JP2000016964A - Production of aromatic carbonic ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing an aromatic carbonic ester from an aromatic hydroxyl compound by one stage in a high yield. SOLUTION: This method for producing an aromatic carbonic ester comprises reacting an aromatic hydroxyl compound with carbon monoxide and oxygen in the presence of (a) a palladium complex compound comprising an organic compound containing at least two or more nitrogen atoms as a ligand, preferably at least one kind of a palladium complex compound selected from a palladium complex compound containing a diimine-based compound as a ligand, a palladium complex compound containing a bipyridyl-based compound as a ligand and a palladium complex compound containing a diamine-based compound as a ligand and (b) a redox catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aromatic carbonate, and more particularly to an aromatic carbonate useful as an intermediate for the synthesis of various organic compounds such as the synthesis of polycarbonate by a transesterification method and as a polycarbonate resin. The present invention relates to a method for efficiently producing a carbonate compound from an aromatic hydroxy compound.

[0002]

2. Description of the Related Art Aromatic carbonate is a useful compound as a raw material for producing polycarbonate by a transesterification method or as an intermediate raw material for various organic syntheses. As a method for producing an aromatic carbonate, 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 of an alkali salt is used. There are some problems such as by-products. Therefore, many methods for producing aromatic carbonates without using phosgene have been proposed. As a general method for producing an aromatic carbonate, a method using an oxidative carbonylation reaction of reacting an aromatic hydroxy compound to be esterified with carbon monoxide and oxygen in the presence of a catalyst has been proposed. I have. 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 a quinone and a tetraalkylammonium halide or an alkali metal halide or an alkaline earth metal halide (JP-A-54-135743, JP-A-54-13).
5744, JP-A-2-104564, JP-A-2-142754, JP-A-6-9505, JP-A-6-172268, JP-A-6-172
269, JP-A-6-271506, JP-A-6-271509, JP-B-6-57678, JP-A-8-89810, JP-A-8-1930
No. 56 and U.S. Pat. No. 4,349,485), a catalyst comprising a palladium compound, an alkali metal or alkaline earth metal, an iodide or onium iodide compound, and a zeolite (JP-A-1-165551);
A catalyst comprising a palladium compound, an alkali metal halide or an alkaline earth metal halide, and activated carbon (JP-A-8-92168) has been proposed. In any case, the reaction rate of the oxidative carbonylation reaction is economical. There is a problem that it is not enough from a technical point of view.

Further, a method using a palladium compound, a copper compound or a lanthanoid compound, 2-hydroxypyridine, and an aprotic polar solvent (JP-A-9-110804)
However, this method is economical in that the reaction rate is sufficient in terms of economy, but an aprotic polar solvent is essential and a solvent recovery step is required. On the other hand, as a production method using no carbonyl oxidation reaction, a production method using a transesterification reaction between dimethyl carbonate and an aromatic hydroxy compound (JP-A-9-176)
No. 094) has been proposed, but this method requires a process for producing dimethyl carbonate as a raw material, and is not necessarily an economical method. Furthermore, a production method by a carbon monoxide removal reaction from diphenyl oxalate (Japanese Patent Application Laid-open No.
In order to produce an aromatic carbonate, it is necessary to carry out a carbonylation reaction using carbon monoxide and methanol as raw materials and a transesterification reaction between dimethyl oxalate and an aromatic hydroxy compound. And the process becomes complicated and not economical.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the conventional method for producing an aromatic carbonate, and provides an aromatic carbonate in one step and at a high yield from an aromatic hydroxy compound. It is an object of the present invention to provide a method for efficiently manufacturing.

