JPH0798766B2 - Method for producing aldehyde - Google Patents

Description

TECHNICAL FIELD The present invention relates to an improvement in a method for producing an aldehyde from an internal olefin as a raw material. More specifically, the present invention uses a highly active catalyst system to hydroformylate an internal olefin with carbon monoxide and hydrogen in a liquid phase to produce an aldehyde with good yield and industrial advantage. Method.

BACKGROUND ART Aldehydes are extremely important compounds as raw materials and intermediates in organic synthesis. As a method for producing them, conventionally, olefins were hydroformylated by reacting olefins with carbon monoxide and hydrogen in the presence of a catalyst. A method of manufacturing by converting into

Examples of the catalyst for hydroformylation of such olefins include cobalt and rhodium carbonyl compounds and cobalt or rhodium organometallic complexes in which a part of the carbonyl group of these compounds is substituted with a basic compound such as alkyl or arylphosphine. A liquid phase homogeneous catalyst using is known, and using this catalyst, a process for producing aldehydes and alcohols from olefins, carbon monoxide and hydrogen has already been developed [catalyst course, Volume 7, page 86 (published by Maruzen in 1985)].

Then, in the hydroformylation of the internal olefin raw material with carbon monoxide and hydrogen, when the above-mentioned cobalt or rhodium organometallic complex catalyst is used, the activity of the catalyst is extremely low, so that the cobalt carbonyl catalyst or rhodium carbonyl catalyst Regarding the rhodium catalyst, which is said to be preferably used, a human roormylation method using a catalyst obtained by treating an oxide of a rhodium compound and a trivalent organic phosphorus compound with carbon monoxide is known (Japanese Patent Laid-Open No. 59-70629). However, in order to stably maintain the activity of the cobalt carbonyl and rhodium carbonyl catalysts in these catalyst systems, a high pressure condition of 200 atm or more is required for hydroformylation, and undesired hydrogenation by-products are required. Has the drawback of being generated. Thus, they are conventional hydroformylation catalysts, especially expensive precious metals. With respect to the catalyst using rhodium, development of a catalyst system exhibiting high activity is desired.

A method using a ternary system consisting of a rhodium compound-phosphine compound-rhenium compound in hydroformylation of an internal olefin is also known (JP-A-54-54).
16418, Comparative Example 1), this method cannot be said to be particularly advantageous as compared with a binary element consisting of a rhodium compound-phosphine compound, and is not a method sufficient for industrial use.

The present invention overcomes the disadvantages of such conventional catalysts in the hydroformylation of internal olefins, and uses a highly active and highly selective catalyst to produce internal olefins, carbon monoxide and hydrogen. The present invention has been made for the purpose of providing a method for producing an aldehyde with high yield and industrial advantage.

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on a hydroformylation catalyst of an internal olefin having high activity and high selectivity, and as a result, have found that a rhodium compound and a rhenium compound, and optionally a more specific phosphorus compound. It was found that the above-mentioned object can be achieved by using a catalyst system consisting of a combination of the addition of the above and based on this finding, the present invention has been completed.

That is, the present invention provides (A) a rhodium compound and (B)
A catalyst comprising a rhenium compound, or the above-mentioned component (A),
(B) component and (C) general formula (In the formula, R ¹ , R ² and R ³ are each an alkyl group, an aryl group, an alkyloxy group or an aryloxy group,
They may be the same or different from each other.) A process for producing an aldehyde, which comprises reacting an internal olefin with carbon monoxide and hydrogen in the presence of a catalyst comprising a phosphorus compound represented by Is provided.

Hereinafter, the present invention will be described in detail.

In the method of the present invention, as the catalyst, a combination of the components (A) and (B), or a combination of the components (A), (B) and (C) is used. It can be used in the liquid phase.

Examples of the component (A) of the catalyst used in the method of the present invention, that is, the rhodium compound, include, for example, rhodium metal and oxides, inorganic salts such as halogen salts, nitrates, carbonates, acetates, oxalates, and acetylacetates. Rhodium salts or chelate compounds of organic salts of Rhodium, rhodium compounds such as amine complexes, metal alkoxide compounds, alkyl metal compounds and carbonyl compounds, and rhodium metal complexes are used. Among these, rhodium carbonyl compounds and rhodium metal complexes are used. Is preferred.
Examples of the rhodium metal complex include RhCl (Ph ₃ P) ₃ and RhH
_{(CO) (Ph 3 P)} 3, RhCl (CO) (Ph 3 P) 2, RhH 2 (Ph 3 P) such as ₃ Cl and the like. In the present invention, these rhodium compounds as the component (A) may be used alone, or 2
You may use it in combination of 2 or more types.

Further, as the rhenium compound as the component (B), for example, rhenium metal, oxides, halogen salts, acetates, carbonyl compounds and the like can be used, and among these, the rhenium carbonyl compound is preferable. In the present invention, these rhenium compounds as the component (B) may be used alone or in combination of two or more kinds.

