JPH08169863A - Production of carbonate ester - Google Patents

Abstract

PURPOSE: To efficiently obtain a carbonate ester useful as a raw material for polycarbonates, an intermediate for medicines, a solvent, etc., little in by- products in a high yield at a high reaction rate and in a long catalyst life by reacting an alcohol with carbon monoxide and oxygen in the presence of a specific catalyst in a gaseous phase. CONSTITUTION: (B) An alcohol such as methanol is reacted with (C) carbon monoxide and (D) oxygen e.g. at a reaction temperature of 30-200 deg.C in a reaction pressure of the atmospheric pressure to 100kg/cm<2> in a gaseous phase in the presence of (A) a solid catalyst produced by carrying a complex compound [e.g. a compound of the formula: PdCu(R-C5 H3 NO)n Xm Yz (X is an organic or an inorganic ion; Y is an electron-donating ligand; R is H, an alkyl, an alkoxy, a halogen, CN; (m), (n) are 0-2, 2-4, respectively; m+n=4; (z) is 0, 1) containing a platinum group metal (salt), copper and a 2-hydroxypyridine compound on a carrier such as active carbon to obtain the objective carbonate ester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an intermediate for producing a polycarbonate, a pharmaceutical intermediate, and a method for producing a carbonic acid ester having use as a solvent.

[0002]

2. Description of the Related Art As a method for producing a carbonic acid ester, a method of reacting alcohol with phosgene is known. According to this conventional method, there are drawbacks such that phosgene is highly toxic and highly corrosive chlorine is by-produced by the reaction between alcohol and phosgene. Therefore, a number of methods for producing carbonic acid esters which eliminate these drawbacks and which do not use phosgene have been proposed. Among them, as a general manufacturing method,
Examples thereof include a method in which an alcohol to be esterified is reacted with carbon monoxide and oxygen by a liquid phase method or a gas phase method in the presence of a catalyst.

Examples of the method for producing a carbonic acid ester by the liquid phase method include, for example, JP-A-5-320098 and JP-A-4.
No. 356446 and Japanese Patent Publication No. 63-38018. The method described in Japanese Patent Application Laid-Open No. Hei 5-32098 is a method in which alcohols, carbon monoxide and oxygen are present in the presence of a platinum group compound such as a palladium compound, a copper compound such as copper chloride and an alkaline earth metal salt such as magnesium chloride. Is a method of reacting with
The method described in Japanese Patent No. 356446 is a method of reacting alcohols with carbon monoxide and oxygen in the coexistence of a platinum group compound such as palladium, a copper compound such as copper acetate, 2-hydroxypyridines and an alkali metal salt. Is. The method described in JP-B-63-38018 is a method of reacting alcohol with carbon monoxide and oxygen in the presence of a copper catalyst composed of cuprous halide such as cuprous chloride.

However, in the case of these liquid phase processes, the catalyst is generally recycled, so that a catalyst separation / recycling step is required. In addition, in a catalyst system using a platinum group metal, the zero-valent reoxidation efficiency of the platinum group metal becomes insufficient, and deactivation and precipitation are likely to occur. In a catalyst system containing a copper compound, water produced as a by-product during the precipitation of copper oxide and / or the formation of carbonic acid diester is changed to basic copper chloride or the like, and is easily insolubilized and precipitated. Further, the catalyst is likely to be precipitated and deactivated in the catalyst recycling step, and in order to continuously produce the carbonic acid diester, it takes a great deal of cost to recover and regenerate the catalyst. Further, in order to prevent deactivation of the catalyst, there is a problem that a large amount of halogen compound is required, which requires a great cost in terms of material of the device.

In order to solve the problems existing in the above liquid phase method, a method of producing a carbonic acid ester by a gas phase reaction using a solid catalyst is disclosed in WO90 / 15791, JP-A-6-145103, and JP-A-6-145103. It is proposed by Kaihei 5-255199. WO90 / 15791
The invention described in Japanese Patent Laid-Open Publication No. 2000-242242 discloses a method in which alcohol is mixed with carbon monoxide and oxygen in the vapor phase in the presence of a solid catalyst having a copper compound and various additives carried on a carrier, such as a catalyst carrying a complex of copper with an organic phosphorus compound. Is a method of reacting according to JP-A-6-14.
The invention described in Japanese Patent No. 5103 is a method of reacting an alcohol with carbon monoxide and oxygen in a gas phase in the presence of a solid catalyst in which a copper compound or a copper compound and a basic nitrogen compound are supported on various carriers. The invention described in Japanese Patent Application Laid-Open No. 5-255199 discloses a method in which an alcohol is added to carbon monoxide and oxygen in the presence of a solid catalyst in which a platinum group metal compound, a copper salt, 2-hydroxypyridine and an alkali metal salt are supported on a carrier. Is a method of reacting with.

