JP2001233830A - Method for producing aromatic carbonic acid ester or aliphatic carbonic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aromatic carbonic acid ester compound or an aliphatic carbonic acid ester compound in high yield and efficiency from an aromatic hydroxy compound or an aliphatic hydroxy compound in one step. SOLUTION: The objective method for the production of an aromatic carbonic acid ester compound or an aliphatic carbonic acid ester compound comprises the reaction of an aromatic hydroxy compound or an aliphatic hydroxy compound with carbon monoxide and oxygen in the presence of a catalyst composition produced by bonding at least one kind of compound selected from (a) an organometallic complex, (b) a compound having redox catalyst activity and (c) a compound capable of activating an aromatic hydroxy compound or an aliphatic hydroxy compound to a carrier.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Aromatic carbonic acid ester compounds are useful as raw materials for producing polycarbonate by a transesterification method or as intermediates for various organic syntheses.
The aliphatic carbonate compound is a compound useful as a solvent for resins and paints, an alkylating agent, a carbonylating agent, a polycarbonate resin raw material, and the like. As a method for producing an aromatic carbonate compound, generally, there is 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 of an alkali salt is used. There are problems such as by-products. Accordingly, many methods for producing an aromatic carbonate compound without using phosgene have been proposed.

As a general method for producing an aromatic carbonate compound, a method using an oxidative carbonylation reaction in which an aromatic hydroxy compound to be carbonated is reacted with carbon monoxide and oxygen in the presence of a catalyst. Proposed. 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 composed of quinones and tetraalkylammonium halides or alkali metal halides or alkaline earth metal halides (JP-A-54-135743, JP-A-54-135744, JP-A-2-1-1).
04564, JP-A-2-142754, JP-A-6-9505, JP-A-6-172268, JP-A-6-172269, JP-A-6-271
506, JP-A-6-271509, JP-B-6-57678, JP-A-8-89810,
JP-A-8-193506 and U.S. Pat.
No. 85), a catalyst comprising a palladium compound, an alkali metal or an alkaline earth metal, an iodide or onium iodide compound, and a zeolite (JP-A-1-165).
551), 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 proposed. 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. 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. further,
In any method, a compound that is dissolved in the reaction solution is used as the catalyst component, and thus it is difficult to separate the catalyst component.

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, the process becomes complicated and 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 several problems, such as by-product of an alkali salt. 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 (Japanese Patent Application Laid-Open No.
However, since nitrite is not only a corrosive gas but also explosive, it poses a problem in safety and requires cost for countermeasures. There is also a problem. 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 the use of glycol as a by-product is required. There is an economic 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. However, such a method is expensive and the reaction speed is extremely slow. is there. 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 for obtaining the same.

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 using a copper compound as a co-catalyst, etc., have been proposed. The catalyst life is not economically sufficient, and it is also difficult to separate the catalyst components. Although there are examples using a supported catalyst, there are problems in terms of reaction rate and catalyst life.

[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 in which an aromatic carbonate compound or an aliphatic carbonate compound can be efficiently produced in one step and in a high yield, and the used catalyst composition can be easily separated.

[0008]

The inventors of the present invention have conducted intensive studies and, as a result, have found that an aromatic or aliphatic hydroxy compound reacts with carbon monoxide and oxygen in the presence of a specific catalyst composition. By doing so, it has been found that the above-mentioned problem can be achieved. 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) an organometallic complex, (b) a compound having a redox catalytic activity, and (c) an aromatic compound. A process for producing an aromatic carbonate or an aliphatic carbonate, wherein at least one compound having the ability to activate a hydroxy compound or an aliphatic hydroxy compound is reacted in the presence of a catalyst composition bound to a carrier. It provides a method.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As described above, the method of the present invention comprises reacting an aromatic or aliphatic hydroxy compound with carbon monoxide and oxygen in the presence of a specific catalyst composition. In 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. For example, aromatic aromatic compounds selected from monohydroxy compounds and dihydroxy compounds Hydroxy compounds. As the aromatic monohydroxy compound, a compound represented by the general formula (I)

[0011]

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Wherein n represents an integer of 1 to 3, X represents a hydrogen atom, a halogen atom (eg, chlorine, bromine, fluorine, iodine), an alkyl group having 1 to 4 carbon atoms, an alkoxyl group,
It represents a cyano group or an ester group, and may be present at any of the o-, m-, and p-positions. And an aromatic monohydroxy compound having 6 to 18 carbon atoms (monohydric phenol). Specifically, phenol, cresol, p-methylphenol, t-butylphenol (p
-T-butylphenol, etc.), 4-cumylphenol,
Phenols such as methoxyphenol, chlorophenol and cyanophenol are exemplified.

The 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. Further, as the dihydroxy compound, a compound represented by the general formula (III)

[0014]

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

[0016]

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

Here, there are various dihydric phenols represented by the general formula (IV).
-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) sulfoxide; bis (4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) sulfide;
Bis (4-hydroxyphenyl) compounds other than bisphenol A such as bis (4-hydroxyphenyl) ketone or bis (3,5-dibromo-4-hydroxyphenyl) propane; bis (3,5-dichloro-4-hydroxyphenyl) ) Halogenated bisphenols such as propane. When these phenols have an alkyl group as a substituent, the alkyl group includes
An alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms is preferable.

