JPH0153261B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing aldehydes by hydroformylating olefinic compounds in the presence of a platinum-based complex catalyst. Several proposals have already been made regarding the use of platinum complexes as catalysts in methods for hydroformylating olefins. For example, a method using a catalyst consisting of a platinum() dihalide complex stabilized by a ligand and a Group B metal halide (Japanese Patent Application Laid-Open No. 1989-1999-
20112), a method using a catalyst consisting of a divalent or tetravalent platinum compound, a ligand such as phosphine, and a metal halide of group B of the periodic table (Japanese Patent Application Laid-Open No. 1983-1999)
50102, 53-65810), a method using a platinum catalyst, a metal halide of group B of the periodic table, and a bidentate ligand (Japanese Patent Laid-Open No. 119407, 1983, 55-100331). Table B Group metal halides include tin () halides, especially tin () chloride
It is known that the best results are obtained when using However, in the hydroformylation reaction of olefins using a platinum-based complex catalyst, olefin isomerization products, low-boiling by-products such as paraffin produced by hydrogenation of olefins, and condensation of reaction products aldehydes, etc. There is a disadvantage that a relatively large amount of high-boiling by-products are produced, and this tendency is remarkable when a metal halide of group B of the periodic table, such as tin chloride, is used in excess of platinum. If the amount of tin chloride (2) used is small, the induction period of the hydroformylation reaction (the time required from when the reaction system is placed under the reaction conditions until the reaction starts) becomes longer, which is a drawback. The present inventors conducted various studies in order to develop a catalyst system with high aldehyde selectivity and no induction period in the hydroformylation reaction of olefinic compounds using a platinum-based complex catalyst. Ligand compounds containing group B elements in the table and general formula Ar ₃ SnX (wherein, Ar represents an aryl group, X is hydrogen,
Represents a hydroxyl group or an acyloxy group. )
A catalyst consisting of a triaryltin compound represented by the formula, and in which the triaryltin compound is present in a ratio of 0.05 to 1 mole per mole of platinum in the platinum compound, is an excellent hydroformylation catalyst. This is what we discovered and arrived at the present invention. The present invention will be explained in detail below. The catalyst used in the hydroformylation reaction of the present invention is a catalyst consisting of a platinum compound, a ligand compound containing an element from group B of the periodic table, and the above-described specific aryltin compound. Zero-valent, divalent and tetravalent platinum compounds can be used as the platinum compound, but considering the stability of the platinum complex in the hydroformylation reaction system, divalent or tetravalent platinum containing a halogen can be used. Compounds are preferred. The platinum compound, the ligand compound containing the Group B element of the periodic table, and the aryltin compound can be separately charged into the reaction system, but the ligand compound containing the Group B element of the periodic table or the aryltin compound can be charged separately. A platinum complex to be used as a ligand can also be prepared in advance and then charged into the reaction system. Platinum compounds that can be used in the method of the present invention include:
Platinum halides such as platinum dichloride and platinum tetrachloride, halogenoplatinic acids such as hexachloroplatinic acid, sodium hexachloroplatinate, potassium hexachloroplatinate, potassium hexabromoplatinate, tetrachloroplatinic acid, potassium tetrachloroplatinate, and their salts , dichloro(1,5-cyclootadiene)platinum(), dichlorobis(benzonitrile)platinum(), dichlorobis(acetonitrile)platinum(), dichlorobis(pyridine)platinum(), dichlorobis(triphenylphosphine)platinum() , dichlorobis(tributylphosphine)platinum(), dichloro[2,3-o-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane]platinum() (hereinafter referred to as PtCl ₂ (DIOP)), dichloro[1,2-bis(diphenylphosphinomethyl)]
Cyclobutane] platinum ()