However, even in these methods, the catalytic activity and the carbon monoxide selectivity are not sufficient, or the carbon monoxide is deactivated in a short time, so that it is not possible to stably produce a carbonate ester for a long time. . Further, a method for producing a carbonic acid ester by reacting a nitrite ester and carbon monoxide in a gas phase in the presence of a solid catalyst obtained by adding copper, molybdenum, and an alkali metal chloride to a platinum group catalyst (JP-A-4-297444). Gazette) is also known, but a nitrite recovery process,
In addition, the manufacturing process is complicated, such as requiring a regeneration step.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have earnestly studied to provide a method for producing a carbonic acid ester from alcohol, carbon monoxide and oxygen by a gas phase method in a processally advantageous manner. When a solid catalyst obtained by supporting a platinum group compound or a salt thereof, a complex compound consisting of copper and 2-hydroxypyridine on a carrier without using an alkali metal salt as a catalyst for the above reaction, The inventors have found that it is possible to reduce the decrease in selectivity due to combustion loss of carbon monoxide and the like and to stably produce a carbonate ester for a long time, and have completed the present invention.

The present invention is a method for producing a carbonic acid ester from alcohol, carbon monoxide and oxygen by a gas phase method, in which a decrease in carbon monoxide selectivity due to combustion loss or the like is minimized and stable for a long time. An object of the present invention is to provide an industrially advantageous method for producing a carbonic acid ester, which produces a carbonic acid ester at a high reaction rate and does not require a step of separating a catalyst and a product.

[0009]

In order to solve the above problems, in the invention described in claim 1, in producing a carbonic acid ester, (1) a platinum group metal or a salt thereof, copper and 2-hydroxypyridine Alcohol in the presence of a solid catalyst prepared by supporting a complex compound containing a group on a carrier.
The means of reacting with carbon monoxide and oxygen in the gas phase is taken. Further, in the invention described in claim 2, in producing the carbonic acid ester, (1)
At least one selected from a complex compound containing a platinum group metal or a salt thereof, copper and 2-hydroxypyridines, and (2) metal copper, a copper salt or a complex compound of copper, and / or (3) 2-hydroxy. In the presence of a solid catalyst in which pyridines are supported on a carrier, alcohol is reacted with carbon monoxide and oxygen in a gas phase.

Hereinafter, the present invention will be described in detail. In the method for producing a carbonate ester according to the present invention, a solid catalyst having the following catalyst components supported on a carrier is used. As the catalyst component,
(1) Platinum group metal or salt thereof, complex compound consisting of copper and 2-hydroxypyridine (hereinafter referred to as "first component"), (2) Metallic copper, copper salt or complex compound of copper (hereinafter referred to as "first component") Two components ") and (3) 2-hydroxypyridines (hereinafter referred to as" third component ").

The platinum group used for preparing the "first component" includes ruthenium, rhodium, palladium,
Examples include iridium and platinum. Among these,
Palladium is preferred. These metals can also be used as salts of metals or halides, nitrates, sulfates, phosphates, acetates and the like.

More specifically, ruthenium chloride, ruthenium iodide, tris (acetylacetonato) ruthenium,
Rhodium chloride, rhodium bromide, rhodium iodide, rhodium nitrate, rhodium nitrate, rhodium sulfate, rhodium acetate, palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium propionate, palladium caproate, palladium nitrate, palladium sulfate , Palladium phosphate, bis (acetylacetonato) palladium, palladium oxalate, iridium chloride, chloroplatinic acid, potassium tetrachloroplatinate, and the like. Further, in the case of palladium, it can also be used as a complex compound in which 2-hydroxypyridines are coordinated in advance.

