JPH0662480B2 - Method for producing α, ω-dialdehyde - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing an α, ω-dialdehyde having 8 to 12 carbon atoms, and more specifically, an α, ω-diolefin having 6 to 10 carbon atoms or a carbon number. The present invention relates to a method for producing an α, ω-dialdehyde having 8 to 12 carbon atoms, which comprises hydroformylating an α, ω-alkenal of 7 to 11 and extracting the obtained reaction mixture.

The α, ω-dialdehyde having 8 to 12 carbon atoms obtained according to the present invention is used as an immobilizing agent for proteins and enzymes, a bactericidal agent, a polymer cross-linking agent, and a starting material for corresponding dicarboxylic acids, diols and diamines. It is a very useful compound.

[Conventional technology]

Α, ω-diorefin or α, ω- having 6 to 10 carbon atoms
8 to 1 carbon atoms by hydroformylating alkenal with hydrogen and carbon monoxide using a rhodium compound modified with a tertiary phosphine compound as a catalyst
It is known that an α, ω-dialdehyde of 2 can be obtained. Since the rhodium catalyst used in such a hydroformylation reaction is expensive, after the reaction, the rhodium catalyst is separated from the α, ω-dialdehyde that has formed, and then regenerated into the hydroformylation reaction without loss and deactivation of the rhodium catalyst. The use is required for industrial implementation of the process for producing α, ω-dialdehyde. When the separation of the rhodium catalyst and the α, ω-dialdehyde is carried out by distillation of the hydroformylation reaction mixture liquid, the reaction mixture liquid is distilled in order to distill α, ω-dialdehyde having a high boiling point. Need to be heated at high temperature. Therefore, according to such a distillation separation method, pyrolysis of the rhodium catalyst occurs during the distillation operation to deposit rhodium metal, or the catalyst is denatured by the compound having a high boiling point as a by-product. Residual liquid cannot be circulated for a long period of time. Therefore, as a method capable of separating the rhodium catalyst and the α, ω-dialdehyde after the hydroformylation reaction without deactivating the rhodium catalyst, a method of subjecting the hydroformylation reaction mixture to extraction has been proposed. (See, for example, JP-A-57-167937, JP-A-58-21638, JP-A-58-157739 and JP-A-58-216138). JP-A-57-167937 discloses that hydroformylation of olefins such as monoolephins having a functional group is carried out in water or a solvent containing water by using a water-soluble sulfonated phosphine, and the resulting aldehyde is formed. Is separated from the reaction mixture by decantation or extraction. Further, JP-A-58-157739 and JP-A-58-216138 disclose that 7-octen-1-al, 1,5-hexadiene or 1,7-octadiene is replaced with sulfolane or 1,4-butanediol. Hydroformylation in the presence of water-soluble sulfonated phosphine in water to extract the reaction mixture with higher alcohols or a mixture of hydrocarbons and hydrocarbons, thereby suppressing elution of the catalyst and reaction solvent into the extraction layer. Linear α, ω-
It is described that only dialdehyde can be selectively extracted and separated as a hemiacetal compound of a higher alcohol. Further, JP-A-58-21638 discloses that a hydroformylation reaction of α, ω-diolephin, α, ω-alkenal or the like is carried out in an organic solvent such as toluene which is insoluble in water, and the obtained reaction mixture is prepared. A method of contacting with an aqueous solution of alkali bisulfite such as sodium bisulfite is described. In this case, the α, ω-dialdehyde produced by the hydroformylation reaction is selectively extracted and separated in the aqueous layer as an adduct of alkali hydrogen sulfite.

[Problems to be solved by the invention]