[0005]

DISCLOSURE OF THE INVENTION In view of the above situation, the present inventors have solved the problems of the prior art and efficiently produced an aromatic carbonate in one step with high yield from an aromatic hydroxy compound. We worked diligently to develop a method. As a result, they have found that the object of the present invention can be achieved by using (a) a palladium complex compound having an organic compound having at least two nitrogen atoms as a ligand and (b) a redox catalyst as catalysts. .
The present invention has been completed based on such findings. That is, the present invention relates to a palladium complex compound having an aromatic hydroxy compound, carbon monoxide and oxygen as a ligand (a) an organic compound having at least two nitrogen atoms as a ligand, preferably a diimine-based compound as a ligand. Comprising at least one palladium complex compound selected from the group consisting of a palladium complex compound having as a ligand, a palladium complex compound having a bipyridyl-based compound as a ligand, and a palladium complex compound having a diamine-based compound as a ligand, and (b) a redox catalyst A process for producing an aromatic carbonate characterized by reacting in the presence of

[0006]

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. And aromatic hydroxy compounds selected from monohydroxy compounds and aromatic dihydroxy compounds. As the aromatic monohydroxy compound, a compound represented by the general formula (I)

[0007]

Embedded image

[Wherein, n represents an integer of 1 to 3;
Represents a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, a cyano group or an ester group;
It may be in any of the m- or p-position. 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)

[0010]

Embedded image

[Wherein, R is a hydrogen atom, a halogen atom (for example, 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)

[0012]

Embedded image The bond represented by is shown. 12-27 carbon atoms represented by
Is an aromatic dihydroxy compound (dihydric phenol).

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) 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.

The carbon monoxide to be reacted with the aromatic hydroxy compound may be a single substance, or may be a substance diluted with an inert gas, for example, an oxygen-containing gas such as air. The catalyst used in the production method of the present invention is composed of the component (a) and the component (b) as described above. Here, as the palladium complex compound as the component (a), any compound may be used as long as it is a palladium complex compound having, as a ligand, an organic compound having at least two nitrogen atoms. Preferred palladium complex compounds include at least one selected from a palladium complex compound having a diimine compound as a ligand, a palladium complex compound having a piperidyl compound as a ligand, and a palladium complex compound having a diamine compound as a ligand. Palladium complex compounds are mentioned. Specific examples of the palladium complex compound having a diimine compound as a ligand include compounds represented by general formula (V):

[0015]

Embedded image

[0016] (R ¹ and R ^4, shows the total aromatic group having 7 to 20 carbon atoms having independently a hydrocarbon group on the aliphatic hydrocarbon group or ring having 1 to 20 carbon atoms, R ² and R ³ is each independently a hydrogen atom or a group having 1 to 2 carbon atoms.
0 represents a hydrocarbon group, and R ² and R ³ may combine with each other to form a ring. A and B each independently represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. )).

In the general formula (V), R ¹ and R
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by each of ⁴ include a linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl Group,
Examples include a tetradecyl group, a hexadecyl group, an octadecyl group, a cyclopentyl group, 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. Further, the total number of carbon atoms having a hydrocarbon group on the ring is 7 to 2
Examples of the 0 aromatic group include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms on an aromatic group such as a phenyl group or a naphthyl group or an aromatic ring such as a phenyl group or a naphthyl group. Examples include groups into which one or more groups have been introduced. As R ¹ and R ⁴ , an aromatic group having a hydrocarbon group on the ring is preferable, and a 2,6-diisopropyl group is particularly preferable. Here, R ¹ and R ⁴ may be the same or different.

The hydrocarbon group having 1 to 20 carbon atoms represented by each of R ² and R ³ includes, for example, a carbon group having 1 to 20 carbon atoms.
20 linear or branched alkyl groups, having 3 to 2 carbon atoms
A cycloalkyl group of 0, an aryl group having 6 to 20 carbon atoms,
Examples thereof include an aralkyl group having 7 to 20 carbon atoms. Here, as the linear or branched alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 20 carbon atoms, the aliphatic carbon group having 1 to 20 carbon atoms represented by each of R ¹ and R ⁴ described above. The same ones as those exemplified for the hydrogen group can be exemplified. Further, as the aryl group having 6 to 20 carbon atoms,
Examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a methylnaphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. R ² and R ³ may be the same or different. Further, they may combine with each other to form a ring.

