JP2003245557A - Catalyst and method for manufacturing carbonate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for directly synthesizing the carbonate at good yield using carbon monoxide as a carbon source of the carbonate, and a method for manufacturing a carbonate. <P>SOLUTION: An aromatic hydroxy compound or an aliphatic hydroxy compound, carbon monoxide and oxygen are subjected to an oxidative carbonylation reaction in the presence of the catalyst for manufacturing the carbonate comprising a carbene type palladium complex and redox catalyst. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing a carbonic acid ester and a method for producing a carbonic acid ester. Aromatic carbonic acid ester compounds useful as solvents and aliphatic carbonic acid ester compounds useful as solvents for resins and paints, alkylating agents, carbonylating agents, polycarbonate resin raw materials, etc. from aromatic hydroxy compounds or aliphatic hydroxy compounds efficiently The present invention relates to a carbonic acid ester production catalyst for producing and a carbonic acid ester production method.

[0002]

2. Description of the Related Art Aromatic carbonic acid ester compounds are useful compounds as raw materials for producing polycarbonate by the transesterification method or as intermediates for various organic syntheses.
The aliphatic carbonic acid ester 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 general production method of these carbonic acid ester compounds, there is a method of reacting an aromatic hydroxy compound or an aliphatic hydroxy compound with phosgene in the presence of an alkali,
In this method, there is a problem that a highly toxic phosgene is used and a stoichiometric amount of alkali salt is produced as a by-product. Therefore,
Many methods for producing carbonate compounds without using phosgene have been proposed.

An oxidative carbonylation reaction in which a corresponding hydroxy compound is reacted with carbon monoxide and oxygen in the presence of a catalyst is known as a method for producing a carbonate compound without using phosgene. As a typical catalyst, a system in which a palladium compound is combined with a copper compound and a base as a co-catalyst (Japanese Patent Publication No. 61-8816, Japanese Patent Publication No. 61-43338), a palladium compound, a co-catalyst, and a quinone System using compounds and ammonium salts or alkali (earth) metal halides (JP-A-54-1)
35743, JP-A-54-135744,
JP-A-2-104564, JP-A-2-14275
4, JP-A-6-9505, JP-A-6-17.
No. 2268, No. 6-172269, No. 6-271506, No. 6-271509, No. 6-57678, No. 8-898.
No. 10, JP-A-8-193056), a palladium compound, an alkali metal or alkali (earth) metal halide, an iodide or onium iodide compound, and a catalyst system comprising zeolites (JP-A-1-16555).
No. 1), a palladium compound, an alkali (earth) metal halide, and activated carbon (JP-A-8-92).
No. 168). However, these methods have a slow reaction rate and an insufficient yield.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the method for producing carbonic acid ester, and uses carbon monoxide as a carbon source of carbonic acid ester without using phosgene or chlorine gas. It is an object of the present invention to provide a catalyst for directly synthesizing a carbonate ester in a good yield and a method for producing a carbonate ester.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that in the presence of a catalyst composition comprising a carbene-type palladium complex and a redox catalyst, an aromatic hydroxy compound or an aliphatic hydroxy compound, The present invention has been accomplished by finding that the above-mentioned problems can be achieved by reacting carbon oxide and oxygen.

That is, the present invention provides the following carbonic acid ester production catalyst and method for producing carbonic acid ester. 1. (A) A catalyst for producing a carbonic acid ester, comprising: a carbene-type palladium complex represented by the general formula (Ia) or the general formula (Ib); and (b) a compound having a redox catalytic ability.

[0007]

[Chemical 2]