Further, as the aliphatic hydroxy compound, various conventionally known aliphatic hydroxy compounds can be used and can be appropriately selected depending on the kind of the desired aliphatic carbonate. For example, aliphatic monohydroxy compounds and aliphatic dihydroxy compounds can be used. The aliphatic hydroxy compounds selected are mentioned. Examples of the aliphatic monohydroxy compound include a compound represented by the general formula R'OH (where R 'represents an aliphatic alkyl group having 1 to 20 carbon atoms. The structure of R' may be any of primary, secondary, and tertiary; Which may optionally contain a structure, a cyclic structure, a halogen atom, etc.). 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 any of a branched structure, a cyclic structure and a cyclic structure. Which may contain a structure, a halogen atom, etc.), specifically, ethylene glycol; 1,2-dihydroxypropane; 1,3-dihydroxypropane; 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. Further, oxygen to be reacted with the aromatic hydroxy compound may be pure oxygen,
Generally, it may be diluted with an inert gas, for example, an oxygen-containing gas such as air.

In the present invention, the above reaction is carried out by (a)
In the presence of a catalyst composition in which at least one of an organometallic complex, (b) a compound having a redox catalytic activity and (c) a compound having an ability to activate an aromatic hydroxy compound or an aliphatic hydroxy compound is bound to a carrier. Done in As such a catalyst composition, general formula (V)

[0023]

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[Wherein, a represents the component (a), b represents the component (b), and c represents the component (c). R ^a , R
^b and R ^c are the components (a) and (b), respectively,
(C) represents a covalent bond that binds the component to a carrier, and represents a substituent having 0 or more carbon atoms, specifically, a single bond, a double bond, a triple bond, and a bifunctional saturated compound having 1 to 20 carbon atoms. Hydrocarbon group, bifunctional unsaturated hydrocarbon group, carbon number 6 or more 2
0 or less bifunctional aromatic hydrocarbon group (the above hydrocarbon group may optionally contain a hetero atom, a metal atom, etc.),
Ester bond, ether bond, thioester bond, thioether bond, amino bond, urea bond, amide bond, imide bond, or a difunctional or trifunctional substituent formed by a combination of these difunctional substituents Represents a group or a tetrafunctional substituent. These bifunctional, trifunctional or tetrafunctional substituents may have a substituent as appropriate. The series of S represents a carrier, and represents a compound having at least one atom composed of one or more kinds of atoms selected from carbon, boron, nitrogen, oxygen, phosphorus, silicon, sulfur, aluminum, zirconium, titanium and the like. Also, at least one selected from R ^a , R ^b and R ^c may be bonded to the same S to form a radial or linear structure. n, n ′ and n ″ are each independently 0 or more, each of which represents an integer of 1 or more, and each may be an arbitrary different value. m independently represents an integer of 1 or more. ] Is exemplified.

Here, as the component (a) represented by a in the general formula (V), (a) an organometallic complex composed of one or more metal centers consisting of only palladium atoms and an organic ligand, or palladium Any compound may be used as long as it is an organometallic complex composed of two or more metal centers consisting of an atom and a metal atom other than a palladium atom and an organic ligand. When two or more metal atoms including a palladium atom are included as a metal center, the respective metal atoms may be directly bonded to each other by a metal bond, or may be bonded via an organic ligand. As organic ligands, phosphine structures, phosphite structures, phosphate ester structures, which are common as ligands such as palladium complexes,
Any structure containing at least one structure selected from a pyridine structure, an imine structure, an amine structure, a nitrile structure, an arsine structure, and a carbonyl structure may be used. Examples of the organic ligand having a plurality of structures include a compound having a plurality of phosphine structures, a compound having a plurality of pyridine structures, a compound having a plurality of imine structures, a compound having a plurality of amine structures, a compound having a plurality of nitrile structures, and a carbonyl structure. A compound containing multiple phosphines and a pyridine structure,
Examples include compounds containing an arsine structure and a pyridine structure. Specific examples of these compounds include a structure in which the ^a portion of the general formula (V) is not bonded to the ^Ra portion (that is, R
^The following organic ligands can be mentioned as a structure having hydrogen instead of the ^a portion).

Examples of the compound containing one organic ligand structure include triphenylphosphine, tricyclohexylphosphine, tri-n-butylphosphine, triphenylphosphite, pyridine, alkylpyridine, hydroxypyridine, quinoline, acetonitrile, and benzo. Specific examples include nitrile. Examples of the organic ligand having a plurality of structures include bis (diphenylphosphino) methane; 1,2-bis (diphenylphosphino) ethane;
1,3-bis (diphenylphosphino) propane;
4-bis (diphenylphosphino) butane; bis (diphenylarsino) methane; 1,2-bis (diphenylarsino) ethane; 1,3-bis (diphenylarsino)
Propane; 2,2'-biquinoline;4,4'-dimethyl-2,2'-biquinoline;2,2'-bipyridine; 6,
6'-dimethyl-2,2'-bipyridine;phenanthroline;2,9-dimethylphenanthroline;adiponitrile;phthalonitrile;pyridylnitrile;2-diphenylphosphinopyridine;di-2-pyridylphenylphosphine; tri-2-pyridylphosphine 2-diphenylphosphinoquinoline; 2-diphenylarsinopyridine; 1,2-di (phenylimino) ethane; 1,2-
Bis (dialkylphenylimino) ethane; 1,2-bis (trialkylphenylimino) ethane; 2,3-di (phenylimino) butane; 2,3-bis (dialkylphenylimino) butane; 2,3-bis ( Specific examples thereof include trialkylphenylimino) butane; acetylacetone, derivatives obtained by introducing a substituent into these organic ligands, and positional isomers thereof. These organic ligands are bonded to the carrier via the R ^a moiety shown in the general formula (V), and the bonding position may be any site, and may be appropriately selected as long as the reaction is not hindered. Can be.