These rhenium compounds enhance the hydroformylation activity of the catalyst and are particularly effective in stabilizing the catalyst.

As the catalyst in the method of the present invention, a combination of the above components (A) and (B) may be used, or the combination of the components (A) and (B) may further comprise the component (C). You may use what combined.

The component (C) has a general formula A phosphorus compound represented by the formula (R ¹ , R ² and R ³ in the formula have the same meanings as described above) is used. R ¹ , R ² and R ³ in the above general formula (I) are each an alkyl group, an aryl group, an alkyloxy group or an aryloxy group, which may be the same or different from each other. However, those having the same R ¹ , R ² and R ³ are preferably used from the viewpoint of easy availability.

Such phosphorus compounds, for example, _{(C 4 H 9) 3 PO} , (C 6
_{H 11) 3 PO, (C} 6 H 5) 3 PO, (CH 3 C 6 H 4) 3 PO, CH 3 PO (OCH 3) 2, C 6
_{H 5 PO (OCH 3) 2} , C 6 H 5 PO (OEt) 2, (C 6 H 11 O) 3 PO, (C 6 H 5 O) 3 P
O, (CH ₃ C ₆ H ₄ O) ₃ PO and the like.

These phosphorus compounds may be used alone or in combination of two or more. These phosphorus compounds are particularly effective in stabilizing the catalyst.

In the present invention, the component (A) and the component (B) in the catalyst are used in a ratio such that the atomic ratio of rhenium to rhodium is usually 0.1 to 100, preferably 0.5 to 50. Further, the phosphorus compound of the component (C) is (A)
It is preferable to use it in a ratio such that the atomic ratio of phosphorus to the component rhodium is 1 or more.

In the method of the present invention, the catalyst may be in the form of a liquid phase homogeneous catalyst or a liquid phase heterogeneous catalyst. When the method of the present invention is carried out in a liquid phase reaction, after the internal olefin, carbon monoxide and hydrogen are reacted with the catalyst in the liquid phase, the resulting aldehyde is separated in a separation device,
The liquid phase catalyst may be recovered, or internal olefin, carbon monoxide and hydrogen may be added to the liquid phase catalyst to remove the aldehyde as a gaseous product outside the reaction system and be recovered.

The solvent used in such a liquid phase reaction needs to be chemically inert under the reaction conditions, and examples of such a solvent include aliphatic saturated carbonization such as decane, tridecane, tetradecane and hexadecane. Aromatic hydrocarbons such as hydrogen, benzene, toluene, and methylnaphthalene; esters such as ethyl benzoate, dioctyl phthalate, dimethyl phthalate, triphenyl phosphate, tricresyl phosphate, and triphenyl phosphite. it can. These solvents may be used alone or in combination of two or more.

In the present invention, the internal olefin used as a raw material component is an olefin in which a double bond is formed between carbon atoms other than the terminal carbon atoms, and examples thereof include 2-butene and 2-butene. Penten, 2-hexene, 3-
Hexene, 2-octene, 3-octene, 2-methyl-2-pentene, 4-methyl-2-pentene, 4-methyl-2-heptene,
Examples thereof include linear, branched or cyclic monoolefins or diolefins having 4 to 12 carbon atoms such as cyclohexene, cyclooctene and 1,5-cyclooctadiene. Further, since the olefin isomer mixture synthesized by oligomerization of ethylene, propylene, butene, isobutylene, etc. contains an internal olefin,
This isomer mixture is also suitable as a raw material.

The ratio of these internal olefins to carbon monoxide and hydrogen is not particularly limited, but usually the molar ratio of olefin: carbon monoxide is 1:10 to 10: 1 and the molar ratio of carbon monoxide: hydrogen is 1. It is desirable to use it at a ratio of 10 to 10: 1.

Although the reaction can produce the desired aldehyde with a high selectivity and a high yield even if the reaction is carried out under normal pressure, it is preferably carried out under pressure in order to increase the specific activity per rhodium atom. the reaction pressure, 350kg / cm ² · G or lower, preferably 8~300kg / cm ² · G.
On the other hand, the reaction temperature is usually 50 to 250 ° C, preferably 80 to 200.
It is selected in the range of ° C. If this temperature is lower than 50 ° C, the reaction rate is too slow to be practical, and if it exceeds 250 ° C, byproducts increase and the aldehyde selectivity tends to decrease.

EFFECTS OF THE INVENTION According to the method of the present invention, in a hydroformylation reaction of an internal olefin with carbon monoxide and hydrogen, by using a specific catalyst system having excellent activity and stability, aldehyde can be industrially produced in high yield and high selectivity. It can be manufactured in an advantageous manner.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The invention is in no way limited by these examples.

