JPH0892169A - Production of carbonic acid ester - Google Patents

Abstract

PURPOSE: To efficiently, stably and continuously obtain a carbonic acid ester useful as an intermediate for polycarbonate by reacting an alcohol with a carbon monoxide and oxygen in the presence of a platinum group metal/copper-based catalyst and a specific cocatalyst. CONSTITUTION: This method for producing carbonic acid ester is to react an alcohol with carbon monoxide and oxygen in the presence of (A) a platinum group metal or its salt, (B) a metal copper, a copper salt or a complex compound of copper, (C) at least one compound of a group comprising a lanthanoid compound, a transition metal compound of the groups IV to VII, an iron compound, a cobalt compound and a nickel compound and (D) 2-hydroxypyridines, preferably at 20-200 deg.C under 0.1-20kg/cm<2> partial pressure of CO2 and 0.1 to 20kg/cm CO partial pressure. Furthermore, the component A includes, e.g. a complex compound of a platinum group metal of the formula [X is an organic or inorganic anion; Y is an electron donating ligand; R is H, an alkyl, etc.; (n) is 2, (m) is 2, Z is 0 or (n) is 2, (m) is 2 and Z is 1, etc.], copper and 2- hydroxypyridines.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art There is a method for producing a carbonic acid ester by reacting an alcohol with phosgene, but phosgene is highly toxic or a large amount of highly corrosive hydrochloric acid is by-produced due to the reaction between alcohol and phosgene. There are problems such as that. Therefore, many methods for producing carbonic acid esters without using phosgene have been proposed. Among them, a general method is a method of reacting an alcohol to be esterified with carbon monoxide and oxygen in the presence of a catalyst. As a typical catalyst used, a system in which a palladium compound, a copper compound and a base are combined (Japanese Patent Publication No. 61-8816, Japanese Patent Publication No. 61-43).
338), a system in which a palladium compound and a weak acid salt and / or halide of copper and a weak acid salt and / or halide of an alkaline earth metal are combined (WO89 / 0758).
There is 7). Furthermore, a system in which 2-hydroxypyridines are further added in the presence of at least one selected from the group consisting of palladium compounds and copper salts, alkali metal salts and alkaline earth metal salts (JP-A-4-356446) is proposed. ing.

However, in these catalyst systems, oxalic acid, which is a by-product of the reaction, increases during the reaction, so that copper reacts with oxalic acid to insolubilize and precipitate as copper oxalate and expensive platinum. There is a problem that it is difficult to continuously use an industrial catalyst because the group compound is easily deposited as a metal, and the expensive platinum group compound is difficult to recover and recycle.

[0004]

In the conventional reaction for obtaining a carbonic acid ester from an alcohol, carbon monoxide and oxygen by using a platinum group metal-copper catalyst, the platinum group metal is precipitated as a metal and copper is Precipitation as copper oxalate and the like reduced the catalytic activity, and it was difficult to recover and recycle expensive platinum group metals, making continuous use of industrial catalysts difficult.

An object of the present invention is to suppress the formation of oxalic acid ester, which is a precursor of oxalic acid, and to suppress the precipitation of copper oxalate in the reaction of obtaining a carbonic acid ester from alcohol, carbon monoxide and oxygen. In addition, the catalyst activity is prevented from lowering by preventing the precipitation of expensive platinum group metals, the catalyst system is stabilized, and the recovery and recycling operations of expensive platinum group metals are facilitated.

[0006]

Means for Solving the Problems The inventors of the present invention have earnestly investigated the search for a cocatalyst for the reaction of obtaining a carbonic acid ester from an alcohol, carbon monoxide and oxygen using a platinum group metal-copper catalyst, Reacting in the presence of at least one selected from the group consisting of lanthanoid compounds, group IV transition metal compounds, group V transition metal compounds, group VI transition metal compounds, group VII transition metal compounds, iron compounds, cobalt compounds and nickel compounds. It was found that the formation of oxalate can be suppressed without lowering the production rate of carbonic acid ester, the formation of copper oxalate can be prevented or significantly reduced, and the precipitation of palladium can be prevented or significantly reduced. Further, they have found that it is possible to circulate and use the catalyst component recovered by the distillation or evaporation of the reaction product liquid in the reaction system, and arrived at the present invention.