As described above, the organometallic complex mentioned as the component (a) of the catalyst composition in the present invention includes an organometallic complex composed of one or more metal centers consisting only of palladium atoms and an organic ligand. Alternatively, any compound may be used as long as it is an organometallic complex composed of a palladium atom and two or more metal centers consisting of a metal atom other than the palladium atom and an organic ligand. As such an organometallic complex, specifically, a of the general formula (V)
A moiety that is not attached to the ^Ra moiety (ie, ^Ra
Structure having hydrogen instead of a moiety)
The following organometallic complexes are mentioned.

Specific examples of the organometallic complex having a metal center consisting of only one palladium atom include tetrakis (triphenylphosphine) palladium; dichlorobis (triphenylphosphine) palladium; dibromobis (triphenylphosphine) palladium; Pyridine) palladium; dibromobis (pyridine)
Palladium; dichlorobis (quinoline) palladium; dibromobis (quinoline) palladium; dichlorobis (acetonitrile) palladium; dichlorobis (benzonitrile) palladium; (2,2′-biquinoline) palladium dichloride; (4,4′-dimethyl-2,2 ′) -Biquinoline) palladium dichloride; (2,2'-biquinoline-4,4'-dicarboxylic acid dipotassium salt) palladium dichloride;
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; '-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′-biquinoline) palladium dibromide; (4,4 ′
-Dimethyl-2,2'-biquinoline) palladium dibromide; (2,2'-biquinoline-4,4'-dicarboxyl acid dipotassium salt) palladium dibromide; (dimethyl 2,2'-biquinoline-4,
4'-dicarboxylate) palladium dibromide;
(2,9-dimethyl-1,10-phenanthroline) palladium dibromide; (2,9-di-t-butyl-1,
10-phenanthroline) palladium dibromide;
(6,6'-dimethyl-2,2'-bipyridyl) palladium dibromide; (2,2'-biquinoline) palladium diiodide; (4,4'-dimethyl-2,2'-biquinoline) palladium diioda (2,2′-biquinoline-4,4′-dicarboxyl acid dipotassium salt) palladium diiodide; (2,9-dimethyl-1,10-phenanthroline) palladium diiodide; (2,9 -Di-t-butyl-1,10-phenanthroline) palladium diiodide; (6,6′-
Dimethyl-2,2'-bipyridyl) palladium diiodide; [1,2-bis (dialkylphenylimino) ethane] palladium dichloride; [2,3-bis (dialkylphenylimino) butane] palladium dichloride.

Examples of the organometallic complex having a metal center composed of two or more palladium atoms include dichlorobis [bis (diphenylphosphino) methane] dipalladium and dibromobis [bis (diphenylphosphino) methane]. Dipalladium, dinitrite bis [bis (diphenylphosphino) methane] dipalladium, diazidobis [bis (diphenylphosphino) methane] dipalladium, dicyanatobis [bis (diphenylphosphino) methane] dipalladium, diisocyanatobis [ Bis (diphenylphosphino) methane] dipalladium, dichlorobis (2-diphenylphosphinopyridine) dipalladium, dibromobis (2-diphenylphosphinopyridine) dipalladium, dinitrite bis (2-diphenylphosphinopy Jin) dipalladium, Jiajidobisu (2-diphenylphosphino pyridine) dipalladium,
Dicyanatobis (2-diphenylphosphinopyridine)
Dipalladium, diisocyanatobis (2-diphenylphosphinopyridine) dipalladium, dichlorobis (2-
Diphenylphosphinoquinoline) dipalladium, dibromobis (2-diphenylphosphinoquinoline) dipalladium, dinitrite bis (2-diphenylphosphinoquinoline) dipalladium, diazidobis (2-diphenylphosphinoquinoline) dipalladium, dicyanatobis (2 -Diphenylphosphinoquinoline) dipalladium,
Diisocyanatobis (2-diphenylphosphinoquinoline) dipalladium, dichlorobis (tri-2-pyridylphosphine) dipalladium, dibromobis (tri-2-
Pyridylphosphine) dipalladium, dinitrite bis (tri-2-pyridylphosphine) dipalladium, diazidobis (tri-2-pyridylphosphine) dipalladium, dicyanatobis (tri-2-pyridylphosphine) dipalladium, diisocyanatobis ( Tri-2-pyridylphosphine) dipalladium, dichlorobis (2-
Diphenylarsinopyridine) dipalladium, dibromobis (2-diphenylarsinopyridine) dipalladium, dinitritebis (2-diphenylarsinopyridine) dipalladium, diazidobis (2-diphenylarsinopyridine) dipalladium, dicyanatobis (2-
Diphenylarsinopyridine) dipalladium, diisocyanatobis (2-diphenylarsinopyridine) dipalladium, tetrachlorobis (2-diphenylphosphinopyridine) tripalladium and the like.