Examples of complex compounds in which 2-hydroxypyridines are pre-coordinated with palladium include, for example, bis (2-hydroxypyridine) palladium chloride, bis (2-hydroxypyridine) palladium bromide and bis (2-hydroxypyridine) palladium. Acetate, bis (4-
Methyl-2-hydroxypyridine) palladium chloride, bis (5-methyl-2-hydroxypyridine) palladium chloride, bis (6-methyl-2-hydroxypyridine) palladium chloride, bis (2-hydroxy-)
4-ethylpyridine) palladium chloride, bis (2-
Hydroxy-4-methoxypyridine) palladium chloride, bis (2-hydroxy-5-methoxypyridine) palladium chloride, bis (4,6-dimethyl-2-hydroxypyridine) palladium chloride, bis (2-hydroxy-4-chloropyridine) ) Palladium chloride, bis (2-hydroxy-6-chloropyridine) palladium chloride and the like. As a general method for preparing these complex compounds, a method of dissolving palladium chloride and sodium chloride in methanol and then adding 2-hydroxypyridines can be mentioned.

The copper compound used to prepare the "first component" is metallic copper or a copper salt compound.
As the copper salt compound, in addition to halides such as cupric chloride, cuprous chloride and cupric bromide, aliphatic carboxylic acids such as copper nitrate, copper sulfate, copper acetate, copper propionate and copper caproate Examples thereof include salts, aromatic carboxylates such as copper benzoate, and phosphates.

The 2-hydroxypyridines used for preparing the "first component" may have a substituent which does not inhibit this reaction in the 2-hydroxypyridine skeleton,
Examples thereof include alkyl groups, alkoxy groups, halogen atoms such as chlorine, bromine, and fluorine. Specifically, 2-
Hydroxypyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxy
-6-methylpyridine, 2-hydroxy-4-ethylpyridine, 2-hydroxy-4-methoxypyridine, 2-hydroxy-5-methoxypyridine, 2-hydroxy-6-methoxypyridine, 4,6-dimethyl-2- Hydroxypyridine,
2-hydroxy-4-chloropyridine, 2-hydroxy-6-
Chloropyridine, 5-cyano-2-hydroxypyridine and the like are used. Preferably, 2-hydroxypyridine, 2-hydroxy-5-methylpyridine, 2-hydroxy
It is preferable to use 2-hydroxyalkylpyridine such as -6-methylpyridine.

The "first component" used in the present invention is represented by the following general formula (I) in which a platinum group metal is coordinated with a nitrogen atom of 2-hydroxypyridines.

Embedded image PdCu (R—C ₅ H ₃ NO) _n X _m Y _z (I)

Where X is an organic or inorganic anion, Y
Is an electron donor ligand, R is hydrogen, an alkyl group, an alkoxy group, a halogen or a cyano group, n is an integer of 2 to 4, m is an integer of 0 to 2, n + m = 4, and Z is 0. Or represents an integer of 1) is preferably used.

The electron pair donor ligand used in preparing the above-mentioned "first component" is a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, or a coordination having a nitrogen atom and an oxygen atom. Is a child. Examples of the compound having a nitrogen atom include nitriles such as acetonitrile, amines such as pyridine and methylpyridine, and amides such as dimethylformamide and N-methylformamide. Examples of the compound having an oxygen atom include alcohols such as methanol, ethanol, phenol and cresol, ketones such as acetone and ethyl methyl ketone, esters such as ethyl acetate and methyl acetate, aldehydes such as acetaldehyde, tetrahydrofuran and diethyl ether. And the like.

Examples of the ligand having a phosphorus atom include phosphines such as triethylphosphine and triphenylphosphine, phosphine oxides such as triethylphosphine oxide and triphenylphosphine oxide, phosphites such as triethylphosphite, and hexamethylphosphole. Examples of amides include amides and hexamethylphosphorus triamide. As the ligand having sulfur, thiophenes such as thiophene and ethyl thiophene,
Examples thereof include dimethyl sulfide, tetramethylene sulfone, dimethyl sulfoxide, carbon disulfide and the like. These electron pair donor ligands are also used as a solvent for dissolving the "first component" in the supporting solution.