On the other hand, examples of the halogen atom represented by each of A and B include chlorine, bromine and iodine, and the hydrocarbon group having 1 to 20 carbon atoms is represented by R ² and R
These are the same as those described for the hydrocarbon group having 1 to 20 carbon atoms represented by each of ³ above. As A or B, a chlorine atom and a bromine atom are particularly preferable. Also, A
And B may be the same or different from each other. Examples of the complex compound represented by the general formula (V) include compounds represented by the following formulas [1], [2], [3] and [4].

[0020]

Embedded image The palladium complex compound having a bipyridyl-based compound as a component (a) as a ligand is specifically represented by the general formula (VI):

[0021]

Embedded image

Where R^Five~ R¹²Are independently charcoal
An aliphatic hydrocarbon group having a prime number of 1 to 20, a hydrocarbon group on a ring
Represents an aromatic group having 7 to 20 carbon atoms or a hydrogen atom
Then R ^FiveAnd R⁶, R⁶And R⁷, R⁷And R⁸, R⁸When
R⁹, R⁹And R^Ten, R^TenAnd R¹¹, R ¹¹And R¹²,like
Adjacent substituents are each bonded to form an aromatic ring or
Or an unsaturated aliphatic ring may be formed. C and D
Are each independently a halogen atom or a group having 1 to 20 carbon atoms.
Represents a hydrocarbon group. Listed are the complex compounds represented by
be able to.

In the general formula (VI), the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by each of R ^{5 to} R ¹² includes a linear or branched alkyl group having 1 to 20 carbon atoms. Or a cycloalkyl group having 3 to 20 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec
-Butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. 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 the ring and having 7 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. Examples thereof include groups into which one or more linear, branched or cyclic alkyl groups of the formulas 1 to 10 have been introduced.

In addition, this R^Five~ R¹²Are identical to each other
Or may be different. R ^Five~ R¹²Each other in
Substituents adjacent to each other are bonded to an aromatic ring or
Or an unsaturated aliphatic ring may be formed. On the other hand, C
And a halogen atom represented by each of D, chlorine,
Bromine, iodine, etc .;
As the hydrogen group, the above R^Five~ R¹²Represented by each of
As described for the hydrocarbon groups of Formulas 1 to 20,
You. C and D are particularly preferably chlorine or bromine.
Good. Further, C and D may be the same or different.
It may be.

Examples of the complex compound represented by the general formula (VI) include (2,2′-biquinolyl) palladium dichloride, (2,2′-bipyridyl) palladium dichloride, (1,10-phenanthrolyl) palladium Dichloride, (2,2′-biquinolyl) palladium dibromide, (2,2′-bipyridyl) palladium dibromide,
(1,10-phenanthrolyl) palladium dibromide, (2,2′-biquinolyl) palladium diiodide, (2,2′-bipyridyl) palladium diiodide, (1,10-phenanthrolyl) palladium diiodide and the like No. Among the palladium complex compounds having a bipyridyl compound as a ligand, particularly preferred are (2,2′-biquinolyl) palladium dichloride and (2,2′-biquinolyl) palladium dibromide. Specific examples of the palladium complex compound having the diamine-based compound (a) as a ligand include compounds represented by the general formula (VII):

[0026]

Embedded image

(Wherein, n ′ represents an integer of 1 to 10. R
^{13 to} R ¹⁶ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a total of 7 to 20 carbon atoms having a hydrocarbon group on the ring.
And the substituents on the same nitrogen such as R ¹³ and R ¹⁴ and R ¹⁵ and R ¹⁶ are respectively bonded to form a saturated aliphatic ring or an unsaturated aliphatic ring. You may. R ′ and R ″ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group having 7 to 20 carbon atoms having a hydrocarbon group on the ring, or a hydrogen atom, It may form a saturated aliphatic ring or an unsaturated aliphatic ring, and when there are a plurality of R 'and R ", a plurality of R' or a plurality of R" may be different substituents. E and F each independently represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.).

