JPH0575461B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a platinum-tin catalyst. Platinum-tin catalysts for the production of aldehydes by hydroformylation reactions can be used as catalysts for various organic chemical reactions, and are particularly useful as catalysts for hydroformylation reactions to produce linear aldehydes with good catalytic activity and high industrial value. It has excellent properties such as high selectivity to Conventionally, as a method for preparing a platinum-tin catalyst, a method has been known in which a platinum compound, a ligand compound, and a tin compound are supplied to a reaction system for a hydroformylation reaction, and a reactive platinum-tin catalyst is formed in the reaction system. It is being However, in this method, a reaction induction period occurs before active species are formed. Therefore,
It is desirable to prepare a reactive platinum-tin catalyst in advance. As a method for preparing platinum-tin complex in the presence of a mixed gas of hydrogen and carbon monoxide, trans-PtHCl
[P(C ₆ H ₅ ) ₃ ] ₂ and SnCl ₂ 2H ₂ O complex, PtH
It is known to prepare ( _{SnCl3 )} (CO)[P( _C6H5 ) ₃ ] ₂ . [J.Amer.Chem.Soc.97, 3553
(1975)] However, when platinum compounds, ligand compounds, and tin compounds are reacted in the presence of hydrogen or a mixed gas of hydrogen and carbon monoxide, platinum metal often precipitates and a platinum-tin complex is formed. The expensive platinum may not be used effectively. In view of the above circumstances, the present inventors have made extensive studies and found that by coexisting hydrogen halide during the above reaction, a platinum-tin catalyst can be prepared without precipitation of platinum metal, and The present invention was completed based on the recognition that when used in a hydroformylation reaction, it has high activity and substantially eliminates the induction period. That is, the present invention aims to provide an industrially advantageous method for producing a platinum-tin catalyst for aldehyde production by an excellent hydroformylation reaction, and aims to provide a method for industrially advantageously producing a platinum-tin catalyst for producing aldehydes by an excellent hydroformylation reaction. A platinum-tin catalyst for producing aldehydes by a hydroformylation reaction, which is characterized in that a child compound, a tin compound, and a hydrogen halide are reacted in the presence of hydrogen or a mixed gas of hydrogen and carbon monoxide in a solvent. The gist is the manufacturing method. The present invention will be explained in more detail below. In this specification, "periodic table" means IUPAC Comptes Rendus unless otherwise specified.
Refers to the Periodic Table of Elements as listed in Conference, p. 183 (1965). As the platinum compound, a zero-valent, divalent or tetravalent platinum compound can be used, but since hydrogen halide is used in the present invention, in order to reduce the amount of hydrogen halide used, it is necessary to use a halogen-containing platinum compound. Preference is given to using valent or tetravalent platinum compounds. In the present invention, in addition to platinum compounds,
A ligand compound containing a group 5B element is used in combination, which improves the stability of the complex and the activity when subjected to a catalytic reaction. These compounds can be charged separately into the reaction system, but a platinum complex having a ligand compound containing a Group 5B element as a ligand can also be prepared in advance and then charged into the reaction system. Examples of platinum compounds that can be used in the present invention include platinum halides such as platinum dichloride and platinum tetrachloride;