The organic or inorganic anion used in preparing the "first component" includes halogen anions such as chlorine, bromine and iodine, nitrate anions, phosphate anions, acetic acid, propionic acid, caproic acid, Examples thereof include carboxylic acid anions such as benzoic acid, paratoluenesulfonic acid anion, trifluoromethanesulfonic acid anion, tetrafluoroboron anion, and heteropolyacid anion. These anions can be introduced into the palladium-copper complex as anions of the starting palladium compound for synthesizing the palladium-copper compound. Further, the anion of the palladium-copper complex can be introduced into the palladium-copper complex by exchanging it with another anion. For example, a complex having various anions can be prepared by reacting a palladium-copper complex having chlorine as an anion with a silver salt having another anion and performing anion exchange.

The details will be described below. For example, general
Complex compound represented by formula (I) (n = 2, m = 2, z =
0) is PdCuCl₂ (C_Five H_Four NO)₂ , P
dCuBr₂ (C_Five H_Four NO)₂ , Complex compounds (n = 2,
m = 2, z = 1), PdCuCl₂ (C_Five H_Four 
NO)₂ (THF), PdCuBr₂ (C_Five H_Four NO)
₂ (THF), PdCuCl₂ (6-CH₃ C_Five H₃ N
O)₂ (EtOH), complex compound (n = 3, m = 1, z =
0) is PdCuCl (C_Five H_Four NO)₃, Complexation
As a compound (n = 3, m = 1, z = 1), PdCuC
l (C_Five H_Four NO)₃ (MeOH), PdCuCl (C
_Five H_Four NO)₃ (EtOH), PdCuBr (C_Five H_Four 
NO)₃ (EtOH), PdCu (NO₃ ) (C_Five H_Four 
NO)₃ (EtOH), PdCuSO₃ CF₃ (C_Five H
_Four NO)₃ (EtOH), complex compound (n = 4, m = 0,
For z = 0, PdCu (C_Five H_Four NO)_Four Etc.
You can

The general method for preparing these complex compounds is as follows. For example, PdCuCl ₂ (C ₅ H
₄ NO) ₂ (THF) can be prepared by reacting bis (2-hydroxypyridine) palladium chloride with copper acetate in THF at room temperature. Pd
CuCl (C ₅ H ₄ NO) ₃ (EtOH) is bis (2
-Hydroxypyridine) palladium chloride and copper acetate can be prepared by reacting in ethanol at room temperature. PdCu (C ₅ H ₄ NO) ₄ can be prepared by reacting bis (2-hydroxypyridine) palladium chloride, copper acetate and 2-hydroxypyridine in methanol at a temperature of 100 ° C.

To prepare a solid catalyst in which the "first component" is supported on a carrier (details will be described later), (a) a platinum group metal compound, a copper compound and 2-hydroxypyridines are added to a supporting solvent. Then, a method of directly supporting it on the carrier, or (b) a method of previously synthesizing and isolating this complex compound and then supporting it on the carrier can be mentioned. (A)
In the case of the above method, the presence or absence of the formation of the complex compound can be detected by measuring the ultraviolet absorption spectrum, for example. That is,
Since a change in absorption of a specific wavelength resulting from the formation of the complex compound is observed, it is possible to confirm whether or not the complex compound is formed. The amount of the “first component” supported is usually 0.01 as a platinum group metal with respect to the supported carrier.
-20% by weight, preferably 0.1-5% by weight.

The "first component" can be used alone by supporting it on a carrier, but in order to achieve higher activity, higher selectivity, long-term stable activity, etc., metallic copper, At least one selected from a copper salt or a copper complex compound (“second component”), and / or
It is preferable to use the 2-hydroxypyridines (“third component”) simultaneously supported on a carrier.

The copper salt used to prepare the "second component" includes halides such as cupric chloride and cuprous chloride, as well as nitrates, sulfates, copper acetate, copper propionate and caproic acid. Aliphatic carboxylic acid salts such as copper, aromatic carboxylic acid salts such as copper benzoate, and phosphoric acid salts are used. The copper complex compound is a complex salt having an organic ligand, for example, a nitrogen atom, an oxygen atom, or a complex salt of a nitrogen atom and an organic ligand having an oxygen atom.

More specifically, examples of the organic ligand having a nitrogen atom include aliphatic amines such as trimethylamine, aromatic amines such as aniline, diamines such as tetramethylethylenediamine, pyridines, imidazoles and quinoxalines. Etc. Examples of the organic ligand having an oxygen atom include N-oxides, β-diketones, salicylic acid derivatives, dicarboxylic acids and the like. More preferred are 2-hydroxypyridines, 2-methoxypyridines, 5-cyanopyridines, tetraalkyldiaminoalkanes, and quinoxalines, and particularly,
2-hydroxypyridines are preferred. The amount of the "second component" used is usually 1 per mol of the platinum group metal atom.
It is used in the range of ˜1000 mol, preferably 1 to 100 mol, particularly preferably 1 to 20 mol.