(R ¹ , R ² , R ⁴ and R ⁵ are hydrogen,
The alkyl group having 1 to 20 carbon atoms, the aryl group, and the aralkyl group including -O-, -S-, and -NH-, which are halogen-substituted, may be the same or different. n is an integer of 0 to 2, R ³ is an alkylene group having 1 to 20 carbon atoms, an alkylidene group is aromatic, —O—, —S.
It may be halogen-substituted, including-and -NH-.
X is an anion, and two Xs bound to the same Pd may be the same or different. ) 2. The catalyst for producing a carbonic acid ester according to the above 1, wherein R ¹ and R ^{2 in} the general formula (I) are t-butyl groups. 3. (B) The catalyst for producing carbonic acid ester according to 1 or 2 above, wherein the compound having a redox catalytic ability is a cerium compound or a manganese compound. 4. The catalyst for producing a carbonic acid ester according to any one of 1 to 3 above, which further contains (c) an onium salt. 5. (C) The catalyst for producing a carbonic acid ester according to the above 4, wherein the onium salt is a phosphonium salt. 6. Further, (d) the catalyst for producing a carbonic acid ester according to 4 or 5, which further comprises a cocatalyst. 7. (D) The catalyst for producing carbonic acid ester according to 6 above, wherein the co-catalyst is a heteropoly acid or an onium salt of a heteropoly acid. 8. Further, (e) the catalyst for producing a carbonic acid ester according to 6 or 7, further comprising a dehydrating agent. 9. 9. A method for producing a carbonic acid ester, which comprises reacting an aromatic hydroxy compound or an aliphatic hydroxy compound with carbon monoxide and oxygen in the presence of the carbonic acid ester production catalyst according to any one of 1 to 8 above.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION First, a main catalyst (a), a carbene-type palladium complex constituting a catalyst for producing a carbonic acid ester of the present invention is represented by the following general formula (Ia) or general formula (Ib). It is a represented palladium compound.

[0010]

[Chemical 3]

(R ¹ , R ² , R ⁴ and R ⁵ are hydrogen,
The alkyl group having 1 to 20 carbon atoms, the aryl group, and the aralkyl group including -O-, -S-, and -NH-, which are halogen-substituted, may be the same or different. n is an integer of 0 to 2, R ³ is an alkylene group having 1 to 20 carbon atoms, an alkylidene group is aromatic, —O—, —S.
It may be halogen-substituted, including-and -NH-.
X is an anion, and two Xs bound to the same Pd may be the same or different. )

Examples of the alkyl group having 1 to 20 carbon atoms, aryl group and aralkyl group of R ¹ , R ² , R ⁴ and R ⁵ are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t
An ert-butyl group, a cyclohexyl group, a phenyl group, a benzyl group, a mesityl group, a tert-octyl group, an α-cumyl group and the like can be mentioned, but there is no particular limitation. Of these, a methyl group and a tert-butyl group are preferable. Further, as the alkylene group having 1 to 20 carbon atoms and the alkylidene group of R ³ ,
For example, ethylene group, propylene group, butylene group, amylene group, hexylene group, ethylidene group, propylidene group, isopropylidene group, butylidene group, benzylidene group,

[0013]

[Chemical 4]

And

[0015]

[Chemical 5]

One having a structure of In addition,
The carbene-type palladium complex may be used in combination with another palladium compound (eg, palladium acetate, palladium chloride, palladium bromide, etc.). The amount of the carbene-type palladium complex used is 100 with respect to the starting hydroxy compound.
It may be about 1 / 10,000 mol or more.

An inorganic redox catalyst or an organic redox catalyst is used as the compound (b) having a redox catalytic ability constituting the catalyst for producing a carbonic acid ester of the present invention. As the inorganic redox catalyst, lanthanoid compounds,
Examples thereof include Group 7 transition metal compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds and the like, and among them, cerium compounds or manganese compounds are preferable. More preferably, it is a cerium compound. For example, as the cerium compound, cerium (III) acetate, tris (acetylacetonato) cerium (III), tetra (2,2,6,6-tetramethyl-3,5-heptanedionato) cerium (IV),
Tetra (tropolonato) cerium (IV) or the like is used. As the manganese compound, manganese (II) acetate, tris (acetylacetonato) manganese (III), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) manganese (IV) and the like are used. Examples of organic redox catalysts include hydroquinone and benzoquinone. These compounds having redox catalytic activity may be used alone or in combination of two or more kinds. The amount used is about 0.1 to 100 mol with respect to the main catalyst.

The (c) onium salt, which is optionally used in the catalyst for producing a carbonic acid ester of the present invention, activates a hydroxy compound. Examples of such onium salts include ammonium salts, oxonium salts, sulfonium salts, phosphonium salts and selenonium salts. Of these, ammonium salts and phosphonium salts are preferable, and phosphonium salts are more preferable. As the ammonium salt, tetra (n-butyl) ammonium bromide, bis (triphenylphosphoranylidene) ammonium bromide or the like is used. Moreover, as the phosphonium salt, tetra (n-butyl) phosphonium bromide, tetraphenylphosphonium bromide, or the like is used. The amount of the onium salt used may be about 0.1 mol% or more based on the hydroxy compound.