Although the mechanism of action is not clear, a lanthanoid compound, a group IV transition metal compound,
The presence of at least one selected from the group consisting of a Group V transition metal compound, a Group VI transition metal compound, a Group VII transition metal compound, an iron compound, a cobalt compound and a nickel compound forms a carbomethoxy complex of a platinum group metal. It suppresses the insertion of carbon monoxide, promotes the reoxidation process of copper, and promotes the reoxidation of 0-valent platinum group metals, thereby suppressing the formation of oxalate ester and suppressing the precipitation of platinum group metals. It is estimated that

That is, the gist of the present invention is (1) platinum group metal or salt thereof, (2) metallic copper, copper salt or copper complex compound, (3) lanthanoid compound, group IV transition metal compound, group V transition. Metal compound, Group VI transition metal compound, VI
In the presence of at least one selected from the group consisting of Group I transition metal compounds, iron compounds, cobalt compounds and nickel compounds and (4) 2-hydroxypyridines,
A method for producing a carbonate ester is characterized in that an alcohol is reacted with carbon monoxide and oxygen.

The present invention will be described in detail below. As the platinum group metal used in the present invention, ruthenium, rhodium, palladium, iridium, platinum and the like are used, with palladium being preferred. These metals are simple substances or halides, nitrates, sulfates, phosphates,
It can also be used as a salt such as a carboxylate. More specifically, ruthenium chloride, ruthenium iodide, tris (acetylacetonato) ruthenium, rhodium chloride, rhodium bromide, rhodium iodide, rhodium nitrate, rhodium sulfate, rhodium acetate, palladium chloride, palladium bromide, iodide Palladium, 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, a complex compound composed of a platinum group metal salt and 2-hydroxypyridines is a complex compound in which a nitrogen atom of 2-hydroxypyridines is coordinated to a platinum group metal, for example, bis (2-hydroxy). Pyridine) palladium chloride, bis (2-hydroxypyridine) palladium bromide, 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 and the like. As a general synthetic method of this complex,
For example, in the case of bis (2-hydroxypyridine) palladium chloride, it can be synthesized by dissolving palladium chloride and sodium chloride in methanol and then adding 2-hydroxypyridine.

The complex compound composed of a platinum group metal, copper and 2-hydroxypyridines is a complex of a platinum group metal and copper having 2-hydroxypyridine as a bridging ligand. It is a complex compound coordinated with a nitrogen atom of the same class. Specifically, in the following general formula

[0012]

[Chemical 2]