The "third component" used in the present invention may be a 2-hydroxypyridine having a substituent on the 2-hydroxypyridine skeleton that does not inhibit this reaction. Examples of the substituent that does not inhibit this reaction include an alkyl group, an alkoxy group, a halogen atom such as chlorine, bromine, and fluorine. Specific examples of 2-hydroxypyridines include 2-hydroxypyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxy-6-methylpyridine, and 2-hydroxy-4-ethyl. Pyridine, 2-hydroxy-4-methoxypyridine, 2-hydroxy-5-methoxypyridine, 2-hydroxy-6-methoxypyridine, 4,6-dimethyl-2-hydroxypyridine, 2-hydroxy-4-chloropyridine, 2 -Hydroxy-6-chloropyridine, 5-cyano-2-hydroxypyridine and the like can be mentioned. Among these, 2-hydroxypyridine and 2-hydroxyalkylpyridines such as 2-hydroxy-5-methylpyridine and 2-hydroxy-6-methylpyridine are preferable. Two
-The amount of hydroxypyridines used is usually 1 to 1000 mol, preferably 1 to 1 mol, per 1 mol of platinum group metal atom.
It is in the range of 00 mol.

To prepare a solid catalyst from the above catalyst component, the catalyst component is supported on a carrier. As the carrier used to support the catalyst component, activated carbon, graffiti, alumina, silica, silica-alumina, diatomaceous earth, asbestos, ion exchange resin, calcium silicate, zeolite, aluminosilicate, polyvinyl pyridine, magnesia,
Examples include titania, zirconia, and cerium oxide.
To prepare a solid catalyst in which a plurality of catalyst components are supported on a carrier, a commonly used method may be used, and a typical method thereof is as follows. (C) First, the "second component" is loaded on the carrier, and then the "first component" and the "third component" are sequentially loaded, (d) "first component", "second"
"Component" is dissolved in an organic solvent, a carrier is added thereto, impregnated and dried, and then the "third component" is carried, or (e) the first component, the second component and the third component are dissolved in the organic solvent. Then, a method of adding a carrier to this solvent, impregnating it, drying and supporting it, and the like can be mentioned.

In the method for producing carbonate ester according to the present invention,
Alcohol, carbon monoxide and oxygen are used as raw materials. The alcohol is preferably a saturated aliphatic alcohol, more preferably a saturated aliphatic alcohol having 1 to 6 carbon atoms such as methanol, ethanol, butanol, ethylene glycol, propylene glycol, 1,4-butanediol. Carbon monoxide and oxygen are
It may be pure, or may be diluted with a reaction-inert gas such as nitrogen, argon or carbon dioxide.

The conditions for producing a carbonic acid ester according to the method of the present invention will be described below. The reaction pressure is from normal pressure to
Range of 100 kg / cm ² , preferably normal pressure to 10 k
It is in the range of g / cm ² , and particularly preferably in the range of atmospheric pressure to 5 kg / cm ² from the viewpoint of good operability. Alcohol partial pressure in the range of 0.001~20kg / cm ^2, preferably in the range of 0.01 to 10 / cm ^2. Carbon monoxide partial pressure is 0.001 to 60 kg / cm
The range is ² , preferably 0.01 to 10 kg / cm ² . Oxygen partial pressure is 0.001 to 20 kg / cm
The range is ² , preferably 0.01 to 5 kg / cm ² . The oxygen partial pressure is preferably adjusted by dilution with an inert gas so that the gas composition in the reaction system will not exceed the explosion limit. The reaction temperature is in the range of 30 to 200 ° C, preferably 60 to 150 ° C. The reaction is
Either a batch system or a continuous system may be used. Above all, a continuous system in which carbon monoxide, oxygen, and alcohol are continuously supplied to a fixed bed or a fluidized bed in which a solid catalyst is present is preferable because a high carbonic acid ester production rate can be obtained. The produced carbonic acid ester can be obtained from the reaction product solution by operations such as distillation and extraction, and a complicated operation for separating the catalyst is not required.

