JPS61167627A - Synthesis of oxygen-containing compound from olefin - Google Patents

Abstract

PURPOSE:To produce an oxygen-containing compound from an olefin, economically, by using water and a composite catalyst containing a platinum-group complex and a transition metal complex capable of forming a coordination bond with oxygen or olefin to form an oxygen complex or olefin complex, as the components of the catalyst. CONSTITUTION:An oxygen-containing component is produced by oxidizing an olefin in the presence of a metal complex catalyst. In the above process, the metal complex catalyst is composed of (A) a composite catalyst containing both complexes of formula MmXn.Ll and formula M'm'X'n'.L'l' (M is transition metal belonging to groups I, IV-VII or iron group of the group VIII of the periodic table; X is Cl<->, Br<->, I<->, BF<->4, PF<->6, etc.; L and L' are organic phosphorus compound or nitrile; L' may be organic fluorine compound; M' is transition metal belonging to platinum-group of the group VIII of the periodic table; m, m', n and n' are numbers determined by the balance of atomic values; land l' are coorination numbers) capable of forming a coordination bond with oxygen or olefin to form an oxygen complex or olefin complex, and (B) water. The objective compound can be produced in high yield and selectivity under mild condition.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for synthesizing oxygen-containing compounds from olefins, and in particular, oxidizing an olefin using a platinum group complex in the presence of water and an oxygen complex, The present invention relates to a method for producing an oxygen-containing compound.

(Prior art) As an example of the oxidation reaction of various olefins that has been carried out industrially, there is the famous Hoechst-Fucka process (Japanese Patent Publication No. 3
No. 6-1475, No. 36-7869). In this method, the catalyst is Pd (2)c7! .

A composite catalyst in which Cu(2)C12 and Cu(2)C12 are dissolved in a hydrochloric acid solution (pH 20-2) is used. For example, to explain the oxidation reaction of ethylene, first, ethylene is oxidized with divalent palladium and water to produce acetaldehyde. The reaction is shown by the following formula.

CH,=CH,+Pd (2)C12+H2O-CH3
CHO+Pd (0) ↓+2HC1 (1) As seen from this reaction formula, pa (2) is reduced to metal palladium (Pd (0)) and precipitated. Therefore, Cu
(2) By allowing a large amount of C1z to coexist, p
It is necessary to oxidize and regenerate a (0) to pa (2).

Pd (0)+2Cu (2)C112-=Pd (2
) C112+2Cu (1) Cj! (2) The poorly soluble Cu(1)C1 produced as a by-product at this time is oxidized with oxygen according to the following formula in the presence of HCl and returned to Cu(2)C12.

2Cu (1) CI+-0□+28CJ→2Cu (2
)CH12+H20(3) (problem to be solved by the invention) In this way, Pd (2)/Pd (0), Cu (
2)/Cu(1) redox system is employed to enable continuous oxidation of ethylene. However, this oxidation is not a direct oxidation of ethylene with oxygen, but a reaction with P dissolved in water.
d (2) ion oxidation, Cu (1) CI
The oxidative regeneration of is the rate-limiting factor. Further, since the solubility of oxygen in water is low, the solubility must be increased, and the oxygen treatment is performed at a high temperature and pressure of 100° C. and 10 atm.

In addition, in the case of higher olefins, the oxidation rate is slow and the reaction time is long, so it is said that they have not been put to practical use with 1-butene or higher (cylindrical, catalyst, !167 (1
979)). Furthermore, high concentration of HC7! Since an aqueous solution is used, corrosion-resistant materials such as titanium and Hastelloy are required.

In this way, the reaction is carried out at high temperatures and pressures, and there has been a desire for a method that can oxidize olefins under milder conditions.

An object of the present invention is to solve these problems and to provide a method for synthesizing oxygen-containing compounds by oxidizing oxidation compounds under milder conditions.