Halogenoplatinic acids and their salts such as hexachloroplatinic acid, sodium hexachloroplatinate, potassium hexachloroplatinate, potassium hexabromoplatinate, tetrachloroplatinic acid, potassium tetrachloroplatinate, dichloro(1,5-cyclooctadiene)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(diphenylphosphine)butane 〕platinum()

[Chemical] Dichloro[1,2-bis(diphenylphosphinomethyl)cyclobutane]platinum ()

Examples include platinum complexes such as [Formula] (hereinafter referred to as PtCl ₂ (DPCB)). A ligand compound containing an element of group 5B of the periodic table has the general formula: AR ⁴ R ⁵ R ⁶ (wherein A represents phosphorus, arsenic, antimony, bismuth or nitrogen, R ⁴ is 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 that may have a substituent, or an alkylene group, cycloalkylene group, arylene group, or bicycloalkylene group bonded to A or A' via an alkylene group or an oxygen atom) represents,
A′ represents phosphorus, arsenic, antimony, bismuth or nitrogen. ), and R ⁵ and R ⁶ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group. ) A monodentate or bidentate ligand represented by is preferably used. Specifically, monodentate ligands include triphenylphosphine, tritolylphosphine, tris(chlorophenyl)phosphine, tris(methoxyphenyl)phosphine, benzyldiphenylphosphine, and bis(2-cyanoethyl)phenylphosphine. , tricyclohexylphosphine, diethyl phenyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, trinaphthyl phosphine, tribenzyl phosphine, diphenylene phenyl phosphine, etc., triethyl Phosphite, tertiary phosphite such as tripropylphosphite, tributylphosphite, tridecylphosphite, triphenylphosphite, tris(chlorophenyl)phosphite, tertiary arsine such as triphenylarsine, tritolylarsine, triethylarsine, etc. , tertiary stibines such as tributylstibine and triphenylstibine, tertiary bismuthins such as triphenylbismuthin, tertiary amines such as tributylamine and triphenylamine, and 1 as a bidentate ligand. , 2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)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, trane-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 5B elements. The tin compound can be selected from various inorganic and organic tin compounds, but preferably has the general formula: ArSnR ¹ R ² R ³ (wherein Ar represents an aryl group that may have a substituent, and R ¹ , R ² and R ³ represent a hydrogen atom, a hydroxy group, an acyloxy group, a halogen atom, or an alkyl group, an alkenyl group, an aryl group, or an alkenyl group that may have a substituent. and General formula: Sn(R)n (wherein R is an oxygen atom or an acyloxy group,
n represents an integer of 1, 2 or 4. ) is used. Examples of the above aryltin compound include (C ₆ H ₅ )
SnCl ₃ , (p-CH ₃・C ₆ H ₄ ) ₂ SnCl ₂ , (C ₆ H ₅ ) ₂
SnCl ₂ , (C ₆ H ₅ ) ₃ SnCl, (C ₆ H ₅ ) ₃ SnBr, (C ₆ H ₅ ) ₃
SnI, (C ₆ F ₅ ) ₃ SnCl, (C ₆ H ₅ ) ₃ SnOCH ₃ , (C ₆ H ₅ ) ₃
SnCH ₃ , (C ₆ H ₅ ) ₃ SnCH ₂・CH ₂ OH, (C ₆ H ₅ ) ₃
Examples include SnCH ₂ CH=CH ₂ . Particularly preferred among the above aryltin compounds are triaryltin compounds represented by the general formula: Ar ₃ SnX (wherein Ar represents an aryl group, and X represents a hydrogen atom, a hydroxyl group, or an acyloxy group). Yes, specifically (C ₆ H ₅ ) ₃ SnH, (C ₆ H ₅ ) ₃ SnOH, (C ₆ H ₅ ) ₃
Examples include SnOCOCH ₃ , (C ₆ H ₅ ) ₃ SnOCOC ₆ H ₅ . Next, a specific example of the oxytin compound is given.
