JPH0827055A - Palladium-copper complex and production of carbonyl compound by using the same complex - Google Patents

Abstract

PURPOSE:To produce the subject new complex containing a hydroxypyridine as a cross-linking ligand and useful for high efficient and high selective synthesis of a carbonyl compound under a low halogen concentration condition or a halogen-free condition. CONSTITUTION:This is a palladium-copper complex of formula I to III [R is H, an alkyl, an alkoxy or a halogen; X is a univalent organic or inorganic anion; Y is an electron pair donating ligand; (n) is 0 or 1]. This palladium- copper complex of formula I can be synthesized, e.g. by reacting a complex between palladium or a palladium salt as palladium and a 2-hydroxypyridine with metallic copper or a copper salt compound preferably in an ether such as tetrahydrofuran as an electron pair donating ligand or a solvent at 20 to 120 deg.C. preferably 20 to 50 deg.C. In addition, if an olefin is reacted with oxygen, water or an alcohol in the presence of the above-mentioned palladium-copper complex, the corresponding carbonyl compound an be synthesized.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a palladium-copper complex having 2-hydroxypyridines as a bridging ligand, and a method for producing a carbonyl compound from an olefin using the complex as a catalyst.

[0002]

As a method for producing a carbonyl compound by reacting an olefin with water in the presence of oxygen, a method using palladium chloride and copper chloride in hydrochloric acid as a catalyst to convert ethylene to acetaldehyde, or The so-called Wacker method for producing acetone from propylene is widely industrialized. Oxidation reaction of olefins using palladium chloride and copper chloride is carried out under conditions of high halogen concentration. A high concentration of halogen causes corrosion of the reactor, which is a process disadvantage. Further, since there are many chlorinated by-products, there are problems such as low selectivity of the target compound. Therefore, it is important to develop a catalyst system that allows the reaction to be carried out efficiently in the presence of halogen at a concentration as low as possible.

[0003]

Means for Solving the Problems As a result of diligent studies on the method for producing a carbonyl compound from an olefin, oxygen and water or an alcohol, the present inventors have found a specific palladium-copper complex, and if the complex is used, High efficiency with low halogen concentration or no halogen,
The inventors have found that a carbonyl compound can be produced with high selectivity and have reached the present invention.

The above reaction is presumed to be due to the catalytic action of divalent palladium, and Pd is reduced to zero valent by the reaction. The mechanism of action has not been clarified so far, but in order to convert 0-valent palladium into divalent palladium by oxidation, an oxidizing agent for 0-valent palladium typified by copper and high-concentration halogen have been required. However, it is speculated that when the specific complex of the present invention is used, the cross-linking structure of palladium-copper and 2-hydroxypyridine promotes the oxidation of 0-valent palladium by copper.

That is, the gist of the present invention is: (1) Palladium-copper complexes represented by the above general formulas (I) to (III) (hereinafter sometimes referred to as compounds I to III, respectively). And (ii) oxygen and (ii) water or alcohol to produce the corresponding carbonyl compound.

The present invention will be described in detail below. Palladium-copper complex of the present invention (Compound I, Compound II, Compound II
Palladium used for producing I) may be used as a simple substance, a salt such as a halide, a nitrate, a phosphate or an acetate, or may be used as a complex compound with 2-hydroxypyridines described later. You can also More specific examples include palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium propionate, palladium caproate, palladium nitrate, and palladium phosphate.

Examples of complex compounds obtained by precoordinating 2-hydroxypyridines with palladium include, for example, bis (2-hydroxypyridine) 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, bis (2-hydroxy-4) -
Ethylpyridine) palladium chloride, bis (2-hydroxy-4-methoxypyridine) palladium chloride,
Bis (2-hydroxy-6-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.

For these complex compounds, a palladium metal compound and 2-hydroxypyridines are added to a reaction solvent and used as they are for the synthesis reaction of a palladium-copper complex.
The complex compound may be synthesized and isolated in advance and then used in the synthetic reaction of the palladium-copper complex. As a general synthetic method of this complex compound, it can be synthesized by dissolving palladium chloride and sodium chloride in methanol and then adding 2-hydroxypyridines.

The copper compound used to produce the palladium-copper complex of the present invention is metallic copper or a copper salt compound, and examples of the copper salt compound include cupric chloride, cuprous chloride and dibromide. In addition to halides such as copper, aliphatic carboxylates such as copper nitrate, copper sulfate, copper acetate, copper propionate, and copper caproate, aromatic carboxylates such as copper benzoate, and phosphates are used. . Preference is given to copper carboxylates having up to 12 carbon atoms per molecule, for example copper acetate being used.

