2 shows the production amount, yield, and production rate of C.

Example 4 Example 2 was repeated except that dichlorobis (2-diphenylphosphinopyridine) dipalladium was replaced by 5.2 mg (12 μmol) of (2,2′-biquinoline) palladium dichloride. Performed in a similar manner to 1. Table 1 shows the reaction conditions of Example 4, and Table 2 shows the amount, yield, and production rate of DPC obtained in Example 4.

Example 5 In Example 1, instead of dichlorobis (2-diphenylphosphinopyridine) dipalladium, (2,9'-dimethylphenanthroline) palladium dichloride was used.
The procedure was performed in the same manner as in Example 1 except that g (12 μmol) was added. The reaction conditions of Example 5 are shown in Table 1, and the amount, yield, and production rate of DPC obtained in Example 5 are shown in Table 2.
It is shown in the table.

Example 6 In Example 1, (6,6′-dimethyl-2,2′-bipyridyl) palladium dichloride was used in place of dichlorobis (2-diphenylphosphinopyridine) dipalladium.
The same operation as in Example 1 was performed except that 4.3 mg (12 μmol) was added. Table 1 shows the reaction conditions of Example 6, and Table 2 shows the amount, yield, and production rate of DPC obtained in Example 6.

Example 7 In Example 1, 5.8 mg (6 μmol) of dichlorocarbonyliridium bis (2-diphenylphosphinopyridine) palladium chloride was used in place of dichlorobis (2-diphenylphosphinopyridine) dipalladium to obtain Mn. (2,2,6,6-tetramethyl-3,5-
Heptane dionate) Instead of ₃ , Ce (2, 2, 6, 6)
6-tetramethyl-3,5-heptanedionate) ₄ 9.
Example 1 except that 6 mg (11 micromol) was used.
Was performed in the same manner as described above. Table 1 shows the reaction conditions of Example 7, and Table 2 shows the amount, yield, and production rate of DPC obtained in Example 7.

[0055] PdBr ₂ 3.2 Comparative Example 1 In Example 1, instead of dichlorobis (2-diphenylphosphino pyridine) dipalladium
The same operation as in Example 1 was performed except that mg (12 μmol) was used. Table 1 shows the reaction conditions of Comparative Example 1, and Table 2 shows the amount, yield, and production rate of DPC obtained in Comparative Example 1.
It is shown in the table.

[0056]

[Table 1]

Pd ₂ (Ph ₂ PPy) ₂ Cl ₂ : dichlorobis (2-diphenylphosphinopyridine) dipalladium Pd ₂ (Ph ₂ PPy) ₂ Br ₂ : dibromobis (2-diphenylphosphinopyridine) dipalladium Pd ₂ ( Ph ₂ PPy) ₂ (NCO) ₂ : dicyanatobis (2-diphenylphosphinopyridine) dipalladium PdCl ₂ (biqu) :( 2,2′-biquinoline) palladium dichloride PdCl ₂ (2,9-Me ₂ phen) :( 2,9′-dimethylphenanthroline) palladium dichloride PdCl ₂ (6,6′-Me ₂ -2,2′-bpy):
(6,6′-dimethyl-2,2′-bipyridyl) palladium dichloride Ir (CO) Cl ₂ (Ph ₂ PPy) ₂ PdCl: dichlorocarbonyliridium bis (2-diphenylphosphinopyridine) palladium chloride TMHD: 2,2 , 6,6-tetramethyl-3,5-heptanedionate (Ph ₃ P =) ₂ NBr: bis (triphenylphosphoranylidene) ammonium bromide

[0058]

[Table 2]

DPC: diphenyl carbonate TOF: DP per unit time, unit palladium catalyst amount
C production (mol-DPC / mol-Pd ・ time)

Example 8 In an autoclave having a capacity of 30 ml, 3.95 g (123 mmol) of methanol and 4.9 mg of dichlorobis (2-diphenylphosphinopyridine) dipalladium were added.
(6 micromol, 12 micromol as Pd), M
n (2,2,6,6-tetramethyl-3,5-heptanedionate) ₃ was 14.5 mg (24 μmol), and bis (triphenylphosphoranylidene) ammonium bromide was 0.15 g (0.24 g). Mmol). By pressurizing and depressurizing with carbon monoxide, the inside of the autoclave was replaced with carbon monoxide. Then, 0.50 in 25 ° C conversion
Carbon monoxide was pressurized so as to be MPa, and air was further pressurized so that the whole pressure was 0.75 MPa.