(X is an organic or inorganic anion, and Y is a charge.
Child-bearing ligand, R is hydrogen, alkyl group, alkoxy
Represents a group or halogen, respectively. ) Compound I satisfying n = 2, m = 2 and z = 0, n = 2,
Compound II satisfying m = 2 and z = 1, n = 3, m = 1?
Compound III satisfying z = 0, n = 3, m = 1 and z =
Compound IV satisfying 1 or n = 4, m = 0 and z = 0
Compound V to be filled. For example, compound I (n = 2,
m = 2 and z = 0), PdCuCl₂(C_Five H_Four
 NO)₂, PdCuBr₂(C_FiveH_FourNO)₂, Compound II
(N = 2, m = 2 and z = 1), PdCuBr
₂(C_FiveH_FourNO)₂(THF), PdCuCl₂(C_FiveH_Four
NO)₂(THF), PdCuCl₂(6-CH₃C_FiveH₃
NO)₂(EtOH), compound III (n = 3, m = 1 and
For z = 0, PdCuCl (C_FiveH_FourNO)₃,
As compound IV (n = 3, m = 1 and z = 1), Pd
CuCl (C_FiveH_FourNO)₃(MeOH), PdCuCl
(C_FiveH_FourNO)₃(EtOH), PdCuBr (C_FiveH_Four
NO)₃(EtOH), PdCuNO₃(C_FiveH_FourNO)₃
(EtOH), PdCuSO₃CF₃(C_FiveH_FourNO)
₃(EtOH), compound V (n = 4, m = 0 and z =
0) is PdCu (C_FiveH_FourNO)_FourIs mentioned.
These complexes include platinum group metals, copper and 2-hydroxypyrrole.
Zinc is added to the reaction solvent to produce a carbonate ester
Even if they are synthesized in the same room, these complex compounds can also be synthesized in advance.
After separating, add it to the reaction system for the production of carbonate
Either is fine. General synthetic methods for these complex compounds
For example, PdCuCl₂(C_FiveH_FourNO)
₂For (THF), bis (2-hydroxypyridyl
) Palladium chloride and copper acetate in THF at room temperature
It can be synthesized by adapting it. Also PdCuCl
₂(C_FiveH_FourNO)₂Is PdCuCl₂(C_FiveH_FourNO)
₂Obtained by heating (THF) to 120 ° C.
It PdCuCl (C_FiveH_FourNO)₃About (EtOH)
Bis (2-hydroxypyridine) palladium chloride
Lido, copper acetate and 2-hydroxypyridine in EtOH
It can be synthesized by reacting at room temperature. Also PdCu
Cl (C_FiveH_FourNO)₃Is PdCuCl (C_FiveH_FourNO)₃
Obtained by heating (EtOH) to 120 ° C.
It PdCu (C_FiveH_FourNO) _FourFor information about screws (2-
(Hydroxypyridine) palladium chloride and copper acetate and 2
-React hydroxypyridine in MeOH at 100 ° C.
It can be synthesized by

The amount of the platinum group metal or its salt, or the complex compound of the platinum group metal or its salt and 2-hydroxypyridine, or the complex compound of the platinum group metal, copper and 2-hydroxypyridine, is usually , Alcohol 1
0.01 to 100 mmo as platinum group metal per liter
It is used in the range of 1, preferably 0.1 to 100 mmol.

A complex consisting of a platinum group metal or a salt thereof and 2-hydroxypyridine or a complex containing copper therein, particularly Compounds I and II, can be made to have a higher activity, and Compounds III to V can provide halogen. Advantageously, the concentration can be reduced or eliminated. Among the copper salts or copper complex compounds used in the present invention, as the copper salt, cupric chloride, in addition to halides such as cuprous chloride,
Aliphatic carboxylates such as copper nitrate, copper sulfate, copper acetate, copper propionate and copper caproate, aromatic carboxylates such as copper benzoate, phosphates and the like are used.

The complex compound of copper may be any complex salt having an organic ligand, for example, a nitrogen atom, an oxygen atom, or a complex salt of an organic ligand having both a nitrogen atom and an oxygen atom is used. 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. . Examples of the organic ligand having an oxygen atom include N-oxides, β-diketones, salicylic acid derivatives, dicarboxylic acids and the like. Examples of the organic ligand having a nitrogen atom and an oxygen atom include hydroxypyridines, hydroxyquinolines, hydroxyanilines and the like. Among them, 2-hydroxypyridines, 2-methoxypyridines, 5-cyanopyridines, tetraalkyldiaminoalkanes and quinoxalines are preferable, and 2-hydroxypyridines are particularly preferable.

The amount of the copper salt or copper complex compound used is usually 1 to 10 ⁵ moles per 1 mole of the platinum group metal atom.
It is preferably used in the range of 1 to 10 ⁴ mol, particularly preferably 1 to 10 ³ mol. In the present invention, the acid and / or 2-hydroxypyridines to be described below are not necessarily present when a complex consisting of a platinum group metal or a salt thereof and 2-hydroxypyridine or a complex containing copper therein is used. However, it is preferable to be present from the viewpoint of stabilization and activity of the complex compound. Further, it is more effective to coexist an acid and 2-hydroxypyridines.