According to the above-mentioned JP-A-57-167937, various olefins such as monoolefin containing a functional group can be used as a reaction raw material, but α, ω having 6 to 10 carbon atoms is used.
-No specific mention is made in the publication of the use of diolephine or α, ω-alkenals having 7 to 11 carbon atoms as a reaction raw material. According to the studies by the present inventors, the hydroformylation method described in JP-A-57-167937 shows a desirable result when the above α, ω-diolephin or α, ω-alkenal is used as a reaction raw material. Invented not to give. That is, since the reaction raw material α, ω-diolefin or α, ω-alkenal is hardly dissolved in water, when water is used as the reaction solvent, the contact efficiency between the reaction raw material and the rhodium catalyst dissolved in water is low. However, the hydroformylation reaction did not proceed at all. When a mixture of water and an organic solvent that can be mixed with water is used as the reaction solvent, α,
It is possible to improve the reaction rate of hydroformylation by increasing the solubility of ω-diolephin or α, ω-alkenal in the reaction solvent. However, the hydroformylation of α, ω-diolephin or α, ω-alkenal is within the range specifically described in JP-A-57-167937 (for example, ethyl alcohol, acetone, acetonitrile, dimethoxyethane). When a homogeneous reaction system is carried out in a mixed solution of water, etc.), the reaction proceeds, but the obtained reaction mixed solution is within the range specifically described in JP-A-57-167937. No matter which extractant (diethyl ether, benzene or toluene) is used, a large amount of reaction solvent and catalyst will elute into the extractant, which is the target product α, ω
-It became clear that the dialdehyde could not be selectively extracted and separated into the extractant. If a large amount of the catalyst component other than the target product in the extraction agent is eluted in the extraction method, it is accompanied by deactivation of the catalyst eluted in the distillation purification step of the target product from the subsequent extraction layer. The method is extremely disadvantageous for industrial implementation. In order to enable the hydroformylation reaction and the subsequent extractive separation of the catalyst from the product to be industrially advantageous, the reaction rate should be set to an industrially satisfactory level for the hydroformylation reaction of a specific olefin. It is necessary to find a suitable combination of a maintainable reaction solvent and an extractant capable of selectively extracting and separating only the hydroformylation product from the resulting reaction mixture.

The methods described in JP-A-58-157739 and JP-A-58-216138 disclose the hydroformylation of α, ω-diolephin or α, ω-alkenal and linear α, from the reaction mixture. This is an excellent method for producing a linear α, ω-dialdehyde, which is carried out by extracting and separating ω-dialdehyde by using a combination of a specific reaction solvent and an extractant. However, in such a method, in order to obtain α, ω-dialdehyde, the linear α, ω-dialdehyde obtained in the extraction and the hemiacetal compound of a higher alcohol are subjected to distillation to decompose into α, ω-dialdehyde. However, not only the recovery operation of higher alcohols is necessary in addition to the above, but also a part of α, ω-dialdehyde is converted into an acetal compound during the distillation operation, which results in α, ω. With the disadvantage that the yield of dialdehyde is likely to be reduced.

Further, the method described in JP-A-58-21638 requires a complicated operation of decomposing an alkali bisulfite adduct to isolate a desired α, ω-dialdehyde from the obtained extracted water layer. Not only is it necessary, but it is also not economical because it consumes a large amount of alkali hydrogen sulfite.

Therefore, it is an object of the present invention to provide a method for industrially advantageously producing α, ω-dialdehyde from α, ω-diolefin or α, ω-alkenal as a raw material.

[Means for solving problems]

According to the present invention, the above object is (i) a weight ratio of sulfolane to water of 15/85 to 75/2.
10 to 30 per 1 gram atom of rhodium in the sulfolane aqueous solution and rhodium compound in the rhodium compound
The following general formula (I) in an amount within the range of 0 mol. [Wherein R ¹ is a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, a saturated alicyclic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group, R ² is a hydrogen atom, a methyl group, A methoxy group or a halogen atom, n is a number of 0 or 1, x is a number of 0, 1 or 2, y and z are numbers of 0, 1, 2 or 3 respectively (where y and z
Does not become 0 at the same time, and the condition x + y + z = 3 is satisfied), and A is Or -C (CH ₃₎ a ₂ COOM, B is -SO ₃ M or -COOM (although, M represents an alkali metal). In the presence of a monodentate coordinating phosphine represented by] the following general formula _{(II) CH 2 = CH- (} CH 2) m -CH = CH 2 (II) ( wherein m is an integer of 2 to 6 .) Represented by the following general formula (I
II) CH ₂ = CH- (CH ₂ ) _m CH ₂ CH ₂ CHO (III) (wherein m represents the same as above), and the α, ω-alkenal is reacted with hydrogen and carbon monoxide. By hydroformylation, and (ii) the reaction mixture obtained in the step (i) is a saturated alicyclic hydrocarbon having 5 to 10 carbon atoms at a temperature of 40 ° C or higher under a mixed gas atmosphere of hydrogen and carbon monoxide. Α, ω-dialdehyde is extracted and separated by extraction in step (iii), and the raffinate layer containing the catalyst component obtained in step (ii) is circulated to the hydroformylation reaction step of step (i), It is achieved by providing a method for producing an α, ω-dialdehyde characterized by:

