JPS58216138A - Preparation of 1,8-octanedial or 1,10-decanedial - Google Patents

Abstract

PURPOSE:To obtain the titled high-purity compound industrially, by subjecting 1,5-hexadiene, etc. to hydroformylation under specific conditions, extracting the titled compound from the reaction mixture with a specified solvent, circulating the remaining layer after the extraction through the reaction process. CONSTITUTION:1,5-Hexadiene or 1,7-octadiene and a mixed gas of H2 and CO are subjected to hydroformylation in an aqueous solution of (a) sulfolane, 1,4- butanediol or 1,6-hexanediol and (b) water in a weight ratio of a/b of (15/85)- (75/25) in the presence of a rhodium complex compound and a compound shown by the formula (M is Na, K or Li). The reaction mixture is extracted with about 5-12C saturated aliphatic primary alcohol or a mixture of the compound and about 5-10C saturated aliphatic or alicyclic hydrocarbon, the titled compound is prepared from the extraction layer, the remaining layer after extraction containing the catalytic component is circulated through the reaction process, to give the titled compound useful as protein and immobilizing agent for enzyme, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 1,8-octanedial or 1.8-octanedial. The present invention relates to a method for producing lO-decandial, and more particularly, it relates to a method for producing 1,8-octanedial or 'il, 10
-Relates to a method for producing decanedial.

4- 1.8-octanedial or 1.10-decanedial is a protein and enzyme immobilizing agent and a bactericidal agent.

It is well known that it is an extremely useful compound as a polymer crosslinking agent and as a starting material for corresponding dicarboxylic acids, diols, and diamines, and its industrial production methods include 1.5-hexadiene or 1.7-hexadiene. A production method using a hydroformylation reaction of octadiene has also been proposed. However, the conventionally proposed method includes the following two technical problems, and perhaps because these have not been resolved, 1.8-octanedial and 1.8-octanedial and 1.8-octanedial and 1. lO-
Decandial has not yet been produced on an industrial scale, and the corresponding dicarboxylic acid esters have only been reagently synthesized by partial reduction methods using very expensive reagents. One of the problems with the conventionally proposed method is that in the hydroformylation reaction of 1,5-hexadiene or 17-octadiene, at least three isomers (n-type dialdehyde, n-type dialdehyde and n-type dialdehyde and i-type dialdehyde), which have boiling points close to each other and are not thermally stable enough,
1,8 which is an n-type product from these isomer mixtures.
- octanedial or 1. It is virtually impossible to separate and obtain lO-decandial with high purity. Another technical problem with the previously proposed method is the deterioration of the catalytic activity of the rhodium catalyst when the reaction product is separated and obtained from the hydroformylation reaction mixture. In other words, in the conventionally proposed method, a distillation separation method is used to separate the rhodium catalyst and the reaction product. In the distillation separation method, it is difficult to avoid the accumulation of high boiling point by-products in the reaction system. In this way, when following the conventionally proposed method, high purity 1.8-octanedial or 1.10
- It is virtually impossible to produce decanedial industrially.

Based on this background, the present inventors produced highly purified 1,8-octanedial or 1.5-hexadiene or 1.7-octadiene. The present invention was achieved as a result of intensive research aimed at completing an industrially viable manufacturing method for lO-decandial. That is, according to the present invention.

(1) Sulfolane, 1,4-butanediol or 1.
M ratio of 6-hexanediol and water is 15/85 to 75
/25 sulfone, 1,4-butanediol or 1
．． (a) rhodium complex compound and (b) diphenylphosphinobenzene-m- in 6-hexanediol aqueous solution
1,5-hexadiene or 1,7- in the presence of sodium, potassium or lithium salts of monosulfonic acids.
Octadiene is hydroformylated using a mixed gas of hydrogen and carbon monoxide.

(It) A saturated aliphatic primary alcohol having about 5 to 12 carbon atoms, or the primary alcohol and a saturated aliphatic alcohol having about 5 to 10 carbon atoms for the reaction mixture obtained in step (1). 1,8-
octanedial or 1. Extract IO-decandial.

The raffinate layer containing the catalyst component is recycled to the hydrophor 7-mylation reaction step of step (1), and 1,8-octanedial or 1°10
- by a method consisting of obtaining decanedial 1
．． 8-octanedial t7Thitl and 10-decanedial can be produced in high yield.