There are no particular restrictions on the type of acid used in the present invention, but it is not limited to the above. Aromatic carboxylic acids such as acids, paratoluene sulfonic acid, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and the like are used. These acids may be used alone as an acid, or may be added in the form of a salt such as an ammonium salt, a phosphonium salt or an onium salt described later. It is also possible to add the acid and salt at the same time. When the acid used is carboxylic acid, it may be used as a solvent. The acid is used in an amount of usually 0.01 to 300 mol, preferably 0.1 to 50 mol, per 1 mol of copper metal atom.

The ammonium salt, phosphonium salt and onium salt include ammonium acetate, cyclohexyl ammonium acetate, methyl ammonium acetate, dimethyl ammonium acetate, trimethyl ammonium acetate, ethyl ammonium acetate, diethyl ammonium acetate, triethyl ammonium acetate, tetraethyl ammonium acetate.
Tetrabutylammonium acetate, pyridium acetate, ammonium caproate, tetrabutylphosphonium acetate,
Tetraphenylphosphonium acetate, bistriphenylphosphiniminium acetate, ammonium chloride, cyclohexyl ammonium chloride, methyl ammonium chloride, dimethyl ammonium chloride, trimethyl ammonium chloride, ethyl ammonium chloride, diethyl ammonium chloride, triethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl chloride Ammonium, pyridinium chloride, ammonium iodide, tetrabutylphosphonium chloride, tetraphenylphosphonium chloride, bistriphenylphosphiniminium chloride and the like are used. It is preferable to use ammonium carboxylate such as ammonium acetate and ammonium caproate. The amount of the ammonium salt, phosphonium salt, or onium salt used is usually 0.01 to 300 mol, preferably 0.1 to 50 mol, per mol of the copper metal.

The 2-hydroxypyridines used in the present invention may have a substituent such as an alkyl group, an alkoxy group or a halogen atom, which does not inhibit the reaction, in the 2-hydroxypyridine skeleton. Includes 2-hydroxypyridine, 2-hydroxy-4-methylpyridine,
2-hydroxy-5-methylpyridine, 2-hydroxy-6-methylpyridine, 2-hydroxy-4-ethylpyridine, 2-hydroxy-4-methoxypyridine, 2-hydroxy-6-methoxypyridine, 4,6-dimethyl-2-hydroxypyridine, 2-hydroxy-4-chloropyridine, 2-hydroxy-6-chloropyridine, 5
-Cyano-2-hydroxypyridine is used. 2-hydroxypyridine and 2-hydroxy-6 are preferred.
It is preferable to use 2-hydroxyalkylpyridine such as -methylpyridine. The amount of the 2-hydroxypyridines used is usually 1 to 10 per 1 mol of the platinum group metal atom.
It is used in an amount of ⁴ mol, preferably 1 to 10 ³ mol.

As the cocatalyst in the present invention, lanthanoid compounds such as lanthanum, cerium and praseodymium,
Of group IV transition metal compounds such as titanium zirconia, group V transition metal compounds such as vanadium and niobium, group VI transition metal compounds such as chromium and molybdenum, group VII transition metal compounds such as manganese, iron compounds, cobalt compounds, nickel compounds Those having redox ability can be used without particular limitation, and among them, it is preferable to use a rare earth metal compound such as lanthanum, cerium, praseodymium, which has a high effect of suppressing the precipitation of 0-valent palladium. The types of cocatalyst salts are chloride, bromide, iodide and other halides, acetates, butanoates, benzoates and other carboxylates, nitrates, sulfates, hydroxides, oxides, etc. Can be used without. The amount used, usually platinum group metal per mole of 0.01 to 10 ⁴ moles, preferably used in the range of 0.1 to 1000 moles.