As the organometallic complex having two or more metal centers consisting of a palladium atom and a metal atom other than palladium, a compound having a palladium atom and a metal atom other than palladium in one polynuclear metal complex compound is used. Any compound may be used as long as it is present. Preferable metal atoms other than palladium of the organometallic complex having two or more metal centers consisting of a palladium atom and a metal atom other than palladium include tin, titanium, iron, zirconium, molybdenum, cobalt, nickel, ruthenium, rhodium,
Examples include iridium, platinum, copper, silver, gold, zinc, aluminum, and lead. In these organometallic complexes having two or more metal centers composed of a palladium atom and a metal atom other than palladium, the number of metal atoms other than palladium and palladium contained in the structure is at least one in each case. I just need. Specific examples of such an organometallic complex having two or more metal centers consisting of a palladium atom and a metal atom other than palladium include bis [(bisdiphenylphosphino) methane]
(Trichlorotin) dipalladium chloride, bis [(bisdiphenylphosphino) methane] bis (trichlorotin) dipalladium, bis [(bisdiphenylphosphino) methane] (trichlorotitanium) dipalladium chloride, bis [(bisdiphenylphospho) Fino) methane]
Bis (trichlorotitanium) dipalladium, bis [(bisdiphenylphosphino) methane] (dichloroiron) dipalladium chloride, bis [(bisdiphenylphosphino) methane] bis (dichloroiron) dipalladium, bis [(bisdiphenylphospho) Fino) methane] (trichlorotin) (trichlorotitanium) dipalladium, bis [(bisdiphenylphosphino) methane] (trichlorotin) (dichloroiron) dipalladium, bis [(bisdiphenylphosphino) methane]
(Trichlorotitanium) (dichloroiron) dipalladium, π-allyl (triphenylphosphine) (trichlorotin) palladium, π-allyl (triphenylphosphine) (trichlorotitanium) palladium, π-
Allyl (triphenylphosphine) (dichloroiron) palladium, bis (trichlorotin) palladium,
Bis (trichlorotitanium) palladium, bis (dichloroiron) palladium, dichlorocarbonyliridium bis (2-diphenylphosphinopyridine) palladium chloride, dichlorocarbonyliridium bis [(bisdiphenylphosphino) methane] palladium chloride, carbonyliridium bis [( Bisdiphenylphosphino) methane] palladium chloride, dichlorocarbonylrhodiumbis (2-diphenylphosphinopyridine) palladium chloride, dichlorocarbonylrhodiumbis [(bisdiphenylphosphino) methane] palladium chloride, carbonylrhodiumbis [(bisdiphenylphosphino) ) Methane] palladium chloride, trichlorodicarbonylruthenium bis (2-diphenylphosphinopyridine) para Um chloride, trichlorodicarbonylruthenium bis [(bisdiphenylphosphino) methane] palladium chloride, chlorodicarbonylrutheniumbis [(bisdiphenylphosphino) methane] palladium chloride, chloroplatinumbis (2-diphenylphosphinopyridine) palladium chloride, Chloroplatinum bis [(bisdiphenylphosphino) methane] palladium chloride, chloronickel bis (2-diphenylphosphinopyridine) palladium chloride, chloronickel bis [(bisdiphenylphosphino) methane] palladium chloride and the like can be mentioned.

In the production method of the present invention, the organometallic complexes listed as component (a) of the catalyst composition may be used alone or in combination of two or more. Further, compounds which can be precursors of these organometallic complexes may be used alone and physically mixed. In addition, (a) of these catalyst compositions
The components include alkyl phosphine or aromatic phosphine, phosphite,
A ligand such as a phosphate ester or a nitrile ligand such as acetonitrile may be combined. These organometallic complexes may be bonded to a carrier at an appropriate position via ^Ra .

In the catalyst composition used in the production method of the present invention, it is not necessary to use the component (b) if the action of the component (b) can be substituted by the component (a), the component (c) or the carrier contained in the catalyst composition. However, if necessary, the above (a)
In addition to the component and the component (c), an appropriate amount of the component (b) represented by b in the above general formula (V) is bound to a carrier and used. As the component (b), a compound having a redox catalytic activity is used. Examples of the compound include a lanthanoid compound, a transition metal compound of Group 5 of the New Periodic Table, and a compound of Group 6
Group 7 transition metal compounds, Group 7 transition metal compounds, iron compounds,
At least one selected from the group consisting of a cobalt compound, a nickel compound, and a copper compound is used, and these may be in any form of an organic complex, an organic salt, and an inorganic salt. 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. The redox catalysts listed as the component (b) of the catalyst composition may be used alone or in combination of two or more. Further, the compounds which can be precursors of these redox catalysts may be used alone and physically mixed. These compounds may be bound to the carrier via R ^b at an appropriate position.

In the catalyst composition used in the production method of the present invention, it is not necessary to use the component (a), the component (b) or the carrier contained in the catalyst composition if the action of the component (c) can be substituted. However, if necessary, the above (a)
In addition to the component and the component (b), an appropriate amount of the component (c) represented by c in the above general formula (V) is bound to a carrier and used. As the component (c), a compound having the ability to activate an aromatic hydroxy compound or an aliphatic hydroxy compound is suitably used. More preferred examples include onium halide compounds, metal compounds having Lewis acidity, and base catalyst compounds. Specific examples of the onium halide compound include a compound represented by the following formula (VI). R ¹ R ² R ³ R ⁴ AB (VI) wherein A is a nitrogen atom or a phosphorus atom, B is a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxy group, an alkoxy group or an aryloxy group Is shown. R ^{1 to} R ⁴ each represent an alkyl group having 1 to 8 carbon atoms or a carbon atom having 6 to 1 carbon atoms;
2, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group,
Examples include an octyl group, a cyclohexyl group, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. R ^{1 to} R
⁴ may be the same or different. Further, R ¹ and R ² , R ³ and R ⁴ are taken together to form-(CH
₂ ) A divalent group represented by n-, wherein n is an integer of 2 to 7 may be formed. Further, as the onium halide compound, bis (triphenylphosphoranylidene) ammonium halides other than the compound represented by the above formula (VI) can also be used. Specific examples thereof include tetra-n-butylammonium bromide, tetraphenylphosphonium bromide, bis (triphenylphosphoranylidene) ammonium bromide, bis (triphenylphosphoranylidene) ammonium hydroxide, and bis (triphenylphosphoranylidene). Ammonium phenoxide and the like. These compounds may be bound to the carrier via R ^c at an appropriate position.