In the present invention, the promoter (d) may be added for the purpose of improving the catalytic activity, the selectivity to the desired product, the yield, or the life. Any promoter can be used as long as it does not adversely affect the reaction,
Heteropolyacids and onium salts of heteropolyacids are preferably used. Examples of the heteropoly acid include phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, phosphotungstomolybdic acid, silicotungstomolybdic acid, and phosphovanadomolybdic acid. Further, it is possible to use these onium salts, alkali metal salts, alkaline earth metal salts, transition metal salts and the like. These may be used alone or in combination of two or more.

In the method of the present invention, water is by-produced during the reaction, but when the amount of the by-product is sufficient to inhibit the reaction, this by-product water is continuously fed from the reaction system. It is preferable to remove it. As a method for removing the by-product water from the reaction system, various conventionally known methods can be used, but in addition to the above components (a) to (d), a dehydrating agent may be added as a component (e). preferable. Examples of particularly preferable dehydrating agents include molecular sieves (zeolite),
Inorganic dehydrating agents such as calcium chloride, calcium oxide, diphosphorus pentoxide, sodium hydride, anhydrous sodium hydroxide,
Examples thereof include organic dehydrating agents such as acetaldehyde dimethyl acetal, acetaldehyde diphenyl acetal, acetone dimethyl acetal, and acetone diphenyl acetal. These dehydrating agents may be used in the form of chips or powder.

Next, the method for producing a carbonic acid ester 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 carbonic acid ester production catalyst. In the method for producing a carbonate ester, the aromatic hydroxy compound is
Various conventionally known compounds can be used and can be appropriately selected depending on the kind of the desired aromatic carbonate ester.
Aromatic hydroxy compounds selected from mono-hydroxy compounds and di-hydroxy compounds can be mentioned. The aromatic monohydroxy compound has the general formula (II)

[0022]

[Chemical 6]

[Wherein n represents an integer of 0 to 5 and X represents
Halogen atoms (eg chlorine, bromine, fluorine, iodine),
It represents an alkyl group, an alkoxyl group, a cyano group or an ester group having 1 to 4 carbon atoms, and may be present at any of the o-, m- and p-positions. ] C6-18 represented by
The aromatic monohydroxy compound (monohydric phenol) of is mentioned. Specifically, phenol, o-, m-, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-tert-amylphenol, p-α-cumylphenol, methoxyphenol, chlorophenol, Phenols such as trichlorophenol, bromophenol, tribromophenol, fluorophenol and cyanophenol are exemplified.

Further, the dihydroxy compound is represented by the general formula (III) HO-Ar-OH (III) [wherein Ar represents an arylene group. ] The aromatic dihydroxy compound (dihydric phenol) represented by this is mentioned. 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 (IV)

[0025]

[Chemical 7]

[In the formula, each R is a halogen atom (for example, chlorine, bromine, fluorine, iodine) or has 1 carbon atom.
~ 8 alkyl groups, and when R is plural, they may be the same or different, and a and b are
Each is an integer of 0 to 4. 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, and 5 to 5 carbon atoms.
15 cycloalkylidene groups, -S-, -SO-, -S
_{O 2 -, - O -,} - CO- bond or the formula

[0027]

[Chemical 8]

The group represented by ] It is a C12-27 aromatic dihydroxy compound (dihydric phenol) represented by this.

Here, there are various dihydric phenols represented by the above general formula (IV).
-Bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. As dihydric phenols other than bisphenol A, 1,1-bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; hydroquinone; 4,4′-dihydroxydiphenyl; bis (4- Hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide;
Bis (4-hydroxyphenyl) sulfone; Bis (4-
Hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether; 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-
Examples thereof include halogenated bisphenols such as dichloro-4-hydroxyphenyl) propane. When these phenols have an alkyl group as a substituent,
As the alkyl group, 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 compounds can be used and can be appropriately selected depending on the kind of the desired aliphatic carbonic acid ester. For example, from aliphatic monohydroxy compounds and aliphatic dihydroxy compounds. Included are selected aliphatic hydroxy compounds. The aliphatic monohydroxy compound is represented by the general formula R′OH (wherein R ′ represents an aliphatic alkyl group having 1 to 20 carbon atoms. The structure of R ′ may be primary, secondary or tertiary, and may be branched. Structures, cyclic structures, halogen atoms and the like may be contained as appropriate)). Specifically, methanol, ethanol, 1-propanol, 2-propanol, 2-
Chloro-1-propanol, 1-chloro-2-propanol, 1-butanol, 2-butanol, isobutanol, tert-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,
Examples include 2-tetradecanol, 1-hexadecanol, 2-hexadecanol, 1-octadecanol, 2-octadecanol, and benzyl alcohol.