The alcohol is not limited to aliphatic or aromatic, but saturated aliphatic alcohol such as methanol or ethanol is advantageous in terms of reaction rate, and is usually used in excess also as a solvent. The solvent used in the production method of the present invention is usually an excessive amount of alcohol, but any solvent inert to the reaction can be used without particular limitation. Specifically, benzene, toluene, aromatic hydrocarbons such as xylene, chlorobenzene,
Halogenated aromatic hydrocarbons such as trichlorobenzene, aliphatic hydrocarbons such as octane and decane, tetrahydrofuran, ethers such as 1,4-dioxane, esters such as ethyl acetate and methyl benzoate, nitriles such as acetonitrile and benzonitrile, N Amides such as -methylpyrrolidone, N, N-dimethylacetamide and DMF, and urea such as tetramethylurea and ethylenedimethylurea can be used. It is preferable to use amides and ureas, which are highly effective in suppressing insolubilization of platinum group metals. Particularly preferably, N-methylpyrrolidone, DM
F, tetramethylurea.

In carrying out the present invention, the carbon monoxide partial pressure is 0.1 to 50 kg / cm ² , preferably 0.1.
The oxygen partial pressure is 0.1 to ² within the range of -30 kg / cm ² .
0 kg / cm ^2, preferably at the range of 0. 1~10kg / cm ^2. Carbon monoxide and oxygen may be pure ones, or may be diluted with a reaction-inert gas such as nitrogen, carbon dioxide, or argon before use. In particular, it is desirable to adjust the oxygen partial pressure so that the gas composition in the reaction system is out of the explosion range.

The reaction of the present invention is carried out within a temperature range of 20 to 200 ° C, preferably 50 to 150 ° C. The reaction is
It can be carried out by any of a batch system, a gas distribution system, and a gas-liquid distribution system. Further, from the reaction product liquid, after the catalyst and the like are separated and recovered, a carbonate ester can be produced and obtained by a commonly used operation such as distillation and extraction. Since the catalyst of the present invention is stable without deactivation and precipitation of the catalyst component due to the reaction, the liquid after the reaction is concentrated by distillation to remove the produced carbonic acid ester and water, and then the catalyst metal component is added. , And can be used for a new reaction without treatment such as regeneration operation.

[0025]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples.
The present invention will be described below, unless the gist thereof is exceeded.
It is not limited to the examples. The abbreviations used in the examples
Has the following meanings. TOF: 1 mol of palladium atom and 1 hour of reaction time
Number of moles of carbonic acid ester produced by ori (1 / h) CO selectivity:
Ratio (%) (Example 1) Internal volume 70 ml Hastelloy Micro Auto
Put a glass inner cylinder in the clave, and bis (2-hydro) there.
Xypyridine) palladium chloride 0.04 mmol,
Copper acetate 0.5 mmol, 2-hydroxypyridine 1.0
mmol, acetic acid 1 mmol, cerium acetate as co-catalyst
Add 0.1 ml and 10 ml of methanol to.
After fully replacing the inside of the autoclave with carbon monoxide,
5 kg / cm of carbon dioxide ²Introduced, then 3.8% by volume of acid
Nitrogen gas containing element 80kg / cm²Press fit. Magne
While stirring with a tick stirrer, raise the reaction temperature to 100 ° C.
Then, after reacting for 30 minutes, it was cooled to room temperature. Release the pressure
After that, the reaction gas and the reaction product solution are subjected to gas chromatography.
It was analyzed and quantified. In addition, solid precipitates are soluble in aqua regia
After solving, palladium and copper in the precipitate using ICP
Was quantified. The results are shown in Table 1.

Example 2 The same reaction as in Example 1 was carried out except that cerium nitrate was added as a cocatalyst instead of cerium acetate. The results are shown in Table 1. (Example 3) The same reaction as in Example 1 was performed except that cerium chloride was added as a cocatalyst instead of cerium acetate. The results are shown in Table 1. (Example 4) The same reaction as in Example 1 was carried out except that lanthanum chloride was added instead of cerium acetate as a co-catalyst. The results are shown in Table 1.