In the general formula (VII), the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by each of R ^{13 to} R ¹⁶ is a linear or branched alkyl group having 1 to 20 carbon atoms. And a cycloalkyl group having 3 to 20 carbon atoms.
Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl , Tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. An appropriate substituent such as a lower alkyl group may be introduced on the ring of the cycloalkyl group. Also,
Examples of the aromatic group having a hydrocarbon group on the ring and having 7 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. And groups into which one or more linear, branched or cyclic alkyl groups of from 10 to 10 have been introduced.

In addition, this R¹³~ R¹⁶Are identical to each other
Or may be different. R ¹³~ R¹⁶Same in
The substituents on the nitrogen at
Or an unsaturated aliphatic ring may be formed. further,
R ′ and R ″ are each independently an aliphatic group having 1 to 20 carbon atoms.
A total of 7 carbon atoms having a hydrocarbon group or a hydrocarbon group on a ring
Represents an aromatic group or a hydrogen atom, and each represents a bond
To form a saturated aliphatic ring or unsaturated aliphatic ring
When there are a plurality of R 'and R ",
R ′ or a plurality of R ″ s are different substituents,
Is also good. A hydrocarbon group having 1 to 20 carbon atoms and
Specific examples of an aromatic group having 7 to 20 carbon atoms having a hydrogen group
The above R¹³~ R¹⁶Similar to that described in
Things.

On the other hand, examples of the halogen atom represented by each of E and F include chlorine, bromine and iodine. For the hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned R ¹³
Like it can be mentioned and described for the hydrocarbon group having 1 to 20 carbon atoms represented by each to R ^16, in particular chlorine and bromine atoms are preferred. E and F may be the same or different from each other. The general formula (VI
Examples of the complex compound represented by I) include (N, N,
N ′, N′-tetramethylethylenediamine) palladium dichloride, (ethylenediamine) palladium dichloride, (N, N, N ′, N′-tetramethylmethylenediamine) palladium dichloride, (methylenediamine)
Palladium dichloride, (N, N, N ', N'-tetramethylethylenediamine) palladium dibromide, (ethylenediamine) palladium dibromide, (N, N,
N ', N'-tetramethylmethylenediamine) palladium dibromide, (methylenediamine) palladium dibromide and the like. Among the palladium complex compounds having a bipyridyl compound as a ligand, particularly preferred are (ethylenediamine) palladium dichloride, (N, N, N ′, N′-tetramethylethylenediamine) palladium dichloride, (N, N, N ', N'-
(Tetramethylmethylenediamine) palladium dichloride and the like.

In the present invention, the complex compound of the component (a) may be used alone or in combination of two or more. Further, a palladium compound which can be a precursor of these complex compounds, and a palladium complex compound having an organic compound having at least two nitrogen atoms as a ligand, preferably a diimine compound, a bipyridyl compound or a diamine compound Each of them may be used alone and may be in a physically mixed form. Also,
These palladium compounds may be appropriately combined with a ligand such as an alkyl phosphine or an aromatic phosphine, a phosphite or a phosphate, or a nitrile ligand such as acetonitrile, as long as the reaction is not hindered.

In the production method of the present invention, a redox catalyst is used as the component (b). The redox catalyst is selected from the group consisting of lanthanoid compounds, Group V transition metal compounds of the periodic table, Group VI transition metal compounds, Group VII transition metal compounds, iron compounds, cobalt compounds, nickel compounds and copper compounds. At least one kind 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.