As the aliphatic dihydroxy compound, 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. And an aliphatic dihydroxy compound represented by the formula, which may contain a halogen atom, etc.) Specifically, ethylene glycol; 1,2-dihydroxypropane; 1,3-dihydroxypropane; -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)
Examples thereof include benzyl alcohol.

The carbon monoxide to be reacted with the aromatic hydroxy compound or the aliphatic hydroxy compound may be a simple substance, or may be diluted with an inert gas or may be a mixed gas with hydrogen. The oxygen 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.

The reaction solvent in the method for producing carbonic acid ester is not particularly limited, and dichloromethane, chloroform, tetrahydrofuran, acetophenone, γ-butyrolactone or the like can be used. Further, when the melting point of the hydroxy compound is equal to or lower than the reaction temperature, it may be carried out without a solvent.

The reaction temperature in the method for producing a carbonic acid ester is 30 to 180 ° C, preferably 50 to 150 ° C, more preferably 80 to 120 ° C. If it is lower than 30 ° C, the reaction may not proceed. If it exceeds 180 ° C, side reaction may occur or the product may be colored, which is not preferable. The reaction time is, for example, 1 to 48 hours in the case of a batch system,
It is preferably 2 to 36 hours, more preferably 3 to 24 hours. If it is less than 1 hour, the yield is low, and if it exceeds 48 hours, the yield is not extended.

The reaction system may be batch, semi-continuous or continuous. Here, the state of the reaction system is in the liquid phase state, the mixed state of the liquid phase and the gas phase, the mixed state of the gas phase and the solid phase, and the mixed state of the liquid phase and the solid phase. , In a mixed state of a liquid phase, a gas phase and a solid phase. 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. Further, 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 even if it is separated by an operation such as filtration after the reaction, it is filled in a reactor or a container or the like. It may be used in a state where it is bound to allow the reaction solution to pass therethrough. The above raw material components and catalyst composition may be diluted and used as necessary. As the diluent, in the liquid phase, in addition to an inert solvent such as a saturated hydrocarbon, a solvent such as an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon, a halogenated hydrocarbon, an ether, an ester, a nitrogen-containing solvent or a sulfur-containing solvent may be used. Used in the gas phase, an inert gas such as nitrogen, argon, ethane or propane is used.

In the production method of the present invention, an aromatic hydroxy compound or an aliphatic hydroxy compound is reacted with carbon monoxide and oxygen as raw materials in the presence of the above catalyst composition to give an aromatic carbonic acid ester compound. Alternatively, an aliphatic carbonic acid ester compound is produced. The target aromatic carbonate compound (ie, aromatic hydroxy compound carbonate ester) or aliphatic carbonate compound (ie, aliphatic hydroxy compound carbonate ester) obtained by this reaction is various. . For example, when an aromatic monohydroxy compound is used, the compound represented by the general formula (V)

[0037]

[Chemical 9]

[In the formula, X and n are the same as in the case of the general formula (II). ] The aromatic carbonic acid ester represented by these is mentioned. When an aromatic dihydroxy compound is used as a raw material, the compound represented by the general formula (VI)

[0039]

[Chemical 10]

[In the formula, R, a, b and Y are represented by the general formula (IV)
Is the same as in. m depends on the molecular weight of the product and is an integer of 1 or more. The terminal structure of the molecule is not particularly specified. ] The aromatic carbonic acid ester represented by these is mentioned. Furthermore, when an aliphatic monohydroxy compound is used, the compound of the general formula (VII)

[0041]

[Chemical 11]

(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 structures, such as a branched structure, a cyclic structure, and a halogen atom. May be included as appropriate). When an aliphatic dihydroxy compound is used as a raw material, the compound of the general formula (VIII)

[0043]

[Chemical 12]

(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, etc. at an arbitrary position. Note that the terminal structure of the molecule is not particularly defined.)