In the catalyst composition used in the production method of the present invention, the components used to bind the components (a) to (c) corresponding to R ^{a to} R ^c in the general formula (V) with the carrier include: Any substituent may be used as long as it does not hinder the reaction. Specifically, a single bond, a double bond, a triple bond (the above bond is considered here as a substituent having 0 carbon atoms), a bifunctional saturated hydrocarbon group having 1 to 20 carbon atoms, a bifunctional Unsaturated hydrocarbon group, carbon number 6 ~ 2
0 bifunctional aromatic hydrocarbon group (the above hydrocarbon group may contain a hetero atom, a metal atom or the like as appropriate), ester bond, ether bond, thioester bond, thioether bond, amino bond, urea A bond, an amide bond, an imide bond, or a difunctional, trifunctional or tetrafunctional substituent formed by combining these bifunctional substituents and bonds may be used. These difunctional substituents, trifunctional substituents or tetrafunctional substituents may have substituents as long as the reaction is not hindered.

The carrier used in the catalyst composition used in the production method of the present invention [corresponding to the series of S in the general formula (V). ] As long as it does not hinder the reaction, as long as it is a compound having one or more atoms selected from one or more atoms selected from carbon, boron, nitrogen, oxygen, phosphorus, silicon, sulfur, aluminum, zirconium, titanium and the like. Any compound can be used. Also, R ^a , R ^b and R
^At least one kind selected from ^c may be respectively bonded to the same S in the general formula (V) to form a radial or linear structure. Preferred specific examples are organic carriers such as organic polymers, dendrimers, fullerenes, carbon nanotubes, saccharides, biopolymers, or zeolites, silica, alumina, zirconia, titania, metal carbonates, metal sulfates. And inorganic carriers such as metal oxides. More preferred carriers include p-
Polystyrenes such as methylpolystyrene and polystyrene, p-methylstyrene-divinylbenzene copolymer,
Styrene-divinylbenzene copolymer, polystyrene,
Examples include polyvinylpyrrolidone, polypyridines, polyesters, polyvinyl alcohol, polyvinyl acetate, silica and the like.

In the catalyst composition used in the production method of the present invention, the components (a), (b), (c),
In addition to the components used to bind the components (a) to (c) to the carrier and the carrier, additives that improve the properties of each component or the carrier, as long as the reaction is not hindered, that is, an organic binder, an inorganic binder, Additives such as a cross-linking agent and a modifier may be added as needed. The shape of the catalyst composition may be any shape as long as it does not hinder the reaction.Because of the type of reaction, the catalyst composition may be in the form of a powder, a pellet, a honeycomb, a plate, or the like. You may. In addition, organometallic complexes, compounds, carriers, additives, etc., which can be precursors of these catalysts, are used alone, respectively.
It may be in a physically mixed form.

In the production method of the present invention, specific examples of particularly preferable catalyst compositions among the above catalyst compositions include (1) an organometallic complex comprising a palladium compound and a compound having a pyridine ring structure, or a palladium compound. And an organometallic complex comprising a compound having a bipyridine ring structure and a p-methylstyrene-divinylbenzene copolymer, and a pyridinium chloride salt simultaneously bound to the same p-methylstyrene-divinylbenzene copolymer A catalyst composition comprising (2) a palladium compound and a triphenylphosphine-bonded styrene-divinylbenzene copolymer; and (3) a catalyst composition comprising a palladium compound, a compound having a redox catalytic activity, and polyvinylpyrrolidone.

In the production method of the present invention, the amount of the catalyst composition to be used is not particularly limited, and may be an ordinary amount of the catalyst. For example, as for the component (a), the amount of the aromatic hydroxy 1 × 10 ⁻⁸ to 1 mol of palladium per mol of compound or aliphatic hydroxy compound
It is 0.5 mol, preferably 1 × 10 ^{−6 to} 0.1 mol. If the amount is less than 1 × 10 ⁻⁸ mol, the reaction rate may be too low to be practical. On the other hand, if it exceeds 0.5 mol, the effect equivalent thereto is not recognized and it is economically disadvantageous. The amount of component (b) used is generally 0.1 to 100 mol, preferably 0.5 to 50 mol, per 1 mol of palladium of component (a). If the amount is less than 0.1 mol, the reaction rate may be slow, which is not practical. If the amount exceeds 100 mol, the oxidative decomposition reaction of the aromatic ester compound or aliphatic carbonate compound produced by the component (b) proceeds, so that it is economical. Disadvantageous. The amount of component (c) used is
(C) Usually 0.1-1 to 1 mol of palladium of the component.
000 mol, preferably 0.5 to 500 mol.
If the amount is less than 0.1 mol, the reaction rate may be low, which is not practical. If the amount exceeds 1000 mol, a side reaction due to the component (c) proceeds, which is economically disadvantageous. The amounts of the catalyst components other than those described above, that is, the amount of the carrier and the like, cannot be specified unconditionally because they depend on the amount of each component bound to the carrier. on the other hand,
Of the component (a), the component (b) and the component (c), one or two components, respectively, may not be contained in the catalyst. In such a case, when it is necessary to add a catalytic function expressed by the component (a), the component (b), the component (c), etc. which are not contained in the catalyst, the respective components (a), ( b) component, component (c) and the like are used alone,
You may use by adding separately. The component (a), component (b), component (c) and the like used at that time may be in a form bound to the carrier or in a form not bound thereto.