The above general formula used as a raw material in the method of the present invention
As α, ω-diorefin represented by (II), 1,5
-Hexadiene, 1,7-octadiene, 1,9-decadiene, etc. are specifically exemplified, and the general formula (III)
Specific examples of the α, ω-alkenal represented by 6-heptene-1-al, 7-octene-1-al, 8-nonene-1-al, 10-undecen-1-al, and the like. Rhodium compounds used in the hydroformylation reaction according to the method of the present invention include:
Any rhodium compound having a hydroformylation catalytic ability under the reaction conditions can be used. Such rhodium compounds include general formulas such as HRh (CO) [P (C ₆ H ₅ ) ₃ ] ₃
Rh ₄ (C) (P ▲ R ³ ₃ ▼) ₃ (R ³ represents an aromatic hydrocarbon group) Rhodium carbonyl complex compound; Rh ₄ (C
Examples thereof include rhodium carbonyl clusters such as O) ₁₂ and Rh ₆ (CO) ₁₆ . In addition, PhCl 〔P (C
₆ H ₅ ) ₃ ] ₃ , rhodium acetylacetonate, rhodium acetate, rhodium chloride, rhodium oxide and other rhodium compounds can be used after activation by a usual method in a separately provided catalyst preparation tank. Rhodium compounds are usually
It is used within a concentration range of 0.05 to 10 milligram atom in terms of rhodium atom per hydroformylation reaction mixture liquid.

In the monodentate phosphine represented by the general formula (I) used in the present invention, R ¹ is a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, a saturated alicyclic hydrocarbon group or a substituted or unsubstituted aromatic group. A hydrocarbon group, specifically, a saturated aliphatic hydrocarbon group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group,
Examples thereof include n-octyl group; a saturated alicyclic hydrocarbon group such as cyclohexyl group and methylcyclohexyl group; and an aromatic hydrocarbon group such as phenyl group, benzyl group and tolyl group. In addition, the aromatic hydrocarbon group may be substituted with a substituent such as a methoxy group, a chloro group, a cyano group or a nitro group. M in -SO ₃ M or -COOM represented by B in the general formula (I) represents an alkali metal, and specifically, lithium, sodium, potassium and the like. In the general formula (I), when B is —SO ₃ M or —COOM, the phosphine is usually used as an alkali metal salt, but instead of the alkali metal salt, a carboxylic acid, a sulfonic acid or an ester thereof is used. Can also be converted into an alkali metal salt by reacting with a salt of an alkali metal hydroxide, heavy carbonate, carbonate or the like in the reaction system or in another reaction vessel. Among the monodentate phosphines represented by the general formula (I), R ¹ is particularly an aromatic hydrocarbon, n is 0 or 1, x is 0, 1 or 2, y is 0 or 1, z is 0, Diaryl phosphines or triaryl phosphines represented by 1, 2 or 3 (provided that y and z are not 0 at the same time and satisfy x + y + z = 3) are preferable. The monodentate phosphine represented by the general formula (I), specifically, _{(C 6 H 5) 2 PCH} 2 CH (CH 3) COONa, (C 6 H 5) 2 PCH 2 CH (CH 3) COOK, and the like _{(C 6 H 5) 2 PCH} 2 CH (CH 3) COOLi To be The amount of these monodentate phosphines used is in the range of 10 to 300 mol, preferably 30 to 2 per gram atom of rhodium.
Within the range of 50 moles.