Particularly preferred redox catalysts include C
e (TMHD) ₄ , Mn (TMHD) ₃ , Ce (Tro
p) ₄ , Mn (Trop) ₃ [where TMHD represents 2,2,6,6-tetramethyl-3,5-heptanedionate ion and Trop represents 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 (VIII). ^{R 17 R 18 R 19 R 20} ZA '··· (VIII)

Wherein Z is a nitrogen atom or a phosphorus atom;
A 'represents a halogen atom such as fluorine, chlorine, bromine and iodine. R ^{17 to} R ²⁰ are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group , Octyl group, cyclohexyl group,
Examples include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. R ^{17 to} R ²⁰ may be the same or different. R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ are taken together to form a divalent group represented by — (CH ₂ ) _n —, wherein n is an integer of 2 to 7. May be. Further, bis (triphenylphosphoranylidene) ammonium halides other than the compound represented by the formula (VIII) can also be used as the onium halide compound. Specific examples thereof include tetra-n-butylammonium bromide, tetraphenylphosphonium bromide, bis (triphenylphosphoranylidene) ammonium bromide and the like.

In the production method of the present invention, the amount of the catalyst used is not particularly limited, and a normal amount of the catalyst may be used.
For example, the component (a) is used in an amount of 1 × 10 ^{−8 to} 0.5 mol, preferably 1 × 10 ⁻⁶ , as palladium, per mol of the aromatic hydroxy compound as a raw material.
It is 1 × 10 ^-2 mol. If the amount is less than 1 × 10 ⁻⁸ , the reaction rate is too low to be practical. On the other hand, if the amount exceeds 0.5 mol, the effect corresponding thereto is not recognized and it is economically disadvantageous. The amount of the component (b) to be used is generally 0.1 to 100 mol, preferably 0.5 to 50 mol, per 1 mol of the palladium complex compound of the component (a). Above usage is 0.
If the amount is less than 1 mol, the reaction rate is slow and impractical.
If the amount exceeds the above range, the oxidative decomposition reaction of the aromatic carbonate produced by the component (b) proceeds, which 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, but if necessary for reasons such as the production process of an aromatic carbonate, the method may be carried out in a solvent. 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, 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 ^{−3 to} 50 MPa, preferably 1 × 10 ^{−2 to} 20 M
Within the range of Pa, the oxygen partial pressure is 1 × 10 ^{−3 to} 30 MPa,
Preferably, it should be in the range of 1 × 10 ^{−2 to} 10 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. Further, the state of the catalyst in the reaction system may be homogeneous or heterogeneous, and can be selected by appropriately selecting the catalyst. The raw material component 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 nitrogen, argon, ethane, or a gaseous phase is used.
An inert gas such as propane is used. The production method of the present invention is to produce an aromatic carbonate by reacting an aromatic hydroxy compound, carbon monoxide and oxygen as raw materials in the presence of the above-mentioned specific catalyst. There are various aromatic carbonates (that is, carbonates of aromatic hydroxy compounds) which 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 (IX)

[0039]

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

[0040]

Embedded image

[Wherein, R, a, b, and Y are the same as those in the general formula III.
Is the same as 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:

[0042]

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 Pd (biquinoline) Cl were added.
₂ , 5.2 mg (12 micromol), Mn (2,2,2)
6,6-tetramethyl-3,5-heptanedionate)
₃ (14.5 mg, 24 micromol) and bis (triphenylphosphoranylidene) ammonium bromide (148.
4 mg (240 μmol) was encapsulated. By pressurizing and depressurizing with carbon monoxide, the inside of the autoclave was replaced with carbon monoxide. Then, 0.50MP in 25 ° C conversion
Carbon monoxide was pressurized so as to obtain a, and air was further pressurized so that the entire pressure became 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 pale yellow homogeneous reaction solution. As a result of analyzing the reaction solutions by gas chromatography, 0.366 mmol of diphenyl carbonate (DPC) was produced. (Yield 2.27%). The reaction conditions of Example 1 were changed to the first
Table 2 shows the production amount, yield, and production rate of the product obtained in Example 1 in Table 2. In addition, the yield of DPC is shown by% on the basis of phenol.
The amount of DPC generated per unit palladium catalyst is defined as TOF (m
ol-DPC / mol-Pd.hour).