[Formula] (hereinafter referred to as PtCl ₂ (DPCB)), PtCl[Sn(C ₆ H ₅ ) ₃ ] (P
Examples include platinum complexes such as (C ₆ H ₅ ) ₃ ] ₂ . The amount of these platinum compounds used is calculated as platinum alone.
The amount is 0.0005 to 50 mmol, preferably 0.01 to 10 mmol per mole of olefin. A ligand compound containing a Group B element of the periodic table has the general formula AR ⁴ R ⁵ R ⁶ (wherein A represents phosphorus, arsenic, antimony, bismuth or nitrogen, and R ⁴ represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group or -B-A'R ⁵ R ⁶ (However, B is an alkylene group or arylene group which may have a substituent, an alkylene group or an oxygen atom) represents an alkylene group, cycloalkylene group, arylene group or bicycloalkylene group bonded to A or A' through
Represents arsenic, antimony, bismuth or nitrogen. ), and R ⁵ and R ⁶ represent an alkyl group, an acroalkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group. ) monodentate or bidentate ligands are used. Specifically, monodentate ligands include triphenylphosphine, tritolylphosphine, tris(chlorophenyl)phosphine, tris(methoxyphenyl)phosphine, benzyldiphenylphosphine, bis(2-cyanoethyl)phenylphosphine, Tertiary phosphine such as tricyclohexylphosphine, diethyl phenyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, trinaphthyl phosphine, tribenzyl phosphine, diphenylene phenyl phosphine, triethyl phosphine, etc. tertiary phosphites such as phosphite, tripropyl phosphite, tributyl phosphite, tridecyl phosphite, triphenyl phosphite, and tris(chlorophenyl) phosphite; tertiary arsines such as triphenyl arsine, tritolylarsine, and triethyl arsine; Examples of bidentate ligands include tertiary stibines such as tributylstibine and triphenylstibine, tertiary bismuthins such as triphenylbismuthin, and tertiary amines such as tributylamine and triphenylamine. 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphine) Pentane, 1-(diphenylphosphino)-2-(diphenylarsino)ethane, 1,2-bis(diphenylarsino)ethane, o-phenylenebis(dimethylarsine),
o-phenylene bis(diphenylphosphine),
1,2-bis(diphenylphosphinomethyl)benzene, 2,2'-bis(diphenylphosphinomethyl)-1,1'-binaphthyl, 2,2'-bis(diphenylphosphinooxy)-1 , 1'-binaphthyl, 1,2-bis(diphenylphosphinomethyl)cyclohexane, 1,2-bis(diphenylphosphinomethyl)cyclobutane, 1,2-bis(diphenylarsinomethyl)cyclobutane, 2,
3-o-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, trans-2,3-bis(diphenylphosphinomethyl)bicyclo[2,2,2]octane, etc. can be mentioned. These ligand compounds are preferably used in an amount of 1 to 10 times the mole of platinum in terms of Group B elements of the periodic table. As the aryltin compound, (C ₆ H ₅ ) ₃ SnH,
(C ₆ H ₅ ) ₃ SnOH, (C ₆ H ₅ ) ₃ SnOCOCH ₃ ,
(C ₆ H ₅ ) ₃ SnOCOC ₆ H ₅ and other general formulas Ar ₃ SnX (wherein, Ar represents an aryl group, X is hydrogen,
Represents a hydroxyl group or an acyloxy group. )
A triaryltin compound represented by is used. The aryltin compound can be used in an amount exceeding equimolar to platinum, but in general, excessive use of the aryltin compound causes undesirable effects such as a decrease in reaction rate and a decrease in aldehyde yield. A major feature of the method of the present invention is that the reaction can be carried out with virtually no induction period when the aryltin compound is used in an amount equal to or less than the equimolar amount relative to platinum. te 0.05
~1 mol is used. The olefinic compound used as a reaction raw material in the method of the present invention is an organic compound having an olefinic double bond in its molecule, and specifically includes ethylene, propylene, butene-1, butene-1, and butene-1.
2, isobutene, pentene-2, hexene-1,
hexene-2, octene-1, dodecene-1, cyclohexene, styrene, α-methylstyrene,
Examples include olefinic hydrocarbons having 2 to 20 carbon atoms such as butadiene, isobrene, and 1,7-octadiene, and olefinic compounds having functional groups such as acrylonitrile, allyl alcohol, vinyl acetate, methyl acrylate, and methyl methacrylate. It will be done. In carrying out the reaction, although it is not essential to use a reaction solvent, the reaction is usually carried out in the presence of a solvent inert to the hydroformylation reaction. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic saturated hydrocarbons such as hexane, isooctane, and decane, alicyclic saturated hydrocarbons such as cyclohexane, acetone, diethyl ketone, and ethyl methyl ketone. , ketones such as cyclohexanone, ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, o-dichlorobenzene, nitriles such as acetonitrile and benzonitrile, esters such as ethyl acetate and methyl propionate, ethanol , alcohols such as butanol, organic acids such as acetic acid and propionic acid, and aldehydes such as propionaldehyde, butyraldehyde, and valeraldehyde. When carrying out a reaction using a solvent, a process is usually adopted in which the reaction liquid flowing out of the reaction zone is distilled, the generated aldehyde fraction is distilled off, and the solvent in which the catalyst components are dissolved is circulated to the reaction zone. However, to enable this process it is necessary to use a solvent with a higher boiling point than the aldehyde produced by the hydroformylation reaction. For example, when carrying out a hydroformylation reaction of propylene, toluene, xylene,
The use of solvents such as diethyl ketone and cyclohexanone is recommended. In carrying out the method of the present invention, the reaction temperature is selected within the range of room temperature to 200°C, preferably 50 to 150°C, and the reaction pressure is selected within the range of normal pressure to 300 atm, preferably 5 to 150°C.
Selected within the range of 200 atm. The _H2 /CO molar ratio of the mixed gas of carbon monoxide and hydrogen is selected within the range of 0.1-10, preferably 0.3-3. The present invention will be explained in more detail below using examples. Examples 1 to 5, Comparative Examples 1 and 2 A predetermined amount of catalyst (listed in Table 1) and 50 ml of toluene were charged into a stainless steel vertically stirred autoclave with an internal volume of 200 ml, and then the inside of the autoclave was heated with nitrogen. Replacement (30Kg/ ^cm2
G×3 times) and 10.5 g of propylene was charged. Then, synthesis gas (H ₂ /CO molar ratio 1.0) was added under stirring.
The autoclave was pressurized to 70 to 75 kg/cm ² G, and the temperature of the autoclave was raised to 100° C. over a period of 25 minutes. At this time, the autoclave internal pressure was 90 to 95 Kg/cm ² G, so
Synthesis gas is injected from a pressure accumulator with an internal volume of 200ml through a constant pressure device, and the internal pressure of the autoclave is 100Kg/cm ² from beginning to end.
The pressure drop in the pressure accumulator was recorded on an automatic recorder to track the progress of the reaction. For convenience, the time when the internal pressure of the autoclave is increased to 100 kg/cm ² G is defined as the start of the reaction, the time required for the pressure to drop in the pressure accumulator to occur is defined as the induction period, and the time when no pressure drop is observed is defined as the end of the reaction. did. After the reaction was completed, the autoclave was cooled and the pressure was released, and the reaction product liquid and gas phase were analyzed by gas chromatography to determine the conversion rate of propylene and the yield of the product. The results are shown in Table-1.