The hydroformylation reaction according to the invention is carried out in an aqueous sulfolane solution in which the weight ratio of sulfolane to water is 15/85 to 75/25. If the concentration of sulfolane in the aqueous sulfolane solution is less than 15 weight percent, the reaction rate decreases. Further, when the concentration of sulfolane in the aqueous solution exceeds 75% by weight, the elution rate of sulfolane and the catalyst component in the extraction layer becomes high in the extraction performed subsequent to the reaction. A particularly desirable weight ratio of sulfolane to water is 25/75
-60/40. The hydroformylation reaction according to the present invention is usually within the range of 40 to 110 ° C, preferably 60 to 9 ° C.
It is carried out at a temperature in the range of 0 ° C. The hydrogen / carbon monoxide molar ratio in the mixed gas of hydrogen and carbon monoxide used in the hydroformylation reaction is usually selected from the range of 1/2 to 5/1 as the input gas composition. It should be noted that any gas inert to the hydroformylation reaction, such as methane, ethane, propane, nitrogen, helium, argon, carbon dioxide, etc., may coexist in the reaction system.
The reaction pressure is generally selected from the range of 1 to 200 atm as the total pressure, but it is preferably 1 to 30 atm in order to particularly increase the selectivity to the linear α, ω-dialdehyde. preferable.

Since the solubility of α, ω-diolefin or α, ω-alkenal in the reaction mixture under the reaction conditions is relatively small, the feeding rate of α, ω-diolefin or α, ω-alkenal is adjusted according to the reaction rate. Therefore, it is desirable to prevent the reaction system from becoming heterogeneous in terms of operation and stabilization of the activity of the rhodium catalyst present in the reaction system. The concentration of α, ω-dialdehyde in the reaction mixture is preferably in the range of 0.5 to 3 mol / from the viewpoint of catalytic activity and product separation.

An appropriate amount of a buffer solution represented by a mixed solution of sodium dihydrogen phosphate and sodium monohydrogen phosphate and the like is allowed to coexist in the hydroformylation reaction system of the present invention to adjust the pH of the reaction mixed solution to 5 to 5.
By carrying out the reaction while keeping it within the range of 7, the activity of the catalyst present in the reaction system can be stabilized.

The reaction mixture obtained by the above hydroformylation reaction is subjected to extraction operation. Specific examples of the saturated alicyclic carbon hydrogen having 5 to 10 carbon atoms used as an extractant in the extraction step according to the method of the present invention include cyclopentane, cyclohexane, methylcyclohexane, decalin, etc., but they are easily available. In view of the boiling point and the like, cyclohexane is particularly preferable. The amount of these extractants used is in the range of 1/5 to 3/1 by volume ratio, preferably in the range of 1/2 to 2/1 with respect to the hydroformylation reaction mixture used for extraction. If the amount of the extractant used is less than ⅕ in volume ratio with respect to the reaction mixture, the extraction rate of production is lowered, which is not preferable. On the contrary, when the amount of the extractant used is more than 3/1 in terms of volume ratio to the reaction mixture, the amount of the extractant is large when the product is separated from the obtained extraction layer, and the recovery amount is large. It is economically disadvantageous because of the cost.

The extraction temperature in the extraction according to the present invention is 40 ° C or higher. There is no particular limitation on the upper limit of the extraction temperature, but the extraction is usually performed because of the relationship with the pressure of the mixed gas of hydrogen and carbon monoxide in the extraction system described later and the fact that there is no advantage of extracting at a temperature above the reaction temperature. , At a temperature below the reaction temperature. Therefore, it is preferable to extract at a temperature in the range of 40 to 110 ° C., particularly preferably 50 to 100.
The temperature is in the range of ° C. When the extraction temperature is less than 40 ° C, the extraction rate of α, ω-dialdehyde into the extractant extract is low and not practical.

The extraction operation is performed in a mixed gas atmosphere of hydrogen and carbon monoxide. The molar ratio of hydrogen to carbon monoxide in the mixed gas is hydrogen / carbon monoxide within the range of 1/10 to 10/1, preferably within the range of 1/5 to 5/1. The extraction operation is carried out by using a mixed gas of hydrogen and carbon monoxide in which the molar ratio of hydrogen / carbon monoxide is less than 1/10 or more than 10/1, hydrogen gas (single), carbon monoxide gas (single),
Alternatively, it is not preferable to carry out the reaction in an atmosphere of an inert gas (single) such as nitrogen, carbon dioxide, or argon because a part of the catalyst is deactivated during the extraction. It is practically advantageous that the atmosphere in the extraction operation is an off-gas atmosphere from the reaction system. It should be noted that there is no problem even if an inert gas such as nitrogen, helium, or argon is allowed to coexist in the extraction system within a range that does not adversely affect the extraction. There is no particular upper limit to the pressure in the extraction system, but the partial pressure of the mixed gas of hydrogen and carbon monoxide is usually selected from the range of 1 to 30 atm. The pressure in the extraction system correlates with the extraction temperature and is related to the stability of the catalyst in the extraction system. Generally, when the extraction temperature is high, it is advantageous to have a high pressure to some extent. When it is within the range, the activity of the catalyst during the extraction operation can be stably maintained under a pressure within the range of 3 to 5 atm. It is industrially preferable to carry out the extraction operation by a continuous method, but the batch method may be used.