[0045]

EXAMPLES The present invention will be described in more detail below 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 methods described in the literature.

Example 1 Phenol 8.29 mmol, Palladium bromide 0.0125 mmol having a methylenebis (N'-methylimidazolyl) type biscarbene ligand, tetra (2,2,6,6)
6-Tetramethyl-3,5-heptanedionato) cerium (IV) 0.075 mmol, hydroquinone 0.375
mmol, tetrabutylammonium bromide 0.3
75 mmol, 1.0 g of 3A-molecular sieve, and 5 mL of methylene chloride were placed in a reaction vessel, and carbon monoxide was 6.0 M.
Pa and oxygen 0.3 MPa were filled at 25 ° C. After sealing, the container was closed and heated at 100 ° C. for 3 hours. After completion of the reaction, the molecular sieve was filtered off and the solvent was distilled off to obtain a crude product. As a result of confirmation by a gas chromatogram using the internal standard method, 25% based on the raw material phenol
Diphenyl carbonate was produced.

Example 2 In Example 1, methylenebis (N'-tert-butylimidazolyl) was used instead of palladium bromide having a methylenebis (N'-methylimidazolyl) type biscarbene ligand.
Example 1 was repeated except that palladium bromide having a biscarbene type ligand was used. 45 based on phenol
% Diphenyl carbonate formed.

Example 3 In Example 1, a methylenebis (N'-cyclohexylimidazolyl) type biscarbene ligand was used instead of palladium bromide having a methylenebis (N'-methylimidazolyl) type biscarbene ligand. The procedure of Example 1 was repeated except that palladium bromide was used. 25% diphenyl carbonate was formed based on phenol.

Example 4 In Example 1, a methylenebis (N'-mesitylimidazolyl) type biscarbene ligand was used instead of palladium bromide having a methylenebis (N'-methylimidazolyl) type biscarbene ligand. The procedure of Example 1 was repeated except that palladium bromide was used. 23% based on phenol
Diphenyl carbonate was produced.

Example 5 In Example 1, the odor having a methylenebis (N'-benzylimidazolyl) type biscarbene ligand instead of palladium bromide having a methylenebis (N'-methylimidazolyl) type biscarbene ligand was used. The procedure of Example 1 was repeated except that palladium chloride was used. 16% based on phenol
Diphenyl carbonate was produced.

Example 6 In Example 1, the odor having a methylenebis (N'-phenylimidazolyl) type biscarbene ligand was used instead of palladium bromide having a methylenebis (N'-methylimidazolyl) type biscarbene ligand. The procedure of Example 1 was repeated except that palladium chloride was used. 14% based on phenol
Diphenyl carbonate was produced.

Example 7 The procedure of Example 1 was repeated except that tetrabutylphosphonium bromide was used instead of tetrabutylammonium bromide. 28% diphenyl carbonate was formed based on phenol.

Example 8 Example 8 was carried out in the same manner as in Example 1 except that tetraphenylphosphonium bromide was used instead of tetrabutylammonium bromide. 31% diphenyl carbonate was formed, based on phenol.

Example 9 The procedure of Example 1 was repeated except that tetrabutylphosphonium bromide was used instead of tetrabutylammonium bromide. 57% diphenyl carbonate was formed, based on phenol.

Example 10 The procedure of Example 1 was repeated except that tetraphenylphosphonium bromide was used in place of tetrabutylammonium bromide. 52% diphenyl carbonate was formed based on phenol.

Example 11 In place of palladium bromide having a methylenebis (N'-methylimidazolyl) type biscarbene ligand in Example 1,

[0057]

[Chemical 13]

The same procedure as in Example 1 was carried out except that
51% of diphenyl carbonate was formed based on phenol.

Example 12 The same procedure as in Example 1 was carried out except that tetraphenylphosphonium bromide was used in place of tetrabutylammonium bromide in Example 1. 59% diphenyl carbonate was formed based on phenol.

Example 13 Instead of palladium bromide having a methylenebis (N'-methylimidazolyl) type biscarbene ligand in Example 1,

[0061]

[Chemical 14]

The same procedure as in Example 1 was carried out except that
47% diphenyl carbonate was formed, based on phenol.