This was heated to 100 ° C. and reacted for 3 hours. After cooling and depressurizing, 20 ml of methylene chloride was added to obtain a dark brown homogeneous reaction solution. As a result of analyzing the reaction solutions by gas chromatography, 0.56 mmol of dimethyl carbonate (DMC) was produced (yield 0.91%). Table 3 shows the reaction conditions of Example 8, and Table 4 shows the amount, yield and production rate of the product obtained in Example 8.
It is shown in the table. The DMC yield is shown in% based on methanol, and the DMC production rate is expressed in unit time and unit (a).
The amount of DMC produced per component amount was calculated as TOF (mol-DMC
/ Mol- (a) · time).

Example 9 In Example 8, dibromobis (2-diphenylphosphinopyridine) dipalladium was used instead of dichlorobis (2-diphenylphosphinopyridine) dipalladium.
The same operation as in Example 8 was carried out except that 4 mg (6 μmol, 12 μmol as Pd) was used. Table 3 shows the reaction conditions of Example 9 and the DMC obtained in Example 9 was used.
Table 4 shows the production amount, yield, and production rate of.

Example 10 Dicyanatobis (2-diphenylphosphinopyridine) dipalladium instead of dichlorobis (2-diphenylphosphinopyridine) dipalladium in Example 8
The same operation as in Example 8 was performed except that 9 mg (6 μmol, 12 μmol as Pd) was used. The reaction conditions of Example 10 are shown in Table 3, and D obtained in Example 10 is shown in Table 3.
Table 4 shows the amount, yield, and production rate of MC.

Example 11 The procedure of Example 8 was repeated, except that dichlorobis (2-diphenylphosphinopyridine) dipalladium was replaced by (2,2′-biquinoline) palladium dichloride (5.2 mg, 12 μmol). 8 was performed.
Table 3 shows the reaction conditions of Example 11, and Table 4 shows the amount, yield, and production rate of DMC obtained in Example 11.

Example 12 In Example 8, instead of dichlorobis (2-diphenylphosphinopyridine) dipalladium, (2,9'-dimethylphenanthroline) palladium dichloride 4.5 m
The same operation as in Example 8 was carried out except that g (12 μmol) was used. Table 3 shows the reaction conditions of Example 12, and Table 4 shows the amount, yield, and production rate of DMC obtained in Example 12.

Example 13 In Example 8, (6,6′-dimethyl-2,2′-bipyridyl) palladium dichloride was used in place of dichlorobis (2-diphenylphosphinopyridine) dipalladium.
The same operation as in Example 8 was carried out except that 4.3 mg (12 μmol) was used. Table 3 shows the reaction conditions of Example 13, and Table 4 shows the amount, yield, and production rate of DMC obtained in Example 13.

Example 14 Example 8 was repeated except that dichlorocarbonyliridium bis (2-diphenylphosphinopyridine) palladium chloride (5.8 mg, 6 μmol) was used in place of dichlorobis (2-diphenylphosphinopyridine) dipalladium. Was carried out in the same manner as in Example 8. Example 14
Table 3 shows the reaction conditions, and Table 4 shows the amount, yield, and production rate of DMC obtained in Example 14.

[0068] PdBr ₂ 3.2 instead of dichlorobis (2-diphenylphosphino pyridine) dipalladium Comparative Example 2 Example 8
mg (12 micromol), and Mn (2, 2, 6,
6-tetramethyl-3,5-heptanedionate) except that 1.2 mg (12 μmol) of cuprous chloride was used instead of ₃ and bis (triphenylphosphoranylidene) ammonium bromide was not used. It carried out similarly to Example 8. Table 3 shows the reaction conditions of Comparative Example 2, and Table 4 shows the amount, yield, and production rate of DMC obtained in Comparative Example 2.