(Means for Solving the Problems) In short, the present invention uses a platinum group complex capable of forming an olefin complex by coordinately bonding the olefin, and oxidizes the olefin activated by complex formation in the presence of water. death,
This method further oxidizes the reduced platinum group complex with activated oxygen that coordinates with a transition metal, and synthesizes an oxygen-containing compound under mild conditions in a water-containing mixed solvent system.

The present inventors have previously proposed that at least one of the catalyst components is a transition metal complex capable of forming an oxygen complex through coordination bonding with oxygen. Using a composite catalyst consisting of a platinum group complex that can form complexes, ethylene activated by complex formation is directly oxidized with oxygen by bound oxygen activated by complex formation, and ethylene is oxidized under mild conditions in a non-aqueous solvent system. proposed a method for synthesizing acetaldehyde (Japanese Patent Application Nos. 58-104291 and 59-41800).

The present invention is based on the discovery in the course of its research that the oxygen complex in the above invention has the ability to efficiently oxidize pd(0) to <Pd(2)C7!2. In other words, to give a typical example, Cu
(1) A complex (Cu (
1) An oxygen complex ((Cu(1)C1-hmpa)2 .02) generated from CJ-hmpa) and a complex ((Cu(1)C1-hmpa)2.02) generated from, for example, Pd(2)Cf2, hmpa, and benzonitrile (PhCN). Pd (2) cz2
・Ethylene complex (P h CN-h m pa ) (
Pd (2) C7! , .P h CN-C2H4) in the presence of water, and is thought to proceed according to the following reaction mechanism.

(a) Generation of ethylene complex and Pd oxidation of ethylene
(2) C12・PhCN-hmpa+C2H4-'Pd
(2) Cjlz ・PhCN-C2H4+hmpa
(4P d (2) ci2' P hCN ' C
1H4”H20-CHz CHO+pd (0)
↓+2HCIt+PhCN (5)(b)Pd
Regeneration of (0) Pd (0) + (Cu (1) C1・hmpa
)2 ・Oz+ 2 HC1+ P h CN + h
m p a → Pd (2) CA2 ・PhCN-hm
pa+Cu (1)C1・hmpa+H20(6)(C
) Regeneration of oxygen complex Cu (1) C1-hmpa + -0°---(Cu
(1) Cjl-hmp a)x ・02
(7) Fig. 1 schematically shows the catalytic cycle of this reaction, and it can be seen that it is completely different from the Hoechst-Fucka method shown in Fig. 2. Furthermore, FIG. 3 shows the ultraviolet absorption spectrum of the complex used in the present invention, and FIG. 4 shows the amount of Pd(0) oxidized by the 02 complex in the present invention and Wa
FIG. 3 is a diagram comparing changes over time in the amount of pa (0) oxidation due to Cucll in the Cucker method.

Furthermore, to explain the characteristics of each reaction in more detail, the rate at 80°C of the oxidation regeneration reaction of Pd (0) to Pd (2) C12 shown in equation (6) is the same as that of Cu (2)
This was about 10 times faster than the regeneration speed by C12 (formula (2)). In addition, here, when the complex forming the above-mentioned oxygen complex is represented by the general formula MmXn-Ll, Cu (
1) CI-hmpa corresponds to the case where m=1, n-1, z=1. For example, when Ti (3) or v (3) is the central metal and the anion is C1-,
The resulting complex is Ti(3)C13・hmpa,V(
3) C23・h m p a, and in either case,
This corresponds to m=1, n=3, and l=1.

By the way, Cu generated by equation (7) (1) CI・h
m p a selectively absorbs oxygen from the air and returns to an oxygen complex, but the rate at 80°C is the same as that of Cu mentioned earlier.
(1) The reoxidation reaction of Cu (2) to CZ2 by (l of 02) is about 8 times faster than the reoxidation reaction (equation (3)). Acetaldehyde synthesis from ethylene can be carried out efficiently if the reaction is carried out under
To give a representative example, Pd (2) C12 is the h
When PhCN was added as a modifying ligand to m p a , a complex consisting of the following new mixed ligands was generated.