The 2-hydroxypyridines used for producing the palladium-copper complex of the present invention include:
-Hydroxypyridine skeleton may have a substituent which does not inhibit this reaction, for example, an alkyl group, an alkoxy group,
Examples thereof include 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-6-methoxypyridine, 4,6-dimethyl-2-hydroxypyridine, 2-
Hydroxy-4-chloropyridine, 2-hydroxy-
6-chloropyridine or the like is used. Further, salts such as alkali metal salts of these compounds can be similarly used.

The electron pair donor ligand is a ligand having a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, or a nitrogen atom and an oxygen atom. Examples of the ligand having an oxygen atom include alcohols such as methanol, ethanol, phenol and cresol, ketones such as acetone and ethylmethylketone, ethylacetate and methylacetate. And esters such as acetaldehyde, ethers such as tetrahydrofuran and diethyl ether, but are not limited thereto. As the ligand having a nitrogen atom, nitriles such as acetonitrile, pyridines such as pyridine, dimethylpyridine, and methylpyridine, and as the ligand containing an oxygen atom and a nitrogen atom, dimethylformamide, N-methylformamide, N Examples include, but are not limited to, amides such as methylpyrrolidone, dimethylurea and tetramethylurea. 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, hexamethylphosphoramide and hexa Examples include, but are not limited to, amides such as methylphosphorus triamide. Examples of the ligand having a sulfur atom include, but are not limited to, thiophenes such as thiophene and ethylthiophene, dimethyl sulfoxide, tetramethylene sulfone, dimethyl sulfide, carbon disulfide and the like. These are used as electron pair donor ligands, but also as solvents for preparing the palladium-copper complex compound I, compound II, and compound III.

As the solvent, the electron pair donor ligand or the electron pair donor ligand and a non-coordinating solvent may be used. Examples of the non-coordinating solvent include aliphatic hydrocarbons such as hexane, heptane, cyclohexane and decalin, aromatic hydrocarbons such as toluene, halides such as chloroform, dichloromethane and carbon tetrachloride. The solvent is used in an amount of 1 liter per 0.1 to 1000 mmol of palladium salt, preferably 1 liter per 1 to 100 mmol of palladium salt.

Examples of monovalent organic or inorganic anions include 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 in the starting palladium compound for synthesizing the palladium-copper complex. It can also be introduced into the palladium-copper complex by exchanging the anions of the palladium-copper complex compounds I and II with other anions. For example, it is possible to synthesize complexes having various anions by reacting a palladium-copper complex compound II having chlorine as an anion with a silver salt having another anion to cause anion exchange.

The estimated production formulas of the palladium-copper complexes (Compound I, Compound II, Compound III) are shown below.

[0015]

Embedded image PdX ₂ + 2 (2-PyOH) ← ――― → PdX ₂ (2-PyOH) ₂ formula PdX ₂ (2-PyOH) ₂ + CuZ ₂ ← ――― → PdCuX ₂ (2-PyO) ₂ + 2ZH formula compound I PdCuX ₂ (2-PyO) ₂ + 2-PyOH ← ――― → PdCuX (2-PyO) ₃ + XH formula compound II PdCuX (2-PyO) ₃ + 2-PyOH ← ―――― → PdCu (2-PyO) ₄ + XH formula Compound III 2-PyOH represents 2-hydroxypyridine. X and Z represent an inorganic or organic anion such as halogen, nitric acid and carboxylic acid.