Example 5 The same reaction as in Example 1 was carried out except that lanthanum nitrate was added instead of cerium acetate as a co-catalyst. (Example 6) The same reaction as in Example 1 was carried out except that 0.5 mmol of chromium nitrate was added as a cocatalyst instead of cerium acetate. The results are shown in Table 1. (Example 7) The same reaction as in Example 1 was performed except that 0.1 mmol of cobalt nitrate was added as a cocatalyst instead of cerium acetate. The results are shown in Table 1. (Example 8) The same reaction as in Example 1 was performed except that 0.1 mmol of manganese nitrate was added as a cocatalyst instead of cerium acetate. The results are shown in Table 1. (Example 9) Palladium acetate as catalyst 0.04 mmo
The same reaction as in Example 1 was performed using 1, 1, copper acetate 0.5 mmol, 2-hydroxypyridine 1.0 mmol, acetic acid 1 mmol, and cerium acetate 0.25 mmol as a cocatalyst. The results are shown in Table 1.

(Example 10) An inner volume of 500 ml was put into a Hastelloy autoclave, and a glass inner cylinder was put therein, and bis (2-hydroxypyridine) palladium chloride 0.6
mmol, copper acetate 7.5 mmol, 2-hydroxypyridine 15 mmol, acetic acid 30 mmol, cerium acetate 1.5 mmol as a cocatalyst, and methanol 135 m.
1, 15 ml of N-methylpyrrolidone is charged and sealed.
Using nitrogen gas containing 4% by volume of oxygen, 30 kg / cm
After raising the pressure to ² , stirring (900 rpm) of the reactor was started. The temperature was raised to 80 ° C. while supplying nitrogen gas containing 4% by volume of oxygen at a rate of 50 l / h. Reactor temperature is 80
After reaching ℃, the supply rate of nitrogen gas containing 4% by volume of oxygen was increased to 200 l / h, and carbon monoxide was further added to 16 l / h.
The reaction was started by feeding at a rate of. The reaction was carried out for 2.5 hours. During this time, the reaction conditions were as follows: reaction temperature 80 ° C., reaction pressure 30 kg / cm 2, carbon monoxide supply rate 16 l / h, nitrogen gas supply rate 200 l containing 4% by volume of oxygen. / H was maintained. During the reaction, the reactor outlet gas was sampled every 30 minutes and analyzed by gas chromatography to quantify the by-product CO ₂ .
After the reaction, the reaction product liquid was extracted after cooling and releasing the pressure, and analyzed by gas chromatography using the internal standard method. The liquid after the reaction was uniformly green and no solid precipitate was observed. The production amount of dimethyl carbonate is 217 mmol,
The average TOF was 145 (1 / h). The average CO selectivity is 88% and the main by-product is carbon dioxide (29
mmol), and dimethyl oxalate was not found.

Example 11 144 ml of the reaction product solution obtained in Example 10 was used in a rotary evaporator.
It was distilled for 2 hours under the conditions of mmHg and 60 ° C. Almost all dimethyl carbonate, unreacted methanol and water were distilled off, and acetic acid was also partially distilled. The residual liquid was N with the catalyst component added as a solvent.
-Dissolved in methylpyrrolidone, no precipitate was observed. In the residual liquid, methanol (1
30 ml), acetic acid was added. Using this liquid, Example 1
According to the method of No. 0, the first recycling reaction was performed under the same conditions as in Example 10. As a result, the liquid after the reaction was uniformly green and no solid precipitate was observed. The amount of dimethyl carbonate produced was 199 mmol, and the average TOF was 138 (1 / h). The average CO selectivity was 86%, and 31 mmol of carbon dioxide was by-produced. Dimethyl oxalate was not found.

(Example 12) 143 ml of the reaction product solution obtained in Example 11 was taken, and the second recycling reaction was carried out in the same manner as in Example 11. As a result, the liquid after the reaction was uniformly green and no solid precipitate was observed. The production amount of dimethyl carbonate is 207 mmol, which is the average TOF.
Was 144 (1 / h). Average CO selectivity is 86%
And carbon dioxide produced 34 mmol as a by-product. Dimethyl oxalate was not found.