Comparative Example 1 The procedure of Example 1 was repeated, except that 3.2 mg (12 μmol) of PdBr ₂ was used instead of Pd (biquinoline) Cl ₂ . Table 1 shows the reaction conditions.
Table 2 shows the amount, yield, and production rate of the obtained DPC.

Example 2 The procedure of Example 1 was repeated, except that Pd [glyoxalbis (2,6-diisopropylphenyl) imine] Cl ₂ was used instead of Pd (biquinoline) Cl ₂ . Table 1 shows the reaction conditions, and Table 2 shows the amount, yield, and production rate of the obtained DPC.

Example 3 The procedure of Example 1 was repeated, except that Pd [diacetylbis (2,6-diisopropylphenyl) imine] Cl ₂ was used instead of Pd (biquinoline) Cl ₂ . Table 1 shows the reaction conditions, and Table 2 shows the amount, yield, and production rate of the obtained DPC.

Example 4 In Example 2, 6.9 mg (11 micromol) of Ce (tropolonate) ₄ instead of Mn (2,2,6,6-tetramethyl-3,5-heptanedionate) ₃ The procedure was performed in the same manner as in Example 2 except for the above. Reaction conditions are first
In the table, the production amount, yield and production rate of the obtained DPC
It is shown in the table.

Example 5 In Example 2, Mn (2,2,6,6-tetramethyl-3,5-heptanedionate) ₃ was replaced by Ce
(2,2,6,6-tetramethyl-3,5-heptanedionate) The same operation as in Example 2 was carried out except that 9.6 mg (11 micromol) of ₄ was used. Table 1 shows the reaction conditions, and Table 2 shows the amount, yield, and production rate of the obtained DPC.

Example 6 The procedure of Example 2 was repeated except that bis (triphenylphosphoranylidene) ammonium bromide was used in an amount of 74.2 mg (120 μmol). Table 1 shows the reaction conditions, and Table 2 shows the amount, yield, and production rate of the obtained DPC.

Example 7 In Example 2, 21.8 mg (36%) of Mn (2,2,6,6-tetramethyl-3,5-heptanedionate) ₃ was used.
The procedure was performed in the same manner as in Example 2 except for using (micromol). Table 1 shows the reaction conditions, and Table 2 shows the amount, yield, and production rate of the obtained DPC.

Example 8 The procedure of Example 2 was repeated, except that the reaction time was changed to 1 hour. Table 1 shows the reaction conditions, and Table 2 shows the amount, yield, and production rate of the obtained DPC.

Example 9 Example 9 was carried out in the same manner as in Example 1 except that Pd (ethylenediamine) Cl ₂ was used instead of Pd (biquinoline) Cl ₂ . Table 1 shows the reaction conditions, and Table 2 shows the amount, yield, and production rate of the obtained DPC.

Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Example 2 except that no redox agent was used. Table 1 shows the respective reaction conditions, and Table 2 shows the amount, yield, and production rate of the obtained DPC.

Example 10 Example 10 was carried out in the same manner as in Example 2, except that carbon monoxide was 0.60 MPa and air was 0.15 MPa. The amount of DPC obtained was 0.110 mmol (yield 0.68%).

Example 11 Example 11 was carried out in the same manner as in Example 2 except that 1.00 MPa of carbon monoxide was used and 0.25 MPa of air was used. The amount of DPC obtained was 0.464 mmol (yield 2.89%).