According to the method of the present invention, when the carbonic acid ester is produced by the gas phase method, the use of the above-mentioned specific solid catalyst can significantly reduce the decrease in the selectivity due to the combustion loss of carbon monoxide. Moreover, it is possible to stably produce the desired carbonate ester for a long time. Although the mechanism of action of these solid catalysts is not clear at present, platinum group metal compounds, copper and 2-hydroxypyridine complex compounds suppress the formation of oxalic acid diesters and carbon dioxide by combustion of carbon monoxide. However, it is presumed that the carbonic acid ester can be stably generated for a long time because the carbonic acid ester of the target is highly selectively produced and the reoxidation of palladium with copper is also efficiently performed. .

[0032]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The abbreviations used in the examples have the following meanings. STY: means the number of moles of carbonic acid ester produced per 1 kg of catalyst and 1 hour of reaction time. CO selectivity: Formula, [carbonic acid ester (mmol) × 10
0] / [carbonic acid ester (mmol) + carbon dioxide (mm
ol) + 2 × oxalic acid ester (mmol) + acetic acid ester (mmol) + formic acid ester (mmol)], which is the value (%).

[Example 1] (i) Preparation of catalyst 0.74 g (4.0 mmol) of cupric anhydride was added to 25 parts of water.
20 ml of activated carbon was added to this aqueous solution,
After impregnating at room temperature for hours, evaporate to dryness, and under a nitrogen stream,
It was dried at 100 ° C for 1 hour and further at 200 ° C for 1 hour (operation 1). Bis (2-hydroxypyridine) palladium chloride 0.3 g (0.81 mmol) and copper acetate 0.
15 g (0.81 mmol) of methanol 100 ml
In the solution obtained by dissolving in, the increase in the relative absorbance at 835 nm was observed by the ultraviolet absorption spectrum measurement, and a constant value was obtained, and the formation of a complex containing palladium, copper and 2-hydroxypyridine was confirmed. Activated carbon carrying dicopper was added and impregnated overnight, then evaporated to dryness (operation 2).
2-hydroxypyridine 0.085 g (0.89 mmol) was added to the solid obtained by the above operation in methanol 20 m.
It was added to the solution dissolved in 1 and impregnated for 1 hour, then evaporated to dryness, and dried under a nitrogen stream at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour (operation 3).

(Ii) Production of carbonic acid ester A Pyrex reactor having an inner diameter of 18 mm and a length of 400 mm was filled with 5.5 ml of the catalyst prepared by the above method, and further glass beads (particle diameter: 2 mm or less) Was filled. The glass bead layer functions as a vaporizer for alcohol. This reactor was fixed vertically in an electric furnace, and while keeping the catalyst layer temperature at 100 ° C., carbon monoxide 35 vol%, oxygen 3.9 vol%, nitrogen 61.
A mixed gas of 1 vol% was continuously supplied to the catalyst layer at a flow rate of 5.5 l / hour, and at the same time, methanol was continuously supplied to the catalyst layer at a flow rate of 5.5 ml / hour. The reaction product was collected by a gas-liquid separator, and the collected liquid was analyzed by gas chromatography and quantified. The exhaust gas was also analyzed by gas chromatography to quantify carbon dioxide. When the reaction was carried out for 2.5 hours,
The STY was 1.74 and the CO selectivity was 94%. Neither carbon dioxide nor the formation of oxalic acid diester was observed. In this example, when the method of the present invention is used, STY, CO
It shows that both the selectivity is high, the production of by-products is small, and the target carbonate ester is obtained in high yield.

Example 2 In the example described in Example 1, (i) in the preparation of the catalyst, 0.39 g (4.1
The catalyst was prepared and the carbonic acid ester was produced by the same procedure as in the same example except that it was changed to (mmol). In this example, STY was 2.52 and CO selectivity was 95%.
This example is also STY, CO when using the method of the present invention.
It shows that both the selectivity is high, the production of by-products is small, and the target carbonate ester is obtained in high yield.

Example 3 In the example described in Example 1, (i) in the preparation of the catalyst, the amount of cupric acetate in Run 1 was 1.48 g (8.0 mmol).
Then, the amount of 2-hydroxypyridine in step 3 was 0.39 g.
(4.1 mmol), except that the catalyst was prepared by the same procedure as in the example except that the carbonic acid ester was produced. In this example, STY was 2.08 and CO selectivity was 94%. This example also shows that according to the method of the present invention, both the STY and CO selectivity are high, the production of by-products is small, and the desired carbonate ester is obtained in high yield.