Example 13 141 ml of the reaction product solution obtained in Example 12 was taken and the third recycling reaction was carried out in the same manner as in Example 11. As a result, the liquid after the reaction was uniformly green and no solid precipitate was observed. The amount of dimethyl carbonate produced is 189 mmol, which is the average TOF.
Was 134 (1 / h). Average CO selectivity is 85%
And carbon dioxide produced 34 mmol as a by-product. Dimethyl oxalate was not found.

(Example 14) 140 ml of the reaction product solution obtained in Example 13 was taken and the fourth recycling reaction was carried out in the same manner as in Example 11. As a result, the liquid after the reaction was uniformly green and no solid precipitate was observed. The amount of dimethyl carbonate produced was 204 mmol, and the average TO
F was 146 (1 / h). Average CO selectivity is 86
%, And carbon dioxide produced 33 mmol of carbon dioxide. Dimethyl oxalate was not found.

Example 15 As a catalyst, 0.01 mmol of palladium acetate, 0.1 mmol of copper acetate, second chloride
Copper 0.15 mmol, cerium acetate 0.1 mmol, 2
-Hydroxypyridine 0.25 mmol, acetic acid 100 m
The same reaction as in Example 1 was performed except that mol was used. The amount of DMC produced was 8.50 mmol, and the CO selectivity was 90.2%. No precipitation of palladium or copper was observed after the reaction was completed.

Comparative Example 1 The same reaction as in Example 1 was carried out except that cerium acetate was not added as a cocatalyst. The results are shown in Table 1. (Comparative Example 2) Cerium acetate 0.5 mm instead of copper acetate
The same reaction as in Comparative Example 1 was performed except that ol was added. The results are shown in Table 1. (Comparative Example 3) The same reaction as in Example 9 was performed except that cerium acetate was not added as a cocatalyst. The results are shown in Table 1.

[0035]

[Table 1]

[0036]

INDUSTRIAL APPLICABILITY The present invention provides a method for efficiently producing a carbonic acid ester, and the carbonic acid ester obtained can be used for various purposes as a raw material for resins and pharmaceuticals and agricultural chemicals. Further, according to the present invention, it is industrially very important in that the precipitation and inactivation of the catalytic metal component can be suppressed and the carbonate ester can be stably and continuously produced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location // C07B 61/00 300 (72) Inventor Mamoru Shiraishi 1-chome, Ohama 1-chome, Amagasaki city, Hyogo Kansai heat Chemical Research Center

Claims (15)