[0057]

[Table 1]

Pb (biqu) Cl ₂ : Pd (biquinoline) Cl ₂ Pb (ArN ＝ CH) ₂ Cl ₂ : Pd [glyoxalbis (2,6-diisopropylphenyl) imine] Cl
₂ Pb (ArN = CCH ₃ ) ₂ Cl ₂ : Pd [diacetylbis (2,6-diisopropylphenyl) imine] Cl
₂ Pb (eda) Cl ₂ : Pd (ethylenediamine) Cl
₂ TMHD: 2,2,6,6-tetramethyl-3,5-heptanedionate Trop: Tropolonate (Ph ₃ P =) ₂ NBr: Bis (triphenylphosphoranylidene) ammonium bromide

[0059]

[Table 2]

[0060]

As described above, according to the production method of the present invention, an aromatic carbonate compound useful as an intermediate for the synthesis of various organic compounds such as the synthesis of a polycarbonate by a transesterification method, or as a polycarbonate resin, etc. It can be efficiently produced in one step and in a high yield from an aromatic hydroxy compound. Therefore, as a method for efficiently producing an aromatic carbonate compound, its utility value is particularly high in the field of polycarbonate production.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 21, 1999 (1999.1.2
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction contents]

Example 1 In a 30 ml autoclave, 3.02 g (32 mmol) of phenol and Pd (biquinoline) Cl were added.
₂ , 5.2 mg (12 micromol), Mn (2,2,2)
6,6-tetramethyl-3,5-heptanedionate)
₃ (14.5 mg, 24 micromol) and bis (triphenylphosphoranylidene) ammonium bromide (148.
4 mg (240 μmol) was encapsulated. By pressurizing and depressurizing with carbon monoxide, the inside of the autoclave was replaced with carbon monoxide. Then, 0.50MP in 25 ° C conversion
Carbon monoxide was pressurized so as to obtain a, and air was further pressurized so that the entire pressure became 0.75 MPa.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction contents]

[0057]

[Table 1]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

Pd (biqu) Cl ₂ : Pd (biquinoline) Cl ₂ Pd (ArN ＝ CH) ₂ Cl ₂ : Pd [glyoxalbis (2,6-diisopropylphenyl) imine] Cl
₂ Pd (ArN = CCH ₃ ) ₂ Cl ₂ : Pd [diacetylbis (2,6-diisopropylphenyl) imine] Cl
₂ Pd (eda) Cl ₂ : Pd (ethylenediamine) Cl
₂ TMHD: 2,2,6,6-tetramethyl-3,5-heptanedionate Trop: Tropolonate (Ph ₃ P =) ₂ NBr: Bis (triphenylphosphoranylidene) ammonium bromide

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hirohisa Ishii 1-1-1 Higashi, Tsukuba-shi, Ibaraki Prefectural Institute of Advanced Industrial Science and Technology Intensive Polymerization Concentration Cooperative Research Institute (72) Inventor Mitsuru Ueda Toichi-ichi Tsukuba-shi, Ibaraki No. 1 in the Institute of Materials Science and Technology, National Institute of Industrial Science (72) Kazuhiko Takeuchi 1-1, Higashi, Tsukuba, Ibaraki Pref.Institute for Materials Science and Technology, National Institute of Advanced Industrial Science and Technology (72) Michihiko Asai, Higashi 1-chome, Tsukuba, Ibaraki No. F-term (Reference) 4G069 AA06 BA21A BA21B BA27A BA27B BC31A BC41A BC43B BC53A BC57A BC61A BC62B BC66A BC67A BC68A BC72A BC72B BE05A BE05B BEB BEB BEB BEB BEA BEB BEA BE46B CB25 CB72 DA02 4H006 AA02 AC48 BA08 BA16 BA25 BA46 BA4 7 BE30 BE40 4H039 CA66 CD30 CD40

Claims (2)

[Claims] 1. A catalyst comprising: (a) a palladium complex compound having, as a ligand, an aromatic hydroxy compound, carbon monoxide and oxygen; and (b) a redox catalyst. A method for producing an aromatic carbonate characterized by reacting in the presence. 2. A palladium complex compound having an aromatic hydroxy compound, carbon monoxide and oxygen as a ligand (a) a diimine compound as a ligand, a palladium complex compound having a bipyridyl compound as a ligand, and a diamine compound (B) at least one palladium complex compound selected from palladium complex compounds having
A method for producing an aromatic carbonate ester which is reacted in the presence of a catalyst comprising a redox catalyst.