Example 4 (i) Preparation of catalyst 0.74 g (4.0 mmol) of cupric anhydride was added to 25 parts of water.
20 ml of activated carbon was added thereto and impregnated at room temperature for 7 hours, then evaporated to dryness, and dried under a nitrogen stream at 100 ° C. for 1 hour and then at 200 ° C. for 1 hour. The obtained activated carbon carrying cupric acetate was treated with PdCuCl (2-Py
O) 3EtOH 0.44 g (0.81 mmol) and copper acetate 0.15 g (0.81 mmol) in methanol 2
It was added to the solution dissolved in 80 ml, impregnated overnight and then evaporated to dryness. The solid obtained by the above operation was added to a solution of 0.77 g (8.1 mmol) of 2-hydroxypyridine dissolved in 40 ml of methanol, and the mixture was immersed for 1 hour, then under a nitrogen stream at 100 ° C. for 1 hour, and further 150 ° C. And dried for 1 hour. (ii) Production of Carbonic Acid Ester In the example described in Example 1, the production operation was carried out in the same procedure as in the same example except that the catalyst described in (i) above was changed. STY in this example is 1.74,
The CO selectivity was 95%.

[Example 5] (i) Preparation of catalyst 1.48 g (8.0 mmol) of cupric anhydride was added to 25 parts of water.
20 ml of activated carbon was added thereto and impregnated at room temperature for 7 hours, then evaporated to dryness, and dried under a nitrogen stream at 100 ° C. for 1 hour and then at 200 ° C. for 1 hour. Screw (2-
Hydroxypyridine) palladium chloride 0.3 g
A solution in which (0.81 mmol) was dissolved in 100 ml of methanol and the relative absorbance at 835 nm was observed to increase by ultraviolet absorption spectrum measurement, and it became a constant value, and formation of a complex containing palladium, copper and 2-hydroxypyridine was confirmed. To the above, the activated carbon carrying cupric acetate obtained above was added and impregnated overnight, and then evaporated to dryness. 0.39 g of 2-hydroxypyridine (4.
(1 mmol) was added to a solution prepared by dissolving 20 ml of methanol and immersed for 1 hour, and then dried under a nitrogen stream at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. (ii) Production of Carbonic Acid Ester In the example described in Example 1, the production procedure was the same as in the same example except that the catalyst was changed to that described in (i) above and the reaction time was 10 hours. I went. Reaction 5
STY is 2.01 and CO selectivity is 94%
And the STY when the reaction was carried out for 10 hours was 1.97,
The CO selectivity was 95%. This example shows that, according to the method of the present invention, the decrease in STY after 5 hours is only 0.04, and even if the catalyst is used for a long time, the decrease in catalyst activity over time is small and the catalyst is stable for a long time. Is shown.

Comparative Example 1 (i) Preparation of Catalyst 1.5 g (8.4 mmol) of cupric acetate anhydride was added to 40 m of water.
10 ml of activated carbon was added to this aqueous solution and impregnated at room temperature for 7 hours, then evaporated to dryness, and the mixture was stirred under a nitrogen stream for 10 hours.
It was dried at 0 ° C for 1 hour and further at 200 ° C for 1 hour. 0.15 g (0.84 mmol) of palladium chloride and 0.10 g (1.7 mmol) of sodium chloride were added to 25 parts of methanol.
To the solution dissolved in ml, the activated carbon carrying cupric acetate obtained above was added, impregnated overnight, and then evaporated to dryness. The solid obtained by the above operation was added to 2-hydroxypyridine 0.8
0 g (8.4 mmol) was added to a solution prepared by dissolving 30 ml of methanol and impregnated for 1 hour. Next, the solid was collected by filtration, evaporated to dryness, and dried under a nitrogen stream at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. (ii) Production of Carbonic Acid Ester The procedure of Example 1 was repeated except that the catalyst was changed to the catalyst described in (i) above and the reaction time was 8 hours. I went. When the reaction was carried out for 5 hours, STY was 2.55, CO selectivity was 95%, and when the reaction was carried out for 8 hours, STY was 2.20, CO
The selectivity was 95%. This example is STY in 3 hours
Of the catalyst reaches 0.35, which shows that there is a large decrease in activity over time when the catalyst is used for a long time, and there is a problem when the catalyst is used for a long time.