In the production method of the present invention, the reaction proceeds in the absence of a solvent or in a solvent. Generally, it is economically advantageous to carry out the method of the present invention in the absence of a solvent.However, if necessary due to the production process of the aromatic carbonate compound and the aliphatic carbonate compound, the solvent may be used in a solvent. May go. Here, examples of the solvent that can be used include aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halogenated hydrocarbons, ethers, esters, nitrogen-containing solvents, sulfur-containing solvents, and the like. It can be appropriately selected depending on the type and combination of the compositions.

In the present invention, the reaction temperature is not particularly limited, but is usually 50 to 200 ° C., preferably 70 to 15 ° C.
0 ° 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. The reaction pressure is generally set to a pressurized state because a gaseous raw material such as carbon monoxide or oxygen is used, and the carbon monoxide partial pressure is 1 × 10
^{−2 to} 20 MPa, preferably 1 × 10 ^{−2 to} 10 MPa, and the oxygen partial pressure is 1 × 10 ^{−2 to} 10 MPa.
a, preferably in the range of 1 × 10 ^{−2 to 5} MPa. In particular, the oxygen partial pressure is preferably 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 an inert gas or hydrogen is used, its 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 a liquid phase state, a mixed state of a liquid phase and a gas phase, a mixed state of a gas phase and a solid phase, and a mixed state of a liquid phase and a solid phase. Or a mixed state of a liquid phase, a gas phase, and a solid phase. Further, the state of the catalyst composition in the reaction system may be homogeneous or heterogeneous, and can be selected by appropriately selecting the catalyst composition. When the catalyst composition is used in a non-uniform state, the catalyst composition is used in a state of being suspended in the reaction system, and separated by an operation such as filtration after the reaction. You may use it in the state couple | bonded and let the reaction liquid pass through this. The above-mentioned raw material components and catalyst composition may be used after being diluted as necessary. Examples of the diluent include solvents such as aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halogenated hydrocarbons, ethers, esters, nitrogen-containing solvents, and sulfur-containing solvents in addition to inert solvents such as saturated hydrocarbons in the liquid phase. An inert gas such as nitrogen, argon, ethane or propane is used in the gas phase.

The production method of the present invention comprises reacting an aromatic hydroxy compound or an aliphatic hydroxy compound with carbon monoxide and oxygen as raw materials in the presence of the above specific catalyst composition to obtain an aromatic carbonate. A compound or an aliphatic carbonate compound is produced. 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, the compound represented by the general formula (VII)

[0043]

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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)

[0045]

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[Wherein R, a, b, and Y represent the above general formula (
). 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, the compound represented by the general formula (IX)

[0047]

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(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 be a branched structure, a cyclic structure, a halogen atom or the like. May be included as appropriate.). When an aliphatic dihydroxy compound is used as a raw material, the compound represented by the general formula (X)

[0049]

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(In the formula, R ″ represents an aliphatic alkylene group having 2 to 20 carbon atoms. The structure of R ″ includes a branched structure, a cyclic structure, an aromatic ring, a halogen atom, and the like at any position. The terminal structure of the molecule is not particularly defined.).

[0051]

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

Example 1 Triphenylphosphine-bonded polystyrene-divinylbenzene copolymer (containing 0.25 milliequivalent of triphenylphosphine unit / g: 0.25 mmol / g)
500 g were stirred at room temperature under a nitrogen atmosphere in toluene (10 ml) for 1 hour. Next, 0.576 g of dichlorobis (benzonitrile) palladium was added to the suspension.
(1.50 mmol) of toluene (30 ml)
The solution was added, and the mixture was further stirred at room temperature under a nitrogen atmosphere for 24 hours. Thereafter, the obtained brown solid was separated by filtration, washed with toluene, and dried under reduced pressure to obtain a catalyst composition Pd-PPh
0.531 g of _2- PS was obtained. As a result of elemental analysis, the palladium content and the phosphorus content in the unit catalyst composition weight were 0.29 mmol / g and 0.22 mmol / g, respectively.

In a 30 ml autoclave, 41.6 mg of the catalyst composition Pd-PPh ₂ -PS was added.
(12 micromol as Pd), phenol 3.0
2 g (32 mmol), 14.5 mg of Mn (2,2,6,6-tetramethyl-3,5-heptanedionato) ₃
(24 micromoles), 0.15 g (0.24 g) of bis (triphenylphosphoranylidene) ammonium bromide.
Mmol). By pressurizing and depressurizing with carbon monoxide, the inside of the autoclave was replaced with carbon monoxide. Thereafter, carbon monoxide is pressurized so as to be 0.50 MPa in terms of 25 ° C., and further, the total pressure is 0.75 M
The air was pressurized to Pa.

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 suspension. The catalyst composition was easily separated by filtering this suspension, and a dark brown homogeneous reaction solution was obtained. As a result of analyzing each of the homogeneous reaction liquids by gas chromatography, diphenyl carbonate (hereinafter abbreviated as DPC) was 0.09%.
8 mmol was produced (0.60% yield). Example 1
Table 1 shows the reaction conditions, and Table 2 shows the amount, yield, and production rate of the product obtained in Example 1. The yield of DPC is represented by% based on phenol, and the DPC production rate is represented by TOF (mol-DPC / mol-Pd-hour), which is the amount of DPC produced per unit time and per unit amount of palladium.