[0069]

[Table 3]

Pd ₂ (Ph ₂ PPy) ₂ Cl ₂ : dichlorobis (2-diphenylphosphinopyridine) dipalladium Pd ₂ (Ph ₂ PPy) ₂ Br ₂ : dibromobis (2-diphenylphosphinopyridine) dipalladium Pd ₂ ( Ph ₂ PPy) ₂ (NCO) ₂ : dicyanatobis (2-diphenylphosphinopyridine) dipalladium PdCl ₂ (biqu) :( 2,2′-biquinoline) palladium dichloride PdCl ₂ (2,9-Me ₂ phen) :( 2,9′-dimethylphenanthroline) palladium dichloride PdCl ₂ (6,6′-Me ₂ -2,2′-bpy):
(6,6′-dimethyl-2,2′-bipyridyl) palladium dichloride Ir (CO) Cl ₂ (Ph ₂ PPy) ₂ PdCl: dichlorocarbonyliridium bis (2-diphenylphosphinopyridine) palladium chloride TMHD: 2,2 , 6,6-tetramethyl-3,5-heptanedionate (Ph ₃ P =) ₂ NBr: bis (triphenylphosphoranylidene) ammonium bromide CuCl: cuprous chloride

[0071]

[Table 4]

DMC: dimethyl carbonate TOF: DM per unit time, unit palladium catalyst amount
C production (mol-DMC / mol-Pd ・ time)

[0073]

As described above, according to the production method of the present invention, an aromatic carbonate compound useful as an intermediate for synthesis of various organic compounds such as polycarbonate synthesis by a transesterification method and as a polycarbonate resin,
In addition, an aliphatic carbonate compound useful as a resin, a solvent for paints, an alkylating agent, a carbonylating agent, a polycarbonate resin, or the like, is efficiently produced in one step and at a high yield from an aromatic hydroxy compound or an aliphatic hydroxy compound. can do. Therefore, it is highly useful as a method for efficiently producing an aromatic carbonate compound and an aliphatic carbonate compound.

Continuing from the front page (72) Inventor Hirohisa Ishii 1-1-1 Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology Intensive Polymerization Concentration Co-operative Research Institute (72) Inventor Mitsuru Ueda 1-1-1 Higashi, Tsukuba, Ibaraki Inside the Institute of Materials Science and Technology, Institute of Industrial Science (72) Inventor Kazuhiko Takeuchi 1-1, Higashi, Tsukuba, Ibaraki Prefecture Inside the Institute of Materials Science and Technology, Institute of Industrial Science (72) Michihiko Asai 1-1, Higashi, 1-1, Tsukuba, Ibaraki Industrial Technology F-term (in reference) 4H006 AA02 AC48 BA25 BA47 BE30 BE40 BJ50 KA60 4H039 CA66 CD10 CF90

Claims (3)

[Claims] 1. A polynuclear metal complex comprising an aromatic hydroxy compound or an aliphatic hydroxy compound, carbon monoxide and oxygen, and (a-1) a palladium atom and a transition metal atom other than palladium belonging to Group VIII of the periodic table. A method for producing an aromatic carbonate compound or an aliphatic carbonate compound, wherein the reaction is carried out in the presence of a catalyst comprising the compound and (b) a redox catalyst. 2. A polynuclear having an aromatic hydroxy compound or an aliphatic hydroxy compound, carbon monoxide and oxygen (a-2) each having a plurality of palladium atoms as metal centers, and crosslinked by a heterobidentate ligand. A method for producing an aromatic carbonate compound or an aliphatic carbonate compound, characterized by reacting in the presence of a catalyst comprising a metal complex compound and (b) a redox catalyst. 3. An aromatic hydroxy compound or an aliphatic hydroxy compound, carbon monoxide and oxygen, and (a-3) a bipyridyl compound having no hydrogen at the α-position carbon of a ring member nitrogen atom as a ligand. A method of producing an aromatic carbonate compound or an aliphatic carbonate compound, wherein the reaction is carried out in the presence of a catalyst comprising the palladium complex compound and a redox catalyst (b).