According to the extraction operation according to the present invention, the products such as α, ω-dialdehyde and the unreacted raw material olefin are separated in the extraction layer (upper layer), and the catalyst components are separated in the raffinate layer (lower layer). The raffinate layer is used as it is or after a part of it is subjected to a known catalyst activation treatment as required, and then recycled to the hydroformylation reaction step for reuse.

It is possible to easily separate and obtain α, ω-dialdehyde with high purity by subjecting the obtained extraction layer as it is or after washing it with a small amount of water to a solvent distillation step and distilling the residue under reduced pressure. it can. The extractant collected at this time can be recycled to the extraction step and reused. Further, it is also possible to recover the unreacted raw materials or the intermediate products α, ω-diolefin and α, ω-alkenal by a distillation operation. In this case, the recovered α, ω-diolefin and α, The ω-alkenal can be reused as a raw material by being recycled to the hydroformylation reaction step. Further, when chemically inducing α, ω-dialdehyde into a corresponding alkanediol, alkanedicarboxylic acid, or alkanediamine, the extraction layer may be washed as it is or with a small amount of water without removing the extractant. It can also be subjected to reactions such as reduction, oxidation and amination.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

Example 1 A stainless steel autoclave of Content 1 equipped with a thermometer, an electromagnetic stirrer, a gas inlet and a gas outlet was used for Ph.
₄ (CO) ₁₂ 0.125 mmol, After charging 50 mmol, 250 ml of water and 250 ml of sulfolane and thoroughly replacing the inside of the autoclave with a hydrogen / carbon monoxide mixed gas (molar ratio 2/1), the pressure inside the autoclave was adjusted to 10 atm by the mixed gas of this composition. While the flow rate of the discharged gas was kept at 10 / hour, the internal temperature was heated under stirring until the internal temperature became constant at 75 ° C., and the stirring was continued for further 30 minutes. Then, with vigorous stirring, 74.3-octen-1-al (64.3 g, containing 500.1 mmol, purity 98% and 2% n-octanal) was continuously fed into the autoclave for 1 hour by a metering pump. Was added. After the addition was completed, stirring was continued for another 1.5 hours. After reacting for a total of 2.5 hours, stirring was stopped and the autoclave was cooled. Then, a very small amount of the reaction mixture was taken out and analyzed by gas chromatography to find that the remaining amount of 7-octen-1-al was 85.3 mmol (conversion rate 82.6%).
And 1,9-nonanediar and 2-methyl-
It was found that 348.5 mmol and 62.2 mmol of 1,8-octanediol were formed, respectively. Then, the reaction mixture was pressure-fed through a pipe into a pressure-resistant glass autoclave kept at an internal pressure of 3 atm with a hydrogen / carbon monoxide mixed gas (molar ratio 1/1). 250 ml of cyclohexane was added to the glass autoclave and the internal temperature was kept at 6 atm with the internal pressure kept at 3 atm.
The temperature was adjusted to 5 ° C. and the mixture was stirred for 5 minutes. Immediately after stirring was stopped, two layers were separated. After standing for 5 minutes, the upper cyclohexane layer was taken out of the system through a pipe using the internal pressure.
Then, cyclohexane 25 was newly added to the pressure-resistant autoclave in which the lower layer remained at an internal pressure of 3 atm and an internal temperature of 65 ° C.
0 ml was added, the mixture was stirred for 5 minutes under the same conditions, and allowed to stand for 5 minutes. The upper cyclohexane layer was taken out of the system and combined with the previously taken cyclohexane layer, and then the extract contained in the cyclohexane layer was analyzed. When analyzed by gas chromatography, 7-octen-1-al as the starting material and 1,9-nonanedial and 2-methyl-1,8-octanedial as products were 8
It was found to be 0.0 mmol, 219 mmol and 42.9 mmol. From this result, the extraction rate of the product α, ω-dialdehyde (1,9-nonanedial and 2-methyl-1,8-octanedial) was 6
Invented to be 3.7%. The amount of sulfolane eluted in the extract was 8.8 g. Furthermore, as a result of atomic absorption analysis and colorimetric analysis of rhodium and phosphorus compounds, the rhodium and phosphorus compounds eluted in the extractant are 0.05 ppm and 2.6 ppm in terms of rhodium and phosphorus atoms, respectively. It has been found. Next, 7 ml of sulfolane was added to the extraction catalyst layer remaining in the glass autoclave, and the catalyst layer was transferred into the above-mentioned stainless steel autoclave (reactor) so as not to contact the air by utilizing the pressure difference. Under the same reaction conditions as the first reaction, 64.3 g of 7-octen-1-al was continuously fed into the reactor for 1 hour, and then the reaction was continued for another 1.5 hours. Then, extraction was performed under the same operation and conditions as in the first time, and 7-octene-1-al, 1,9-nonanedial and 2-methyl-1,8-octanedial were 84.4 in the cyclohexane layer respectively. Mmol, 288 mmol and 54.
8 mmol had been extracted. The amount of sulfolane eluted in the extractant was 9.8 g, and the amounts of rhodium and phosphorus compounds eluted in the extractant were 0.041 ppm and 2.0 ppm in terms of rhodium and phosphorus atoms, respectively. Then
After adding 7.8 ml of sulfolane to the raffinate catalyst layer, the same reaction and extraction operation as the second time was repeated up to five times. During this period, except that 7.8 ml of sulfolane was added to the raffinate catalyst layer,
Rhodium catalyst and phosphine compound were not added at all. Table 1 shows the analysis results of the compounds extracted in the cyclohexane layer obtained in the third, fourth and fifth operations.