P d (2) Cjl2 (hrnp a) 2
+P h CN ;'Pd(2)Cf2 ・PhC
N-hmpa+hmpa (8) The general formula for this complex is M'm''Xn?・L'β.

In this case, m'=1, n'=2) l'=1.

This new pa (2) complex can be combined with ethylene (4) for example.
An ethylene complex is formed according to the formula, but in the generated ethylene complex, ethylene is significantly activated, so the oxidation reaction (formula (5)) by Pd (2) in the complex proceeds easily, and acetaldehyde is oxidized under mild conditions. , it can be synthesized in one step.

Pd (2) C1lt ・PhCN-hmpa+c2
H4Pd(2)Cffiz・PhCN-CzH
4+hmpa (4) Pd (2) C112・P
h CN-Cz H4+l(,0-CH:I CHO+
Pd (0) ↓+2HCjl+phcN (
5) The generated Pd (0) easily returns to the original Pd (2) complex by the oxygen complex as described above.

As described above, in the present invention, ethylene is activated as a complex, and Pd (0) generated by oxidizing ethylene with the oxidizing power of Pd (2) can be oxidized and regenerated with the activated oxygen in the oxygen complex. For example, acetaldehyde can be synthesized with high selectivity and high yield in a short time under mild conditions such as under normal pressure and at 80° C. or lower. Moreover, since it can be synthesized using a one-stage method, it is possible to significantly reduce equipment, cost, and utility compared to conventional methods.

In the composite catalyst system of the present invention, M in MmXn-LJ as a complex catalyst capable of forming an oxygen complex includes Cu s A g of Group 1 of the periodic law, Ti, Zr of Group 2,
Group V ■, Nb, Group ■Cr %M o s W
Transition metals such as Mn of group ■, Fe5(:, o, etc. of group ■) are preferable, and Cu (1), Ti (3), ■
(3) is more preferred. In addition, as X, Cl-1B
r-, Br- tllgenide ion, BF4PI'
Anions such as , -, CH3COO-, and S042- are preferred, and C12-, Br-, and Br- are more preferred. Ligands include nitriles, phosphoric acid derivatives such as triphenylphosphine oxyto, hexamethylphosphoramide, and mono-, di-, or triester formed from the reaction of phosphoric acid with methanol, ethanol, etc., as well as dimethyl methylphosphonate, Methyl dimethylphosphinate, or derivatives of phosphorous acid, mono-, di-, or triesters produced by the reaction of phosphorous acid with methanol, ethanol, etc.; phenylphosphonite, dimethylphosphinate, triethylphosphine, Preferred examples include organic phosphorus compounds represented by phenylphosphine, and in particular, hexamethylphosphoramide (hm pa), benzonitrile (PhCN
) is preferred.

On the other hand, a complex catalyst (M'm"X
Among metals belonging to the platinum group, Pd and Pt are preferable as Mo in n'·L''lo).

Preferred examples of the ligand include nitriles such as acetonitrile, propionitrile, and benzonitrile, the above-mentioned organic phosphorus compounds, and organic fluorine compounds such as fluorinated toluene and pensitrifluoride.

As the solvent for the reaction system, it is preferable to use a solvent that dissolves the composite catalyst, easily separates it from the generated oxygen-containing compound, and also reduces the viscosity of the catalyst solution and promotes mass transfer. For example, heptane, toluene, etc. , methylcyclohexane, dioxane, propylene carbonate, chlorobenzene, N-methylpyrrolidone, tetrahydrofuran,
and at least one solvent selected from various solvents such as ethers such as ethylene glycol dibutyl ether and diethylene glycol monomethyl ether, or a mixture thereof;
If “ is a liquid, it can also be used as a solvent.

In addition, in order to increase the selectivity and yield of the reaction, sulfolane, dimethylsulfolane,
It is preferable to coexist a basic (electron-donating) compound such as dimethyl sulfoxide, dimethylformamide, trimethylmethane, dimethyl sulfone, etc. in the reaction system.