[Claims] 1. (1) Platinum group metal or salt thereof, (2) Metal copper, copper salt or complex compound of copper, (3) Lanthanoid compound, Group IV transition metal compound, Group V transition metal compound, V
In the presence of at least one selected from the group consisting of a Group I transition metal compound, a Group VII transition metal compound, an iron compound, a cobalt compound and a nickel compound and (4) 2-hydroxypyridines, an alcohol is mixed with carbon monoxide and oxygen. A method for producing a carbonic acid ester, which comprises reacting. 2. (1) Platinum group metal or salt thereof, (2) Metal copper, copper salt or copper complex compound, (3) Lanthanoid compound, Group IV transition metal compound, Group V transition metal compound, V
At least one selected from the group consisting of Group I transition metal compounds, Group VII transition metal compounds, iron compounds, cobalt compounds and nickel compounds, (4) 2-hydroxypyridines and (5) acids, ammonium salts, phosphonium salts and oniums. A method for producing a carbonate ester, which comprises reacting an alcohol with carbon monoxide and oxygen in the presence of at least one selected from the group consisting of salts. 3. A complex compound comprising (1) a platinum group metal or a salt thereof and 2-hydroxypyridines, (2) copper metal,
Copper salt or copper complex compound and (3) lanthanoid compound, group IV transition metal compound, group V transition metal compound, V
Carbonic acid ester characterized by reacting alcohol with carbon monoxide and oxygen in the presence of at least one selected from the group consisting of Group I transition metal compounds, Group VII transition metal compounds, iron compounds, cobalt compounds and nickel compounds Manufacturing method. 4. A complex compound comprising (1) a platinum group metal or a salt thereof and 2-hydroxypyridines, (2) copper metal,
Copper salt or copper complex compound (3) Lanthanoid compound, I
At least one selected from the group consisting of Group V transition metal compounds, Group V transition metal compounds, Group VI transition metal compounds, Group VII transition metal compounds, iron compounds, cobalt compounds and nickel compounds; and (4) 2-hydroxypyridines, A method for producing a carbonate ester, which comprises reacting an alcohol with carbon monoxide and oxygen in the presence of at least one selected from the group consisting of an acid, an ammonium salt, a phosphonium salt and an onium salt. 5. (1) Complex compound of platinum group metal, copper and 2-hydroxypyridines, (2) metal copper, copper salt or copper complex compound and (3) lanthanoid compound, IV
An alcohol with carbon monoxide in the presence of at least one selected from the group consisting of a group transition metal compound, a group V transition metal compound, a group VI transition metal compound, a group VII transition metal compound, an iron compound, a cobalt compound and a nickel compound. A method for producing a carbonic acid ester, which comprises reacting with oxygen. 6. (1) Complex compound of platinum group metal, copper and 2-hydroxypyridine, (2) metal copper, copper salt or copper complex compound, (3) lanthanoid compound, group IV transition metal compound, V At least one selected from the group consisting of group transition metal compounds, group VI transition metal compounds, group VII transition metal compounds, iron compounds, cobalt compounds and nickel compounds, and (4) 2-hydroxypyridines,
A method for producing a carbonate ester, which comprises reacting an alcohol with carbon monoxide and oxygen in the presence of at least one selected from the group consisting of an acid, an ammonium salt, a phosphonium salt and an onium salt. 7. A complex compound of a platinum group metal, copper and 2-hydroxypyridine is represented by the following general formula: (X represents an organic or inorganic anion, Y represents an electron donor ligand, and R represents hydrogen, an alkyl group, an alkoxy group or halogen.) Compound I satisfying n = 2, m = 2 and z = 0 , N = 2,
Compound II satisfying m = 2 and z = 1, n = 3, Compound III satisfying m = 1 and z = 0, n = 3, m = 1 and z =
7. The method according to claim 5 or 6, which is compound IV satisfying 1 or compound V satisfying n = 4, m = 0 and z = 0. 8. The molar ratio of metallic copper, a copper salt or a copper complex compound to the platinum group metal is in the range of 1 to 1000.
The described method. 9. A lanthanoid compound, a group IV transition metal compound, a group V transition metal compound, a group VI transition metal compound, VI.
9. The method according to claim 1, wherein the molar ratio of at least one selected from the group consisting of Group I transition metal compounds, iron compounds, cobalt compounds and nickel compounds to the platinum group metal is in the range of 0.1 to 1000. 10. The method according to claim 1, wherein the temperature is maintained in the range of 20 to 200 ° C. 11. The method according to claim 1, wherein the oxygen partial pressure is 0.1 to 20 kg / cm ² . 12. The method according to claim 1, wherein the carbon monoxide partial pressure is 0.1 to 50 kg / cm ² . 13. The method according to claim 1, wherein the reaction is carried out in the presence of a nitrogen-containing solvent. 14. A catalyst component recovered by distilling or evaporating at least a part of the reaction product solution produced by the carbonic acid ester according to any one of claims 1 to 11 and 12 to distill a part or all of the carbonic acid ester, alcohol and water. Alternatively, a method for producing a carbonic acid ester, characterized in that a solution containing a catalyst component is recycled to the reaction system. 15. The method according to claim 13 or 14, wherein the nitrogen-containing solvent is selected from the group consisting of N-methylpyrrolidone, DMF and tetramethylurea.