Example 1 Tetrarodium dodecacarbonyl [Rh ₄ (CO) ₁₂ ] 16.8 mg
(2.25 × 10 ^-2 mmol), rhenium carbonyl [Re ₂ (C
O) ₁₀ ] 117.5 mg, (0.19 mmol), cyclohexene 1.0 g (1
2.2 mmol) and 5.0 g of benzene as a solvent are put in a 30 ml autoclave, and a mixed gas of carbon monoxide and hydrogen (CO
/ H ₂ molar ratio = 1) 50 atm (gauge pressure) was introduced, and the reaction was carried out at 120 ° C. for 1 hour while stirring. After the reaction, the gas component and liquid phase component in the autoclave were qualitatively and quantitatively analyzed by gas chromatography and NMR. As a result, a conversion of cyclohexene of 96.8% and a yield of cyclohexenecarboxaldehyde of 96.3% were obtained.

When rhenium carbonyl was not added in the above reaction, the conversion of cyclohexene was 92.6%, and the yield of cyclohexenecarboxaldehyde was 92.1%.

Example ² Tetrarodium dodecacarbonyl 8.4 mg (1.12 × 10 ⁻² mmo
l), rhenium carbonyl 58.7 mg (0.09 mmol), triphenylphosphine oxide 626 mg, 3-hexene 1.0 g and solvent benzene 5.0 g were placed in a 30 ml autoclave and reacted under the same conditions as in Example 1 The product was analyzed. As a result, the conversion of 3-hexene was 87%, and the yield of the produced aldehyde was 80%. The distribution of aldehydes produced was 1-heptanal 32%, 2-methylhexanal 45%, 2-
It was 23% of ethyl pentanal.

Further, when rhenium carbonyl was not added in the above reaction, the conversion of 3-hexene was 87% and the yield of aldehyde was 70%. The distribution of the produced aldehyde was 1-heptanal 30%, 2-methylhexanal 46%, and 2-ethylpentanal 24%.

Example 3 Tetrarodium dodecacarbonyl 8.4 mg (1.12 × 10 ⁻² mmo
l), rhenium carbonyl 58.7 mg (0.09 mmol), triphenylphosphine oxide 626 mg, 3-heptene 1.0 g and solvent benzene 5.0 g were placed in a 30 ml autoclave and the reaction was carried out in the same manner as in Example 1. Was analyzed.

As a result, the conversion of 3-heptene was 89%, and the yield of the produced aldehyde was 75%. The distribution of the produced aldehyde was 1-octanal 27%, 2-methylheptanal 42%, 2-ethylhexanal 21%, and 2-propyl-pentanal 10%.

When rhenium carbonyl was not added in the above reaction, the conversion of 3-hexene was 83% and the aldehyde yield was 70%. The distribution of the produced aldehyde was similar to the above result.

Example 4 Tetrarodium dodecacarbonyl 8.4 mg, rhenium carbonyl 58.7 mg, triphenylphosphine oxide 626 m
g, 2-octene (1.0 g) and solvent benzene (5.0 g) were placed in a 30 ml autoclave, the reaction was carried out in the same manner as in Example 1, and the reaction product was analyzed. As a result, 2-octene conversion rate
The yield was 85% and the aldehyde yield was 75%. The aldehyde distribution is 1-nonanal 28%, 2-methyloctanal 43%, 2-
16% ethylheptanal, 13% 2-propylhexanal
Met.

When rhenium carbonyl was not added in the above reaction, the 2-octene conversion was 83%, the aldehyde yield was 70%, and the distribution of the produced aldehyde was similar to the above result.

Example 5 Tetrarodium dodecacarbonyl 8.4 mg, rhenium carbonyl 58.7 mg, triphenyl phosphate 831 mg, 2-hexene 1.0 g and solvent benzene 5.0 g were placed in a 30 ml autoclave, and the reaction temperature was set to 100 ° C. The reaction was carried out as in Example 1 and the reaction products were analyzed.

As a result, 2-hexene conversion rate 96%, aldehyde yield 87%
Met. Product aldehyde distribution is 1-heptanal 26%,
2-Methylhexanal 46%, 2-Ethylpentanal 28%
Met.

When rhenium carbonyl was not added in the above reaction, the conversion of 2-hexene was 93% and the aldehyde yield was 77%. The generated aldehyde distribution was similar to the above result.

Claims (2)

[Claims] 1. A process for producing an aldehyde, which comprises reacting an internal olefin with carbon monoxide and hydrogen in the presence of a catalyst composed of a rhodium compound (A) and a rhenium compound (B). 2. A rhodium compound (A), a rhenium compound (B) and a general formula (C). (In the formula, R ¹ , R ² and R ³ are each an alkyl group, an aryl group, an alkyloxy group or an aryloxy group,
They may be the same or different from each other.) A process for producing an aldehyde, which comprises reacting an internal olefin with carbon monoxide and hydrogen in the presence of a catalyst comprising a phosphorus compound represented by .