The compound I can be synthesized, for example, as follows. As the palladium, a palladium salt or a complex compound of palladium and 2-hydroxypyridines is used. When a palladium salt is used, copper is added in an amount of 0.01 to 10 with respect to 1 equivalent of the palladium salt.
An equivalent amount, preferably 1 to 2 equivalents, is used, and 2-hydroxypyridines are used in 0.01 to 20 equivalents, preferably 2 to 3 equivalents. When a complex compound of palladium and 2-hydroxypyridines is used, 0.01 to 10 equivalents of copper, preferably 1 to 2 are added to 1 equivalent of the palladium compound.
It is used in an equivalent amount and 2-hydroxypyridines are used in an amount of 0 to 20 equivalents, preferably 0 to 1 equivalents. Examples of the electron pair donating ligand or solvent include ether such as tetrahydrofuran.
Tellers are preferred. When an electron-donating ligand or solvent other than ethers such as alcohols is used, 2-hydroxypyridines having a substituent at the 6-position are preferably used. The reaction is 20-120
It is carried out at a temperature of C, preferably at a temperature of 20 to 50C. The reaction pressure is not particularly limited as long as it is a pressure sufficient to keep the reaction solution in a liquid state. Atmospheric pressure is usually used for ease of operation. The reaction atmosphere may be an inert gas such as nitrogen or argon, or a gas containing oxygen such as air. The reaction product can be easily separated by appropriately removing the solvent from the solution after the reaction by distillation or the like. It is also possible to obtain a solid precipitate by adding a nonpolar solvent such as pentane or hexane to the solution after the reaction. Furthermore, by using an electron pair donating ligand and a nonpolar solvent such as pentane or hexane as a reaction solvent, the produced complex can be precipitated as a precipitate. The product thus isolated is usually obtained as a complex in which an electron pair donating ligand is coordinated (compound I, n = 1). When this is heated and the electron pair donating ligand is eliminated, compound I (n =
0) is obtained. The heating temperature is 50 to 200 ° C,
80-120 degreeC is used preferably.

The compound II can be synthesized, for example, as follows. As the palladium, a palladium salt or a complex compound of palladium and 2-hydroxypyridines is used. When a palladium salt is used, copper is added in an amount of 0.01 to 10 with respect to 1 equivalent of the palladium salt.
An equivalent amount, preferably 1-2 equivalents, is used, and 2-hydroxypyridines are used in 0.01-30 equivalents, preferably 3-4 equivalents. When a complex compound of palladium and 2-hydroxypyridines is used, 0.01 to 10 equivalents of copper, preferably 1 to 2 are added to 1 equivalent of the palladium compound.
It is used in an equivalent amount and 2-hydroxypyridines are used in an amount of 0 to 30 equivalents, preferably 1 to 2 equivalents. It is preferable to use alcohols as the electron pair donating ligand or solvent. The reaction is carried out at a temperature of 20 to 120 ° C, preferably 20 to 50 ° C. The reaction pressure is not particularly limited as long as it is a pressure sufficient to keep the reaction solution in a liquid state. Atmospheric pressure is usually used for ease of operation. The reaction atmosphere may be an inert gas such as nitrogen or argon, or a gas containing oxygen such as air. The reaction product can be easily separated by appropriately removing the solvent from the solution after the reaction by distillation or the like.
It is also possible to obtain a solid precipitate by adding a nonpolar solvent such as pentane or hexane to the solution after the reaction. Furthermore, by using an electron pair donating ligand and a nonpolar solvent such as pentane or hexane as a reaction solvent, the produced complex can be precipitated as a precipitate. The product thus isolated is usually obtained as a complex in which an electron pair donating ligand is coordinated (compound II, n = 1). When this is heated and the electron pair donating ligand is eliminated, compound II (n = 0) is obtained. The heating temperature is 50 to 200 ° C., preferably 80 to 120
C is used.

The compound III can be synthesized, for example, as follows. As the palladium, a palladium salt or a complex compound of palladium and 2-hydroxypyridines is used. When a palladium salt is used, copper is added in an amount of 0.01 to 5 with respect to 1 equivalent of the palladium salt.
0 equivalents, preferably 1 to 25 equivalents, and 2-hydroxypyridines are used in 0.01 to 100 equivalents, preferably 10
Use ~ 50 equivalents. When a complex compound of palladium and 2-hydroxypyridine is used, 0.01 to 10 equivalents, preferably 1 to 2 equivalents of copper are used for 1 equivalent of the palladium compound, and 2-hydroxypyridines are used. 0
~ 100 equivalents, preferably 10-50 equivalents are used. The reaction is carried out at a temperature of 20 to 200 ° C., preferably 80 to 1
It is carried out at a temperature of 20 ° C. There is no particular limitation on the reaction pressure,
The pressure may be sufficient to keep the reaction solution liquid. The reaction atmosphere is under an inert gas such as nitrogen or argon,
It may be under a gas containing oxygen such as air. The reaction product can be easily separated by filtering the precipitate of the compound III produced after the reaction, or by appropriately removing the solvent from the solution after the reaction by distillation or the like. It is also possible to obtain a solid precipitate by adding a nonpolar solvent such as pentane or hexane to the solution after the reaction. Furthermore, by using an electron pair donating ligand and a nonpolar solvent such as pentane or hexane as a reaction solvent, the produced complex can be precipitated as a precipitate.