SnO, SnO ₂ , Sn(OCOCH ₃ ) ₂ , Sn(OCOCH ₃ ) ₄ and the like, with Sn(OCOCH ₃ ) ₂ being particularly suitable. These tin compounds are preferably used in an amount of 0.5 to 2 moles relative to platinum. Hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide are used as hydrogen halides. The form in which they are added to these reaction systems is not particularly limited, and they may be used in a gaseous state or dissolved in an aqueous solution (hydrohalic acid) or an organic solvent such as methanol, ethanol, acetone, or dioxane. It is possible. The concentration of hydrogen halide when used dissolved in a solvent is not particularly limited and can be arbitrarily adjusted within the range of solubility. For example, in the case of hydrochloric acid, a commercially available product with a concentration of 35% is sufficient. The amount of these hydrogen halides to be used varies depending on the form of the platinum compound used and is not necessarily uniquely determined. For example, if a zero-valent platinum compound is used, hydrogen halide is consumed by oxidative addition to platinum, so a larger amount is required than a dihalogenated platinum type compound. Also, if used in large amounts, problems such as corrosion will occur, so it is preferable to use as little as possible within the range in which a platinum-tin catalyst is formed, usually in the range of 0.05 to 5 times the mole of platinum. It is preferably used in A solvent is used in the method of the invention. Specific examples of solvents include methanol, ethanol,
Alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, Sec-butyl alcohol, cyclohexanol, ethers such as diethyl ether, dioxane, tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diethyl ketone, acetamide, propion Amides, amides such as amide, N,N-dimethylformamide and N,N-dimethylacetamide, nitriles such as acetonitrile, propionitrile and benzonitrile, esters such as ethyl acetate and methyl propionate, and sulfoxides such as dimethyl sulfoxide. , carboxylic acids such as acetic acid, pyridyls such as pyridine and methylpyridine,
Examples include aldehydes such as acetaldehyde and propionaldehyde, hydrocarbons such as benzene, toluene, xylene, and decane, and halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, and o-dichlorobenzene. 2
Used as a mixture of more than one species. Particularly preferred solvents are benzene, toluene, acetone, dioxane, tetrahydrofuran, and the like. The amount of these solvents used is
There is no particular limitation as long as the amount is at least capable of dissolving the ligand compound containing the group element and the tin compound. In carrying out the present invention, the reaction temperature is usually selected within the range of room temperature to 200°C, preferably 50 to 150°C, and the pressure of hydrogen or a mixed gas of hydrogen and carbon monoxide is adjusted to the reaction temperature. It depends, but usually normal pressure ~ 300
The pressure is preferably selected within the range of 5 to 200 atmospheres. H ₂ /CO, a gas mixture of hydrogen and carbon monoxide
The molar ratio is usually selected within the range from 0.1 to 10, preferably from 0.3 to 3. The reaction time may generally be about 10 minutes to 4 hours. The resulting platinum-tin catalyst can be isolated by crystallization using a conventional method. The platinum-tin catalyst produced by the method of the present invention can be used in homogeneous complex catalytic reactions for the production of aldehydes by hydroformylation reactions, but in such cases the reaction product can be obtained without isolating the platinum-tin catalyst. Either leave the liquid as it is, or if the platinum-tin catalyst precipitates, add an appropriate solvent to dissolve it.
It can also be used as a catalyst liquid. In such cases, it is particularly preferred to prepare the platinum-tin catalyst in the solvent used for the catalytic reaction. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist of the present invention is exceeded. Example 1 PtCl ₂ (DPCB) was placed in a stainless steel spinner-stirring micro autoclave with an internal volume of 100 ml.
0.18g, (C ₆ H ₅ ) ₃ SnOCOCH ₃ 0.102g, 35% hydrochloric acid
Charge 0.025ml and 20ml of dioxane and replace the inside of the autoclave with nitrogen (20Kg/cm ²・G x 3 times)
Then, a mixed gas of hydrogen and carbon monoxide (H ₂ /CO molar ratio 1.0) was injected up to 60 kg/cm ² G, and the mixture was heated at 100°C for 30 minutes.
Allowed time to react. After the reaction was completed, the reaction solution taken out was a yellow homogeneous solution. The mixture was dropped into about 10 times the volume of n-hexane under an argon gas atmosphere, and the precipitate was separated and dried under vacuum to obtain 0.196 g of a yellow solid. The elemental analysis values of the obtained solid are shown below. Pt Sn P 20.3 14.6 7.4 Cl C H 12.4 40.5 3.7 (wt%) Reference example 1 The yellow solid obtained in Example 1 was placed in a stainless steel vertically stirred autoclave with an internal volume of 200 ml.
After charging 0.098 g and 50 ml of toluene and sealing the autoclave, the inside of the autoclave was replaced with nitrogen and propylene was added.