Examples 2 to 4 and Comparative Examples 1 to 8 The same operation as the first reaction and extraction operation of Example 1 was performed except that the type of extractant or the extraction temperature was changed as shown in Table 2. Natsuta. The results obtained are shown in Table 2.

Example 5 The same reactor used in Example 1 was charged with Rh ₆ (CO) ₁₆
0.1 mmol, After charging 45 mmol, 250 ml of water and 250 ml of sulfolane and thoroughly replacing the inside of the autoclave with a hydrogen / carbon monoxide mixed gas (molar ratio 3/1), the pressure inside the autoclave was adjusted to 10 atm by the mixed gas of this composition. While maintaining the temperature, the temperature was raised until the internal temperature reached a constant temperature of 80 ° C., and stirring was continued for 30 minutes. Then, 40 g (364 mmol) of 1,7-octadiene was continuously added into the autoclave by a metering pump over 1.5 hours with vigorous stirring. After the addition was completed, stirring was continued for another 1.5 hours. During the reaction, a hydrogen / carbon monoxide mixed gas (molar ratio 3/1) was used, the internal pressure of the autoclave was 10 atm, and the discharge gas flow rate was 10
It was introduced into the autoclave through the pressure control valve while maintaining the time. After performing the reaction for a total of 3 hours, a very small amount of the reaction mixture was taken out and analyzed by gas chromatography. The residual amount of unreacted 1,7-octadiene was 5
7.5 mmol (conversion rate 84.2%), 1,10
-Decandial was found to have formed 152 mmol. In addition, 2-methyl-1,9-nonanedial, 2,7-dimethyl-1,8-octanedial, 8-nonen-1-al and 2-methyl-7-octen-1-al are 35 mmol each. 3 mmol, 104 mmol and 12 mmol had formed.
Then, extraction was performed in the same manner as in Example 1. As a result of analyzing the obtained cyclohexane layer by gas chromatography, 1,7-octadiene and 1,10-extracted were extracted.
Decandial, 2-methyl-1,9-nonanediol, 2,7-dimethyl-1,8-octanediol, 8
-Nonene-1-al and 2-methyl-7-octen-1-al are 54.6 mmol, 98.0 mmol, 22.6 mmol, 1.9 mmol and 85.2, respectively.
It was found to be mmol and 9.9 mmol.
From this result, the extraction rate of dialdehyde was 64.7%. Furthermore, as a result of atomic absorption analysis and colorimetric analysis of rhodium and phosphorus compounds, the rhodium and phosphorus compounds eluted in the extractant were 0.04 ppm and 2.3 ppm in terms of rhodium and phosphorus atoms, respectively.
It was. Next, after adding 5 ml of sulfolane to the extraction residue catalyst layer, it was transferred into the reactor while avoiding contact with air by utilizing the pressure difference. After 40 g of 1,7-octadiene was continuously fed and reacted under the same reaction conditions as in the first reaction, the reaction was carried out in the same manner as in the first reaction.
In this way, the reaction and extraction operations were repeated 5 times in total. During this period, the catalyst and phosphine were not added to the raffinate catalyst layer except 7.5 ml of sulfolane. Table 3 shows the analysis results of the compounds extracted in the cyclohexane layer obtained in the second and subsequent repetitions.