Above, reaction examples have been described in which an oxygen complex and an olefin complex are formed, and an olefin is oxidized in the presence of water to synthesize an oxygen-containing compound.Next, the present invention will be explained in more detail with reference to Examples.

(Example) Example 1 Cu (1) (1'
35 g (0.35 mol) and 10 h m p a
0 g to prepare 97 ml of Cu (1) C1l-hmpa complex solution. Furthermore, another 100mj! Pd (2) C1z 1.3g (7
, 5 mlJ mol) and 15.5 gShm of PhCN.
Prepare 79g of p a, Pd (2) cIt, ・PhC
N・hmpa li body temperature solution 92mjlQ product. After sowing, both were transferred to reactor No. 11, 392 g of sulfolane was added thereto, and Q, 7 was added as Cu(1)C#.
m.

it/1, Pd (2) (0.015mol as 12
/7! 500 mj of catalyst solution! was prepared. 49 for this
g (9%) of water was added, air was introduced at 30°C under normal pressure, and the oxygen complex concentration was 0.145 m o j! / 12
A solution was prepared. After that, it was heated to 40°C and nitrogen gas was passed through it, but only the oxygen remaining in the gas phase of the reactor and the physically dissolved oxygen were removed, and the combined oxygen was removed from the oxygen complex in the liquid. No separation was observed, and the oxygen absorption reaction was irreversible. This is extremely advantageous in terms of safety in the actual process.

After this operation, ethylene was added at a flow rate of 0.2 J/mi at 40°C.
It was confirmed by gas chromatography that 2.1 g of acetaldehyde was produced in 30 minutes when aerated at a rate of n.

Examples 2 to 9 When an experiment was conducted in Example 1 under the conditions shown in Table 1, the amount of CH3CHO produced after 30 minutes at 40°C was as shown in the rightmost column of Table 1.

Table 1 From these results, the higher the concentration of PhCN, the higher the CH3CH
The amount of O produced tends to be large. However, when the sulfolane concentration is set to OM, the amount of CH3CHO produced decreases.

Example 10 Example 8 except that CH3CN is used instead of PhCN
When the same experiment was conducted, 12 g of CH3CHO was obtained.

Example 11 An experiment similar to Example 8 was conducted except that the reaction temperature was increased from 40°C to 60°C.
12.8 g of CHO was obtained.

Example 12 Cu (1) CI! The concentration of 0.7M was changed to 0.5M, and the pH
Set CN concentration 6.0M to 5.0M, 02 concentration 0.35
The same example as Example 8 was carried out except that M was changed to 1.4M. CH3C8012,7
I got g.

Example 13 In Example 8, when the amount of water added was 15 g (3%), 9.0 g of CH3CHO was obtained in 30 minutes. Also,
When the amount of water added was 88 g (15%), 8.6 g of CH3CHO was obtained in 30 minutes. From this example and example 8, it is considered that a water content of around 9% is optimal for this reaction system.

Example 14 Ti (3) instead of Cu (1) CI 0.7M
) An experiment similar to Example 8 was conducted except that 0.7 M of cj13 was used, and 9 g of CH3CH0 was obtained in 30 minutes.

Example 15 Cu (1) C1O, V (3) C1 instead of 7M
An experiment similar to Example 8 was conducted except that 30.7M was used, and 9.6 g of CH3CHO was obtained in 30 minutes.

Example 16 Pd(2)C1zO,015M was replaced with pt(
2) When the same experiment as in Example 8 was conducted except that 0.015M of C1z was used, CH3CHO was
12g was obtained.

Example 17 The catalyst liquid of Example 8 was kept at 40°C, and a mixed gas of 20% air and 80% ethylene was fed at a flow rate Q, 'l l/min
When aerated for 30 minutes at the rate of CH3CHOO07
I got g.

Examples 18-29 An experiment was conducted in the same manner as in Example 1, except that propylene was used instead of ethylene and the reaction temperature was 60°C instead of 40°C. After 30 minutes, CH3COCH
The amount of No. 3 produced was as shown in the rightmost column of Table 2.