Example 2 In Example 1, instead of Mn (2,2,6,6-tetramethyl-3,5-heptanedionato) ₃ , Ce (2,2) was used.
2,6,6-tetramethyl-3,5-heptanedionato) ₄
Was carried out in the same manner as in Example 1 except that 9.6 mg (11 μmol) was used. Separation of the catalyst composition was facilitated by filtration. Table 1 shows the reaction conditions of Example 2, and Table 2 shows the amount, yield, and production rate of DPC obtained in Example 2.

Example 3 p-Chloromethylpolystyrene-divinylbenzene copolymer (containing 4.3 meq / g chloro units / g:
A suspension obtained by mixing 1.00 g, 0.745 g (4.3 mmol) of 2-quinoline carboxylic acid, pyridine (5 ml) and dimethyl sulfoxide (20 ml) at 100 ° C. under a nitrogen atmosphere. At 7
Stir for 2 hours. Then, the obtained brown solid was separated by filtration, washed with dimethyl sulfoxide and methanol, and dried under reduced pressure. This solid was then stirred in toluene (10 ml) for 1 hour. 0.825 g of dichlorobis (benzonitrile) palladium was added to this suspension.
(2.15 mmol) of toluene (20 ml)
The solution was added, and the mixture was further stirred at room temperature under a nitrogen atmosphere for 24 hours. Then, the obtained brown solid was separated by filtration, washed with toluene, and dried under reduced pressure to obtain a catalyst composition Pd-2qu.
1.41 g of CO ₂ -Py ⁺ -PS was obtained. As a result of elemental analysis, the palladium content in the unit catalyst composition weight was 0.3
The content was 7 mmol / g and the nitrogen content was 2.7 mmol / g. Subsequent experiments operations, Example 1 in the catalyst composition Pd-PPh ₂ -PS instead the Pd-2quCO ₂ -
Using 32.4 mg of Py ⁺ -PS (12 μmol as Pd), bis (triphenylphosphoranylidene)
Example 1 except that no ammonium bromide was used.
Was carried out in the same manner as Separation of the catalyst composition was facilitated by filtration. Table 1 shows the reaction conditions of Example 3.
Table 2 shows the amount, yield, and production rate of DPC obtained in Example 3.

Example 4 In Example 3, 1.02 g (2.15 mmol) of dipotassium 2,2'-biquinoline-4,4'-dicarboxylate trihydrate was used in place of 2-quinolinecarboxylic acid. the catalyst composition in place of the catalyst composition ^{_{Pd-2quCO 2 -Py + -PS Pd}} -biqCO 2 -Py + -PS
(Palladium content 0.29 mmol / g, nitrogen content 2.8 mmol / g). For subsequent experimental operations,
The resulting catalyst composition Pd-biqCO ₂ -Py ⁺ -PS
Was carried out in the same manner as in Example 3 except that 41.4 mg (12 μmol as Pd) was used and bis (triphenylphosphoranylidene) ammonium bromide was not used. Separation of the catalyst composition was facilitated by filtration. 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 1.34 g (12 mmol in monomer units) of polyvinylpyrrolidone, 0.460 g (1.2 mmol) of dichlorobis (benzonitrile) palladium, Mn
(2,2,6,6-tetramethyl-3,5-heptanedionato) ₃ was dissolved in 1.451 g (2.4 mmol) and ethanol (30 ml), and stirred at room temperature for 24 hours. The catalyst composition Pd-Mn-PVP (palladium content is 0.39 mmol / g, manganese-containing) is distilled off, suspended in hexane, filtered, washed with toluene, and dried under reduced pressure. The amount is 0.
76 mmol / g, nitrogen content 4.1 mmol / g)
I got In an autoclave having a capacity of 30 ml, 30.8 g (32 mmol) of phenol was added to the catalyst composition P.
30.8 mg of d-Mn-PVP (12 micromol as Pd) and 0.15 g (0.24 mmol) of bis (triphenylphosphoranylidene) ammonium bromide
Enclosed. The subsequent experimental operation was performed in the same manner as in Example 1. Separation of the catalyst composition was facilitated by filtration. Table 1 shows the reaction conditions of Example 5, and Table 2 shows the amount, yield, and production rate of DPC obtained in Example 5.

Comparative Example 1 In Example 1, 3.19 mg of palladium bromide (PdBr ₂ ) (1) was used in place of the catalyst composition Pd-PPh ₂ -PS.
Example 2 was carried out in the same manner as in Example 1 except that 2 μmol) was used. Regarding the separation of the catalyst composition, a dark brown homogeneous reaction solution was obtained after the reaction, so that separation by filtration was not possible. Thus, reprecipitation using a solvent in which the catalyst component is not easily dissolved, recrystallization by cooling, and the like were attempted, but the catalyst component could not be separated. 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.

[0060]

[Table 1]

The symbols in the table represent the following. TMHD: 2,2,6,6-tetramethyl-3,5-heptanedionate, (Ph ₃ P =) ₂ NBr: bis (triphenylphosphoranylidene) ammonium bromide

[0062]

[Table 2]

Example 6 The procedure of Example 1 was repeated, except that 3.95 g (123 mmol) of methanol was used instead of 3.02 g (32 mmol) of phenol. Separation of the catalyst composition was facilitated by filtration. Table 3 shows the reaction conditions of Example 6, and Table 4 shows the amount, yield, and production rate of dimethyl carbonate (hereinafter abbreviated as DMC) obtained in Example 6. Hereinafter, the yield of DMC is shown in% on the basis of methanol, and the rate of DMC generation is expressed by TOF based on the amount of DMC generated per unit palladium per unit time.
(Mol-DMC / mol-Pd · time).