Comparative Example 2 (i) Preparation of catalyst 0.76 g (4.2 mmol) of cupric acetate anhydride was added to 18 parts of water.
10 ml of activated carbon was added to this aqueous solution,
After impregnating at room temperature for 1 hour, evaporate to dryness, and under nitrogen flow, 1
It was dried at 00 ° C for 1 hour and further at 200 ° C for 1 hour. Bis (2-hydroxypyridine) palladium chloride 0.
To a solution obtained by dissolving 15 g (0.42 mmol) in 40 ml of methanol was added the activated carbon carrying cupric acetate obtained above, impregnated overnight, and then evaporated to dryness. The solid obtained by the above operation was added with 0.40 g of 2-hydroxypyridine (4.
(2 mmol) was added to a solution dissolved in 10 ml of methanol, impregnated for 1 hour, evaporated to dryness, and heated to 100 ° C under a nitrogen stream.
And dried at 150 ° C. for 1 hour. (ii) Production of Carbonic Acid Ester In the example described in Example 1, the production procedure was the same as in the same example except that the catalyst was changed to that described in (i) above and the reaction time was 10 hours. I went. Reaction 5
STY is 2.03, CO selectivity is 95%
And the STY when the reaction was carried out for 10 hours was 1.72,
The CO selectivity was 95%. This example shows S in 5 hours
The decrease in TY reached 0.31, indicating that there was a large decrease in activity over time when the catalyst was used for a long time, indicating a problem when the catalyst was used for a long time.

[0041]

INDUSTRIAL APPLICABILITY The present invention has the following advantageous effects, and its industrial utility value is extremely large. 1. According to the method of the present invention, the selectivity of carbon monoxide is sufficient, the production of byproducts such as carbon dioxide and oxalate can be minimized, and the desired carbonate can be obtained in high yield. 2. According to the method of the present invention, the desired carbonate ester can be obtained at a high reaction rate. 3. According to the method of the present invention, the catalytic activity lasts for a long time, which is industrially advantageous. 4. According to the method of the present invention, it is not necessary to separate the target carbonic acid ester and the catalyst, which is an industrially advantageous process.

Claims (8)

[Claims] (1) Alcohol, carbon monoxide and oxygen in the presence of a solid catalyst prepared by supporting a complex compound containing a platinum group metal or a salt thereof, copper and 2-hydroxypyridines on a carrier, A method for producing a carbonic acid ester, which comprises reacting in a gas phase. 2. A complex compound containing (1) a platinum group metal or a salt thereof, copper and 2-hydroxypyridines, and (2)
In the presence of at least one selected from metallic copper, a copper salt, or a complex compound of copper, and / or (3) a solid catalyst prepared by supporting 2-hydroxypyridines on a carrier, alcohol, carbon monoxide and A method for producing a carbonate ester, which comprises reacting with oxygen in a gas phase. 3. A platinum group metal or a salt thereof, copper and 2-
As a complex compound composed of hydroxypyridines, the following general formula (I): PdCu (R—C ₅ H ₃ NO) _n X _m Y _z (I) {(I) In the formula (I), X is an organic compound. , Or an inorganic anion,
Y represents an electron donor ligand, R represents hydrogen, an alkyl group, an alkoxy group, a halogen or a cyano group, n is an integer of 2 to 4, m is an integer of 0 to 2, n + m = 4, and Z is A compound represented by the formula (expressing an integer of 0 or 1) is used, and the method for producing a carbonate ester according to claim 1 or 2, characterized in that: 4. The reaction temperature is 30 to 200 ° C.
The method for producing a carbonic acid ester according to any one of claims 1 to 3, characterized in that: 5. The pressure during the reaction is from atmospheric pressure to 100 k
The method for producing a carbonic acid ester according to any one of claims 1 to 3, wherein the range is g / cm ² . 6. The method for producing a carbonate ester according to claim 1, wherein methanol is used as the alcohol. 7. The method for producing a carbonate ester according to claim 1, wherein activated carbon is used as a carrier. 8. The method for producing a carbonate ester according to claim 1, wherein palladium is used as the platinum group metal.