Table 2 Example 30 The same operation as in Example 28 was carried out except that IM was used instead of CuC10.7M, and 9 g of acetone was obtained in a reaction time of 5 minutes. Cu (1)C1 at a constant 0□ concentration
As the concentration increases, the oxidation rate increases.

Examples 31 to 41 The same operation as in Example 1 was performed except that 1-butene was used instead of ethylene, the reaction temperature was 60°C instead of 40°C, and the reaction time was 20 minutes instead of 30 minutes. The results shown in the table were obtained.

Below is a margin Table 3 Example 42 Cu (1! Using 0.5M instead of 0.7M,
Using 0.125M instead of 020.145M, ph
Use 5M instead of cN 6M, mouth S0□ 0.3
When the same operation as in Example 41 was performed except that 1.4M was used instead of 5M, MEK was obtained within 20 minutes of reaction time.
17.5g was obtained.

Example 43 Using 1-pentene instead of ethylene, reaction temperature 40
The same experiment as in Example 8 was conducted except that the temperature was 60°C instead of 60°C, and 15g of 2-pentanone was obtained in a reaction time of 10 minutes.

Example 44 In Example 43, Cu (1) Ti instead of C12
(3) C1: + or V (3) When the same operation was performed except that cz3 was used, 2-pentanone 10
1 g of g5 l was obtained.

Example 45 In Example 43, Cu (1) Cj2 0.7M,
phcN 6MS [)02 0.5M, 5M, and 1.4M were used in place of 0.35M, and the same procedure was repeated except that 13.5 g of 2-pentanone was obtained.

Example 46 4.2 g (50 mmol) of 1-hexene was dissolved in the catalyst solution of Example 8, and the same procedure as in Example 1 was performed to obtain 0 oxygen complex.
．． When 145 mol/l of the reaction salt was prepared and the reaction salt was kept at 60°C, 4 g of 2-hexanone was obtained in a reaction time of 10 minutes.

Example 47 In Example 46, 4.9 g (50 mmol) of 1-heptene was used instead of 1-hexene, and the reaction temperature was changed to 80 mmol.
When the temperature was maintained at ℃ and the other operations were carried out in the same manner, the reaction time was 10
5.1 g of 2-heptanone was obtained in minutes.

Example 48 In Example 46, 5.6 g (50 mmol) of 1-octene was used instead of 1-hexene, and the reaction temperature was changed to 80 mmol.
When the temperature was maintained at ℃ and the other operations were carried out in the same manner, the reaction time was 10
5.8 g of 2-octanone was obtained in minutes, and 6.3 g in 20 minutes.

From the above results, it can be seen that the catalyst liquid of the present invention is extremely effective for the oxidation of higher olefins.

Example 49 Giant reticulated styrene/divinylbenzene Jl1 combination beads (particle size approximately 1 wmφ, specific surface area 700 to 800 rr)
r/g, Amberlight XAD manufactured by Organo 4) 5
0 ml was impregnated with a catalyst solution containing an oxygen complex having the composition shown in Example 8, and filtered under suction to cleave the granular catalyst. This was filled into a hard glass reaction tube with an inner diameter of 20 wφ and heated to 60°C.
After heating, ethylene was aerated at l 1 /min (5 V = 1200 hHz), and acetaldehyde in the outlet gas was analyzed using a gas chromatograph. As a result, the product was only acetaldehyde, and the yield based on ethylene was 60% from the start of the reaction to 30 minutes.

After that, the exit gas was recycled and the acetaldehyde yield based on the combined oxygen in the oxygen complex was determined to be 90%.
reached. Furthermore, the oxidation experiment was carried out again under the above conditions by temporarily stopping the supply of ethylene and aerating air to regenerate the combined oxygen consumed in the reaction, but similar results were obtained.

From the above, it has become clear that even if the complex catalyst of the present invention is supported on a carrier, the main oxidation reaction due to the bound oxygen in the oxygen complex proceeds.