10.5g was press-fitted. Then inside the autoclave
The temperature was raised to 100° C. in about 20 minutes, and a mixed gas of hydrogen and carbon monoxide (H ₂ /CO molar ratio 1.0) was pressurized to bring the pressure inside the autoclave to 100 Kg/cm ² ·G. Continue stirring while keeping the internal temperature of the autoclave at 100℃, and keep the internal pressure at 100Kg/cm ²・G.
Mixed gas of hydrogen and carbon monoxide (H ₂ /CO molar ratio
1.0) was replenished, and the reaction was carried out for a predetermined period of time. After the reaction was completed, the reaction solution taken out was a yellow homogeneous solution. Table 1 shows the reaction rate determined from the results of analyzing the product using a gas chromatograph and the supply rate of the supplied mixed gas of hydrogen and carbon monoxide. (Run-1) In order to compare the activity, PtCl ₂ was used instead of the yellow solid without preparing the platinum-tin catalyst in advance.
(DPCB) 0.0755g and (C ₆ H ₅ ) ₃ SnOCOCH ₃
When the same treatment was carried out except that 0.0429 g was used, a small amount of black precipitate was observed in the reaction solution. The reaction results are also listed in Table-1. (Run-2)

[Table] Comparative Example 1 When the same treatment as in Example 1 was performed except that hydrochloric acid was not used, a black precipitate caused by metalization was observed in the taken out reaction solution. Example 2 PtCl ₂ [P(C ₆ H ₅ )] was added to the micro autoclave.
₃ ] ₂ 0.395 g, (C ₆ H ₅ ) ₃ SnOCOCH ₃ 0.204 g, 0.05 ml of 35% hydrochloric acid and 15 ml of acetone were charged, and the same procedure as in Example 1 was taken, except that the reaction time was 2 hours. The reaction solution was a yellow homogeneous solution, and 0.385 g of an orange solid was similarly obtained from the solution.
Of this, 0.192 g was dissolved in acetone and purified by reprecipitation with n-hexane, resulting in 0.09 g of a reddish-orange solid. Based on the results of elemental analysis, 15.6wt%
of Pt, 17.5 wt% of Sn, and 5.5 wt% of P. Comparative Example 2 The same procedure as in Example 2 was carried out except that hydrochloric acid was not used, and a black precipitate was observed in the reaction solution taken out. Example 3 Instead of (C ₆ H ₅ ) ₃ SnOCOCH ₃ and acetone, 0.118 g of Sn(OCOCH ₃ ) ₂ and 25 ml of dioxane
0.339 g of an orange solid was obtained by processing in the same manner as in Example 2, except that each of these was used. Reference Example 2 When a hydroformylation reaction of propylene was carried out in the same manner as in Reference Example 1 except that 0.17 g of the orange solid obtained in Example 3 was used, it was observed that the reaction proceeded without an induction period.

Claims (1)

[Claims] 1. Reaction of a platinum compound, a ligand compound containing a Group 5B element, a tin compound, and a hydrogen halide in the presence of hydrogen or a mixed gas of hydrogen and carbon monoxide in a solvent. 1. A method for producing a platinum-tin catalyst for producing an aldehyde by a hydroformylation reaction. 2. In the method for producing a platinum-tin catalyst for producing an aldehyde by a hydroformylation reaction according to claim 1, the tin compound has the general formula: ArSnR ¹ R ² R ³ (wherein Ar represents a substituent). represents an optional aryl group, R ¹ , R ² and R ³ are hydrogen atoms,
It represents a hydroxyl group, an acyloxy group, a halogen atom, or an alkyl group, an alkenyl group, an aryl group, or an alkoxy group that may have a substituent. ) A method characterized in that the compound is a compound represented by 3. In the method for producing a platinum-tin catalyst for producing aldehydes by hydroformylation reaction according to claim 1, the tin compound has the general formula: Sn(R)n (wherein R is an oxygen atom or acyloxy n represents an integer of 1, 2 or 4).