Example 14 Instead of palladium bromide having a methylenebis (N′-methylimidazolyl) type biscarbene ligand in Example 1,

[0064]

[Chemical 15]

The same procedure as in Example 1 was carried out except that
50% diphenyl carbonate was formed based on phenol.

Comparative Example 1 In Example 1, instead of palladium bromide having a methylenebis (N′-methylimidazolyl) type biscarbene ligand, palladium chloride was used, and cerium tetrakis (tetramethylheptanedione) was used instead of tris (acetyl). Acetonato) manganese (III) was used, and the same procedure as in Example 1 was performed. 5% diphenyl carbonate was formed based on phenol.

[0067]

Industrial Applicability According to the method of the present invention, aromatic carbonic acid ester compounds useful as intermediates for the synthesis of various organic compounds such as polycarbonate synthesis by the transesterification method and as polycarbonate resins and resins, paints, etc. An aliphatic carbonic acid ester compound useful as a solvent, an alkylating agent, a carbonylating agent, a polycarbonate resin, or the like can be efficiently produced from an aromatic hydroxy compound or an aliphatic hydroxy compound in a single step in a high yield. Therefore, the present invention is highly useful as a method for efficiently producing an aromatic carbonate compound or an aliphatic carbonate compound in a high yield.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kenichi Okuyama             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Inside the Tsukuba Center, National Institute of Advanced Industrial Science and Technology (72) Inventor Ritsuko Nagahata             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Inside the Tsukuba Center, National Institute of Advanced Industrial Science and Technology (72) Inventor Kazuhiko Takeuchi             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Inside the Tsukuba Center, National Institute of Advanced Industrial Science and Technology (72) Inventor Mitsuru Ueda             2-12-1, Ookayama, Meguro-ku, Tokyo (72) Inventor Michihiko Asai             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Inside the Tsukuba Center, National Institute of Advanced Industrial Science and Technology F-term (reference) 4G069 AA06 AA08 BA07B BA21A                       BA21B BA27A BA27B BB07A                       BC43A BC43B BC62A BC72A                       BC72B BE13A BE13B BE17A                       BE17B BE28A BE28B BE33A                       BE33B BE37A BE37B BE38A                       BE38B CB75 DA02 FA01                       ZA02B                 4H006 AA02 AC48 BA08 BA16 BA25                       BA35 BA45 BA47 BA51 BA75                       BE30 BE40 KA60                 4H039 CA66 CD10 CF90

Claims (9)

[Claims] 1. (a) General formula (Ia) or general formula (I)
A carbene-type palladium complex represented by -b), and (b)
A catalyst for producing a carbonic acid ester, which comprises a compound having a redox catalytic ability. [Chemical 1] (R ¹ , R ² , R ⁴ and R ⁵ are hydrogen and 1 to 2 carbon atoms.
An alkyl group, an aryl group or an aralkyl group of 0 is -O-,
They may be the same or different, including those containing -S- and -NH- and substituted with halogen. n is 0
Is an integer of 2 to 2, R ³ is an alkylene group having 1 to 20 carbon atoms, an alkylidene group is aromatic, —O—, —S—, —NH.
It may contain-and may be halogen-substituted. X is an anion, and two Xs bound to the same Pd may be the same or different. ) 2. The general formula (Ia) or the general formula (Ib).
The catalyst for producing a carbonic acid ester according to claim ¹ , wherein R ¹ and R ^{2 of} are a t-butyl group. 3. The catalyst for producing a carbonic acid ester according to claim 1, wherein the compound (b) having a redox catalytic activity is a cerium compound or a manganese compound. 4. The catalyst for producing carbonic acid ester according to claim 1, further comprising (c) an onium salt. 5. The catalyst for producing a carbonic acid ester according to claim 4, wherein the onium salt (c) is a phosphonium salt. 6. The catalyst for producing a carbonic acid ester according to claim 4, further comprising (d) a cocatalyst. 7. The catalyst for producing a carbonic acid ester according to claim 6, wherein the co-catalyst (d) is a heteropoly acid or an onium salt of a heteropoly acid. 8. The catalyst for producing a carbonic acid ester according to claim 6, further comprising (e) a dehydrating agent. 9. An aromatic hydroxy compound or an aliphatic hydroxy compound is reacted with carbon monoxide and oxygen in the presence of the carbonic acid ester production catalyst according to any one of claims 1 to 8. Method for producing carbonate ester.