Examples 6 to 8 and Comparative Examples 9 to 11 The first reaction and extraction operation of Example 5 except that the extraction temperature or the extraction atmosphere was changed as shown in Table 4 and the extraction time was changed to 2 hours. Performed the same operation as.
Furthermore, the second reaction was carried out using the extraction catalyst liquid obtained in the same manner as in the second reaction operation of Example 5. The ratio of the conversion of 1,7-octadiene in the second reaction to the conversion of 1,7-octadiene in the first reaction is shown in Table 4 as the specific activity of the catalyst.

Example 9 Into the same reactor used in Example 1 Charge 50 mmol, 300 ml of water and 200 ml of sulfolane, and mix hydrogen / carbon monoxide gas (molar ratio 1/1).
The hydroformylation reaction of 7-octen-1-al was carried out in the same manner as in Example 1 except that the pressure was kept at 15 atm and the reaction temperature was 80 ° C. After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find that the unreacted 7-
The remaining amount of octene-1-al is 51.5 mmol (conversion rate 90%), and the amount of 1,9-nonane dial and 2
-Methyl-1,8-octanediol is 376 each
It was found that 1 mmol and 71.0 mmol had been produced. The reaction mixture was extracted under the same conditions as in Example 1. 7-octen-1-al, 1,9 in the extraction solvent
49.9 mmol, 236 mmol and 51.8 mmol of 2-nonanedial and 2-methyl-1.8-octanedial were extracted (extraction rate 64.
4%). The amount of sulfolane eluted in the extract was 8.2 g.
The amounts of the rhodium and phosphorus compounds eluted were 0.06 ppm and 3.5 ppm in terms of rhodium and phosphorus atoms, respectively.

Example 10 The same reactor used in Example 5 was charged with Ph ₄ (CO) ₁₂ 0.
25 mmol, 100 mmol, 300 ml of water and 200 ml of sulfolane
After heating, the temperature was raised to 41 g of 1,5-hexadiene.
(500 mmol) was continuously added into the autoclave over 1 hour, and the reaction was performed under the same conditions as in Example 5 except that the reaction was continued for 2.5 hours after the addition was completed. After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find that the residual amount of 1,5-hexadiene was 15 mmol (conversion rate 97%), and 1,8-octanedial, 2-methyl-1, 7-Heptane Diar, 2,5-
Dimethyl-1,6-hexanedial and 6-hepten-1-al were 310.4 mmol, 69.
It was found that 8 mmol, 7.8 mmol and 87.3 mmol were produced. Then, the extraction temperature is 70 ℃
And 5 with hydrogen / carbon monoxide mixed gas (molar ratio 3/1)
The extraction operation was performed in the same manner as in Example 5 except that the atmospheric pressure was used. 1,5-hexadiene, 1,8-octanedial, 2-methyl-1,7-heptanedial, 2,5-dimethyl-1,6-hexanedial and 6-heptene-1 are included in the extractant. 13.5 mmol, 192.4 mmol, 43.3 mmol, 4.9 mmol and 69.8 mmol of Earls were respectively extracted (total extraction of dialdehyde was 62%). The amount of sulfolane extracted in the extraction agent was 7.4 g, and the rhodium and phosphorus compounds were 0.0 and 10 in terms of rhodium and phosphorus atoms, respectively.
It was 5 ppm and 2.6 ppm.