The palladium-copper complex of the present invention can be used for oxidative carbonylation reaction, hydroformylation reaction, hydroesterification reaction and the like, and is particularly suitable for olefin oxidation reaction. The type of olefin of the substrate used for the oxidation reaction may be an optionally substituted alkene having 2 to 20 carbon atoms per molecule, or 3 to 20 carbon atoms per molecule, optionally It is a substituted cycloalkene. The carbon-carbon double bond is not limited to one monoolefin, but two diolefins are also included, but a monoolefin having 2 to 12 carbon atoms, particularly a linear monoolefin, is preferable. For example, ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-
Pentene, 1-hexene, 2-hexene, 1-octene, 2-octene, styrene, cyclopentene, cyclohexene and the like. These compounds can also be used as a mixture.

Palladium-copper complexes are compound I, compound
The solution after preparation of II and compound III can be used as it is for the oxidation reaction of olefin, or the compound I, compound II and compound III can be isolated from the solution after preparation and used. When the compound I, the compound II, and the compound III are used after being isolated from the prepared solution, they can be used without further purification or can be used after purification. For the purification of Compound I, Compound II and Compound III, there is a method of washing the produced solid with a non-polar organic solvent such as toluene. As the washing solvent, pentane, hexane, cyclohexane, aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as toluene and mixtures thereof are used, but pentane and hexane are preferably used because they are easily removed after purification. To be

The amount of the palladium-copper complex used in the olefin oxidation reaction is 0.
01-100 mmol, preferably 0.1-100 mmo
Used in the l range. Further, the palladium-copper complex of the present invention is supported on a carrier such as activated carbon, graffiti, alumina, silica, silica-alumina, diatomaceous earth, asbestos, ion exchange resin, calcium silicate, aluminosilicate, polyvinyl pyridine, magnesia, titania, zirconia. It can also be used in the reaction described below. The method of loading on a carrier may be a commonly used method, for example, compounds I 1, I 2
A method in which I and III are dissolved in an organic solvent and a carrier is added thereto, impregnated, dried and supported, or a palladium compound and a copper compound are first supported on the carrier, and then 2-hydroxypyridines and the like are sequentially supported. The method of doing is adopted.
The amount of the palladium-copper complex supported on the carrier is usually 0.01 to 20% by weight as palladium or copper metal, and more preferably 0.1 to 10% by weight.

When carrying out the oxidation reaction of olefins using the palladium-copper complex of the present invention, the partial pressure of oxygen is usually 0.1 to 100 kg / cm ² , preferably 0.1 to 100 kg / cm ² .
It is performed in the range of 50 kg / cm ² . Oxygen may be pure, but for safety reasons, it may be diluted with an inert gas such as nitrogen or argon before use. In particular, the oxygen partial pressure is preferably adjusted so that the gas composition in the reaction system is out of the explosion range.

The oxidation reaction of the olefin of the present invention is 30 to 2
3 within the temperature range of 00 ° C, preferably 60-150 ° C
It is performed for 0 minutes to 10 hours. The palladium-copper complex of the present invention can be used alone, or can be used in the reaction in combination with any acid. As the acid, carboxylic acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, toluenesulfonic acid,
Trifluoroacetic acid, heteropoly acid or the like is used.
Specific examples of the carboxylic acid include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, pivalic acid and monochloroacetic acid, and aromatic carboxylic acids such as benzoic acid. Particularly, p-toluenesulfonic acid is preferable. The amount used varies depending on the type of the acid used, but normally, an equivalent amount to 100 equivalents relative to the catalyst metal is used.

As the cocatalyst, copper, iron, vanadium,
A compound of a metal selected from the group consisting of cobalt and / or manganese is used. These metals are preferably
It is used in the form of salts such as nitrates, sulphates, carboxylates (preferably carboxylates having up to 12 carbon atoms per molecule), perchlorates and sulphonates. A cupric compound is particularly preferable. Specific examples thereof include copper acetate, copper propionate, copper caproate, and copper carboxylates such as benzoic acid. The amount of promoter used is palladium
-Used in the range of 1 to 10 ⁵ equivalents, preferably 1 to 10 ³ equivalents, relative to the metal amount of the copper complex.

The palladium-copper catalyst of the present invention can be easily separated from the product by distillation of the product solution and repeatedly used. Further, by using a solvent having a boiling point higher than that of the carbonyl compound produced by the olefin oxidation reaction, it is possible to easily separate the mixture of the catalyst and the solvent and the product by reactive distillation. Further, the catalyst can be repeatedly used by continuously supplying the olefin as the substrate.

Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, T in the examples
OF is 1 mol of palladium and the number of moles of 2-octanone produced per 1 hour of reaction (mol / mol Pd / h
r).

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples unless the gist thereof is exceeded. Example 1 Synthesis of Compound I (n = 1) All reaction operations were performed in air. After dissolving palladium chloride and sodium chloride in methanol, 6-methyl-
1.7 mmol of copper acetate equivalent to 1.7 mmol of bis (6-methyl-2-hydroxypyridine) palladium chloride synthesized by adding 2-hydroxypyridine was added to 100 ml of ethanol. After stirring at room temperature for 20 minutes, the obtained homogeneous solution was filtered, and the solvent ethanol was removed in vacuo until the reaction solution reached 10 ml. The precipitated brown powder was separated, washed with ethanol and hexane, and dried. Yield 0.23 mg, yield about 27% based on charged Pd metal, composition formula: PdCuCl ₂ (C ₆ H ₆ NO) ₂ · C ₂ H ₅ OH elemental analysis value (%); Pd 22.5, Cu 12.0 , C 32.5, H 3.32, N 5.62, CL 14.32, theoretical value (%); Pd 21.14, Cu 12.63, C 33.39, H 3.58, N 5. 56, CL 14.11

Example 2 Synthesis of Compound I (n = 1) All reaction operations were carried out in air. After dissolving palladium chloride and sodium chloride in methanol, 1.7 mmol of bis (2-hydroxypyridine) palladium chloride synthesized by adding 2-hydroxypyridine and an equivalent amount of copper acetate were added to 100 ml of tetrahydrofuran. After stirring at room temperature for 20 minutes, the obtained homogeneous solution was filtered, and the solvent was removed in vacuo until the reaction solution became 10 ml. The precipitated brown powder was separated, washed with ethanol and hexane, and dried. Yield 0.30mg, Pd charge
Yield about 35% based on metal, composition formula; PdCuCl ₂ (C ₅ H ₄ NO) ₂ · C ₄ H ₈ O elemental analysis value (%); Pd 22.5, Cu 12.0, C 33.07, H 3.13, N 5.61, CL 13.95, theoretical value (%); Pd 21.23, Cu 12.68, C 33.52, H 3.19, N 5.59, CL 14.17.

Example 3 Synthesis of Compound II (n = 1) All reaction operations were carried out in air. After dissolving palladium chloride and sodium chloride in methanol, 0.5 mmol of bis (2-hydroxypyridine) palladium chloride synthesized by adding 2-hydroxypyridine and an equivalent amount of copper acetate were dissolved in 100 ml of ethanol.
Stir at room temperature for 20 minutes to dissolve uniformly, filter, and then 2
-0.5 mmol of hydroxypyridine was added and the reaction was left overnight. The precipitated brown crystals were separated, washed with ethanol and hexane, and dried. Yield 190mg
, Yield about 71% based on charged Pd metal, composition formula; PdCuCl (C ₅ H ₄ NO) ₃ · C ₂ H ₅ OH elemental analysis value (%); Pd 20.1, Cu 12.0, C 37.5 , H 3.10, N 7.88, CL 6.68, theoretical value (%); Pd 19.93, Cu 11.91, C 38.22, H 3.37, N 7.87, CL 6. 65

Example 4 Synthesis of Compound III 10 mmol of 2-hydroxypyridine, 0.4 mmol of bis (2-hydroxypyridine) palladium chloride, 5.0 mmol of copper acetate in a 300 cc autoclave.
1 and 100 ml of methanol are added. After thoroughly replacing the inside of the autoclave with nitrogen, nitrogen gas is 50 kg / cm
2 press fit. The reaction temperature was raised to 100 ° C. and the mixture was stirred for 2.5 hours. After completion of the reaction, the reactor was cooled, the precipitate was collected, and washed with methanol and hexane. Yield 0.155 g, yield 71% based on charged Pd, composition formula: PdCu (C ₅ H ₄ NO) ₄ elemental analysis value (%); Pd 19.38, Cu 10.89, C 43.58, H 2 .98, N 9.99, theoretical value (%); Pd 19.47, Cu 11.63, C 43.93, H 2.93, N 10.25.