Example 7 The procedure of Example 2 was repeated except that 3.02 g (32 mmol) of phenol was replaced by 3.95 g (123 mmol) of methanol. Separation of the catalyst composition was facilitated by filtration. Table 3 shows the reaction conditions of Example 7 and the DMC obtained in Example 7 was used.
Table 4 shows the production amount, yield, and production rate of.

Example 8 The procedure of Example 3 was repeated, except that 3.95 g (123 mmol) of methanol was used instead of 3.02 g (32 mmol) of phenol. Separation of the catalyst composition was facilitated by filtration. Table 3 shows the reaction conditions of Example 8 and the DMC obtained in Example 8 was used.
Table 4 shows the production amount, yield, and production rate of.

Example 9 The procedure of Example 4 was repeated, except that, in place of 3.02 g (32 mmol) of phenol, 3.95 g (123 mmol) of methanol was used. Separation of the catalyst composition was facilitated by filtration. 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 The procedure of Example 5 was repeated, except that 3.05 g (32 mmol) of phenol was replaced by 3.95 g (123 mmol) of methanol. Separation of the catalyst composition was facilitated by filtration. 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.

Comparative Example 2 The procedure of Comparative Example 1 was repeated, except that 3.05 g (32 mmol) of phenol was replaced by 3.95 g (123 mmol) of methanol. Regarding the separation of the catalyst composition, a dark brown homogeneous reaction solution was obtained after the reaction, so that separation by filtration was not possible. Thus, reprecipitation using a solvent in which the catalyst component is not easily dissolved, recrystallization by cooling, and the like were attempted, but the catalyst component could not be separated. 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. In Table 3, TMHD indicates 2,2,6,6-tetramethyl-3,5-heptanedionate, and (Ph ₃
P =) ₂ NBr is bis (triphenylphosphoranylidene)
2 shows ammonium bromide.

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

As described above, according to the method of the present invention, aromatic carbonate compounds and resins useful as intermediates for the synthesis of various organic compounds, such as polycarbonate synthesis by transesterification, and as polycarbonate resins. To efficiently produce aliphatic carbonate compounds useful as solvents, alkylating agents, carbonylating agents, polycarbonate resins, etc., from aromatic hydroxy compounds or aliphatic hydroxy compounds in a single step and in a high yield from solvents such as oils and paints, alkylating agents, carbonylating agents and polycarbonate resins. Can be. Further, the separation of the catalyst composition can be easily performed. Therefore, the present invention has high utility as a method for efficiently producing an aromatic carbonate compound or an aliphatic carbonate compound in high yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Minakshigoyaru, 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Japan Institution for Promotion of Chemical Technology (72) Inventor, Mitsuru Ueda 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Inside the Technical Research Institute (72) Inventor Kazuhiko Takeuchi 1-1-1, Higashi, Tsukuba, Ibaraki Pref.Institute of Materials Science and Technology (72) Inventor Michihiko Asai 1-1-1, Higashi, Tsukuba, Ibaraki Pref. On-site F-term (reference) 4H006 AA02 AC48 BA05 BA07 BA08 BA09 BA10 BA11 BA14 BA16 BA19 BA20 BA21 BA22 BA23 BA24 BA25 BA26 BA34 BA35 BA37 BA43 BA47 BA48 BA51 BA52 BA53 BA67 BA69 BA82 BE30 BE40 BJ50 KA60 4H039 CA66 CD10 CD90

Claims (7)

[Claims] 1. An aromatic hydroxy compound or an aliphatic hydroxy compound, carbon monoxide and oxygen, (a) an organometallic complex, (b) a compound having a redox catalytic activity, and (c) an aromatic hydroxy compound or an aliphatic compound A method for producing an aromatic carbonate or an aliphatic carbonate, comprising reacting at least one compound having the ability to activate an aromatic hydroxy compound in the presence of a catalyst composition bound to a carrier. 2. An organometallic complex in which the component (a) is composed of one or more metal centers consisting of only palladium atoms and an organic ligand, or two or more consisting of palladium atoms and metal atoms other than palladium atoms. The method for producing an aromatic carbonate or an aliphatic carbonate according to claim 1, which is an organometallic complex comprising a metal center and an organic ligand. 3. The method for producing an aromatic carbonate or an aliphatic carbonate according to claim 1, wherein the component (b) is a cerium compound or a manganese compound. 4. The method for producing an aromatic carbonate or an aliphatic carbonate according to claim 1, wherein the component (c) is at least one of a halogen onium compound, a metal compound having Lewis acidity and a base catalyst compound. . 5. An organometallic complex comprising a palladium compound and a compound having a pyridine ring structure or an organometallic complex comprising a palladium compound and a compound having a bipyridine ring structure is bonded to a p-methylstyrene-divinylbenzene copolymer, Pyridinium chloride salt with the same p-
The method for producing an aromatic carbonate or an aliphatic carbonate according to claim 1, wherein a catalyst composition simultaneously bonded to a methylstyrene-divinylbenzene copolymer is used. 6. The method for producing an aromatic carbonate or an aliphatic carbonate according to claim 1, wherein a catalyst composition comprising a palladium compound and a triphenylphosphine-bonded styrene-divinylbenzene copolymer is used. 7. A method for producing an aromatic carbonate or an aliphatic carbonate, comprising using a catalyst composition comprising a palladium compound, a compound having a redox catalytic activity and polyvinylpyrrolidone.