Example 11 Example 10 was repeated except that 69 g (500 mmol) of 1,9-decadiene was used as the starting diene in Example 10.
The reaction was performed in the same manner as in. After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find 1,9-
The residual amount of decadiene was 30 mmol (conversion rate 94%), and 1,12-dodecanedial, 2-methyl-1,
11-undecandial, 2,9-dimethyl-1,1
0-decandial and 10-undecen-1-al are 277.9 mmol, 61.7 mmol, respectively.
It was invented that 3.5 mmol and 114.3 mmol were produced. Then, as a result of performing the extraction operation under the same conditions as in Example 10, 1,9-decadiene,
2,12-dodecanedial, 2-methyl 1,11-undecanedial, 2,9-dimethyl-1,10-tecandial and 10-undecen-1-al are 28.5 mmol and 180.6 mmol, respectively. 40.1
Mmol, 2.3 mmol, and 99.4 mmol were extracted (total dialdehyde extraction rate: 65%). The amount of sulfolane eluted in the extract was 8.0 g, and the rhodium and phosphorus compounds were 0.04 ppm and 3.3 ppm in terms of rhodium and phosphorus atoms, respectively.

Comparative Example 12 The same reaction operation was carried out as in Example 4, except that the reaction solvent was changed to a mixed solvent of water and sulfolane to 500 ml of water. After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find that the amount of unreacted 1,7-octadiene remaining was 480 mmol (conversion rate 4%), indicating that almost no reaction had occurred.

〔The invention's effect〕

According to the invention, as is apparent from the above examples,
The α, ω-dialdehyde can be easily produced from α, ω-diolefin or α, ω-alkenal in good yield. According to the present invention, the expensive rhodium catalyst used in the hydroformylation reaction step can be recycled and reused with almost no reduction in activity, and the loss of the rhodium catalyst, monodentate phosphine and sulfolane present in the hydroformylation reaction system can be reduced. Because there is almost no
The method for producing α, ω-dialdehyde provided by the present invention is industrially extremely advantageous.

Claims (4)

[Claims] 1. The weight ratio of (i) sulfolane to water is 15/8.
A rhodium compound in an aqueous solution of 5-75 / 25 sulfolane and an amount of the following general formula (I) within the range of 10 to 300 mol per 1 gram atom of rhodium in the rhodium compound. [Wherein R ¹ is a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, a saturated alicyclic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group, R ² is a hydrogen atom, a methyl group, A methoxy group or a halogen atom, n is a number of 0 or 1, x is a number of 0, 1 or 2, y and z are numbers of 0, 1, 2 or 3 respectively (where y and z
Does not become 0 at the same time and satisfies the condition x + y + z = 3), and A is Or -C (CH ₃₎ a ₂ COOM, B is -SO ₃ M or -COOM (although, M represents an alkali metal). In the presence of a monodentate coordinating phosphine represented by] the following general formula _{(II) CH 2 = CH- (} CH 2) m -CH = CH 2 (II) ( wherein m is an integer of 2 to 6 .) Represented by the following general formula (I
II) CH ₂ = CH- (CH ₂ ) _m CH ₂ CH ₂ CHO (III) (wherein m represents the same as above), and the α, ω-alkenal is reacted with hydrogen and carbon monoxide. By hydroformylation, and (ii) the reaction mixture obtained in the step (i) is a saturated alicyclic hydrocarbon having 5 to 10 carbon atoms at a temperature of 40 ° C or higher under a mixed gas atmosphere of hydrogen and carbon monoxide. Α, ω-dialdehyde is extracted and separated by extraction in step (iii), and the raffinate layer containing the catalyst component obtained in step (ii) is circulated to the hydroformylation reaction step of step (i), A method for producing an α, ω-dialdehyde characterized by: 2. The process according to claim 1, wherein the saturated alicyclic hydrocarbon used in step (ii) is cyclohexane. 3. The extraction temperature in step (ii) is 40 to 110.
The manufacturing method according to claim 1 or 2, which is within the range of ° C. 4. The method according to claim 1, wherein the extraction operation in step (ii) is carried out in a mixed gas atmosphere of hydrogen and carbon monoxide having a hydrogen / carbon monoxide molar ratio of 1/10 to 10/1. The manufacturing method as described in the first item, the second item, or the third item.