Example 7 Hastelloy C with an internal volume of 70 ml
A glass inner cylinder was placed in a micro-autoclave, and 0.04 of the compound I (n = 1) obtained in Example 1 was placed therein.
mmol, N-methyl-2-pyrrolidone 10 ml, water 0.5 ml, and 1-octene 0.8 ml are added. After sufficiently replacing the inside of the autoclave with nitrogen, a nitrogen gas containing 3.8% by volume of oxygen is introduced under a pressure of 80 kg / cm ² . The reaction temperature was set to 80 ° C., the reaction was carried out for 1 hour, and then the mixture was cooled to room temperature. After releasing the pressure, the reaction product solution was analyzed by gas chromatography. Products other than 2-octanone were in trace amounts. TOF is 12 mmol / mol Pd / hr
Met.

Example 8 Compound I obtained in Example 2
Example 7 except that 0.04 mmol of (n = 1) was used.
When the reaction was performed in the same manner as above, TOF was 37 mmol.
It was / molPd / hr.

Example 9 Compound II obtained in Example 3
When the reaction was performed in the same manner as in Example 7 except that 0.04 mmol was used, TOF was 10 mmol / molP.
It was d / hr.

(Example 10) When 0.1 mmol of p-toluenesulfonic acid was added and the reaction was carried out for 0.5 h in the same manner as in Example 9, TOF was 44 mmol / molP.
It was d / hr.

Example 11 A reaction was performed in the same manner as in Example 7 except that 1.0 mmol of p-toluenesulfonic acid and 0.04 mmol of Compound III were used, and TO
F was 33 mmol / mol Pd / hr.

(Example 12) Bis (2-hydroxypyridine) palladium chloride and copper acetate were added to 0.04 mm.
When the reaction was performed in the same manner as in Example 7 except that ol was used, the TOF was 37 mmol / mol Pd / hr.

Example 13 A reaction was performed in the same manner as in Example 7 except that 0.1 mmol of p-toluenesulfonic acid, 0.04 mmol of bis (2-hydroxypyridine) palladium chloride and copper acetate were used. TO
F was 56 mmol / mol Pd / hr.

Comparative Example 1 Instead of using a palladium-copper complex, palladium chloride 0.04 mmol, copper chloride 0.0
The reaction was carried out in the same manner as in Example 7 using 4 mmol.
As a result, TOF was 38 mmol / mol Pd / hr.

(Comparative Example 2) The reaction was performed in the same manner as in Comparative Example 1 except that 0.1 mmol of p-toluenesulfonic acid was added, and TOF was 42 mmol / molPd /.
It was hr.

[0040]

INDUSTRIAL APPLICABILITY The present invention provides a novel palladium-copper complex and a method for efficiently oxidizing an olefin using the palladium-copper complex to produce a carbonyl compound.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junichi Yasumaru 1-chome, 1-chome, Ohamacho, Amagasaki City, Hyogo Prefecture Kansai Thermochemical Co., Ltd.

Claims (9)

[Claims] 1. A general formula: The palladium-copper complex represented by. (In the formula, R represents hydrogen or a substituent selected from the group consisting of an alkyl group, an alkoxy group, and a halogen atom, X represents a monovalent organic or inorganic anion, and Y represents an electron pair donor ligand. ,
n represents 0 or 1. ) 2. A general formula: The palladium-copper complex represented by. (In the formula, R represents hydrogen or a substituent selected from the group consisting of an alkyl group, an alkoxy group, and a halogen atom, X represents a monovalent organic or inorganic anion, and Y represents an electron pair donor ligand. ,
n represents 0 or 1. ) 3. A general formula: The palladium-copper complex represented by. (In the formula, R represents hydrogen or a substituent selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom). 4. Palladium according to claim 1
In the presence of the copper complex, the olefin is converted into (i) oxygen and (i)
i) A method of producing a corresponding carbonyl compound by reacting with water or alcohol. 5. Palladium-according to any one of claims 1 to 3.
A method for producing a corresponding carbonyl compound by reacting an olefin with (i) oxygen and (ii) water or alcohol in the presence of a copper complex and an acid. 6. The method according to claim 4, wherein a compound of a metal selected from the group consisting of copper, iron, vanadium, cobalt and manganese is present as a cocatalyst. 7. The molar ratio of cocatalyst to palladium-copper complex is 1.
7. The method of claim 6, wherein the method is ˜1000. 8. The method according to claim 4, wherein the temperature is maintained in the range of 20 to 200 ° C. 9. The method according to claim 4, which is carried out at an oxygen partial pressure of 0.1 to 50 kg / cm ² .