[Table] Examples 6 to 9, Comparative Example 3 0.42 mmol of the compound listed in Table 2 was used instead of 1,4-bis(diphenylphosphino)butane as a ligand compound, and only Comparative Example 3 An experiment was carried out in the same manner as in Example 5, except that 0.105 mmol of SnCl ₂ .2H ₂ O was used as the tin compound. However, although the reaction was in progress, the reaction was stopped after 5 hours of reaction time and the yield of butyraldehyde was determined. The results are shown in Table-2.

[Table] Example 10 An experiment was carried out in the same manner as in Example 1 except that 6.8 g of 1-hexene was used instead of propylene and benzene was used instead of toluene. Comparative Example 4 An experiment was conducted in the same manner as in Example 10, except that SnCl ₂ .2H ₂ O was used as the tin compound. The results are shown in Table-3.

[Table] Examples 11, 12 Butene-1 instead of propylene (Example 11)
or cis-butene-2 (Example 12), respectively.
The experiment was conducted in the same manner as in Example 1 except that 12.4 g or 13.7 g was used and m-xylene was used instead of toluene. The results are shown in Table-4.

【table】

Claims (1)

[Claims] 1. A platinum compound, a ligand compound containing an element of Group VB of the periodic table, and a compound having the general formula Ar ₃ SnX (wherein, Ar represents an aryl group, X represents hydrogen,
Represents a hydroxyl group or an acyloxy group. )
In the presence of a triaryltin compound represented by and in a ratio of 0.05 to 1 mole per mole of platinum in the platinum compound, the olefinic compound is converted to carbon monoxide and hydrogen. A method for producing an aldehyde, which comprises reacting with.