Note that porous carriers such as silicates, activated carbon, and porous glass can be used as carriers, and as treatment methods after impregnation, various methods such as heated gas ventilation and low-temperature calcination can be used in addition to suction filtration. It was confirmed that it can be used.

(Effects of the Invention) According to the present invention, an olefin coordinated to a platinum group complex and activated is oxidized by a specific composite catalyst system without direct contact between olefin gas and oxygen gas, and further,
Since the reduced platinum group element is oxidized by oxygen coordinated to the transition metal complex and activated, oxygen-containing compounds can be synthesized with high selectivity and high yield under normal pressure and around room temperature. . In the present invention, even if air is used as an oxygen source, oxygen is selectively absorbed, so that exactly the same effect as using pure oxygen gas can be obtained. Further, since oxygen absorption is irreversible, excess free oxygen can be easily removed after forming an oxygen complex, which is extremely advantageous in terms of safety.

[Brief explanation of drawings]

FIG. 1 is a diagram schematically explaining the method of the present invention, and FIG. 2 is a diagram schematically explaining the method of the present invention (Pd (2)/Pd (0), Cu (2
)/Cu (1) Redox method), FIG. 3 is a diagram showing the ultraviolet absorption spectrum of the complex used in the present invention, and FIG. 4 is a diagram schematically showing the ultraviolet absorption spectrum of the complex used in the present invention. Oxidation amount and Cu in Wacker method
Cj! FIG. 2 is a diagram comparing changes over time in the amount of Pd(0) oxidized by No. 2. Agent: Patent Attorney Takenaga Kawakita, Figure 1 Figure 2 Oz (g) 14 Visiting Figure 3 Figure 4

Claims (7)

[Claims] (1) Oxidizing olefins in the presence of a metal complex catalyst,
In the method of synthesizing oxygen-containing compounds, a complex (MmXn.
A composite catalyst containing a complex (M'm' Chapter IV
~A transition metal belonging to the iron group of Group VII or Group VIII, where X is a halogen such as Cl^-, Br^-, I^- or BF_
4^-, PF_6^-, CH_3COO-, SO_4^
Anion such as 2^-, the ligand L is an organic phosphorus compound, a nitrile, L' is a nitrile, an organic fluorine compound or an organic phosphorus compound, M' is a transition metal belonging to the platinum group of Group VIII of the periodic law, L' is a nitrile, an organic fluorine compound, or an organic phosphorous compound, m, m', n, n' are constants determined by the valence balance, l, l' indicate the coordination number) as the catalyst component. A method for synthesizing oxygen-containing compounds from olefins. (2) In claim 1, the organic phosphorus compound as the ligands L and L' is a compound represented by an alkoxy, alkyl or amide derivative of phosphoric acid or phosphorous acid. How to do it. (3) The method according to claim 1 or 2, characterized in that a basic (electron-donating) compound such as sulfolane, dimethylsulfolane, dimethylsulfoxide, dimethylformamide, etc. is added to the catalyst solution. (4) In any one of claims 1 to 3, the solvent for the complex is an aliphatic, aromatic, or alicyclic hydrocarbon, an oxygen-containing organic compound, an organic halide,
A method characterized in that at least one compound selected from nitrogen-containing compounds, organic sulfur compounds, organic fluorine compounds, and heterocyclic compounds is used. (5) The method according to any one of claims 1 to 4, characterized in that the ligands L and L' are liquids, and the ligands themselves also serve as a solvent. (6) In any one of claims 1 to 5, an oxygen-containing mixed gas is passed through the solution of the complex to form an oxygen complex, and an olefin is introduced into the solution in the presence of water. A method characterized by carrying out a reaction. (7) In any one of claims 1 to 6, the complex is dissolved in a solvent, impregnated and supported on a porous carrier, and an oxygen-containing gas and an olefin are brought into contact with the complex in the presence of water. A method characterized by carrying out the reaction below.