In addition, according to the present invention, the extraction operation In of the step (I[)
- A primary alcohol selected from the group consisting of hexanol, n-heptatool, n-octatool, n-nonanol and n-decanol, or the primary alcohol and hexane, heptano.

10 to 60 using a mixture of saturated aliphatic hydrocarbons or saturated alicyclic hydrocarbons selected from the group consisting of octane, decane, cyclohekinane and methylcyclohexane.
1.8-octanedial or 1.8-octanedial by washing the resulting extracted layer with water and keeping it at a temperature of 0-50°C. lO-Decanedial has the general formula (A) 8- (where n is 6 or 8 and R has 6 to 10 carbon atoms)
(representing a straight-chain saturated aliphatic hydrocarbon group) in the form of crystals of dihemiacetal, and branched dials do not precipitate crystals of dihemiacetal under the same conditions. Very high purity 1.8-octanedial can be obtained by separating and obtaining Fil,
10-decandial can be obtained.

1,5-hexadiene or H 1 according to the method of the invention
．． As the rhodium complex compound used in the hydroformylation reaction of 7-octadiene, any rhodium complex compound having a hydroformylation catalytic ability under the reaction conditions can be used. Many such rhodium complex compounds are already known, and most of these conventionally known rhodium complex compounds can be used in the method of the present invention. Specifically, HRh(CO)(PAa)3(A; aryl group),
Examples include Rh4(CO), 2-9- and Rha(CO)Is. Also.

Rha(PAa)3. Rh(acac)a (aea
e; 7 cef ru ace) f-to group), Rh(O
Ac) a (OAc; acetoxyl group), (Rh(C
O)2(PAs)2]2. It is also possible to use rhodium (complex) compounds such as Rhα3.3H20 and Rh20s after activation by a conventional method in a separate catalyst adjustment tank. The rhodium complex compound is usually 0.05 to 1 in terms of rhodium atoms per 1 liter of hydroformylation reaction solution.
It is used in a concentration range of O milligram atom. The sodium salt, potassium salt, and lithium salt of luciphenylphosphinobenzene-m-monosulfonic acid used in the hydroformylation reaction of the present invention are expressed by the following general formula (wherein M is Na, Ki, or Li ((represents) These diphenylphosphinobenzene-m-monosulfonic acid salts are used in an amount of 10 equivalents or more, preferably 25 equivalents or more per gram of rhodium. 1,5-hexadiene according to the method of the present invention and c1.
The hydroformylation reaction of 7-octadiene is carried out using sulfolane, 1.4-butanediol t*itl, sulfolane with a weight ratio of 6-hexanediol and water of 15/85 to 75/25, ■, 4-butanediol or 1.6 - carried out in aqueous hexanediol solution.

Among these, it is more preferable to use a sulfolane aqueous solution in consideration of reaction results, subsequent product separation steps, and chemical stability. The concentration of sulfolane, 1,4-butanediol or 1,6-hexanediol in the aqueous solution is 1
If the amount is less than 5% by weight, the reaction rate will decrease and the layer separation property in step (n) will deteriorate, which is not preferable. Furthermore, if the concentration of the aqueous solution exceeds 75% by weight, the elution rate of the solvent and catalyst components into the extraction layer will increase in step (n), which is not preferable. Particularly preferred sulfolane, 1,4-butanediol or 1°6
-The concentration of hexanediol aqueous solution is sulfolane, 1.4
-Butanediol or 1,6-hexanediol and water in a weight ratio of 25/75 to 60/40.

This hydroformylation reaction is usually carried out at a temperature of 40 to 110°C, preferably 60 to 90°C. In the hydrogen/carbon oxide mixed gas used in the reaction, the molar ratio of hydrogen to carbon monoxide is usually selected within the range of 0.5 to 5 as a major gas composition. The reaction pressure is generally selected from within the range of 1 to 30 atmospheres. The hydroformylation reaction can be carried out in a stirred reactor or a bubble column reactor in a continuous mode or in a patch mode. Since the solubility of the raw material diene and the reaction intermediate monoaldehydes in the reaction mixture under the reaction conditions is relatively low, 1,5-hexadiene or 1,7-octadiene is supplied depending on the reaction rate. It is desirable to control the rate, which can prevent the reaction system from becoming heterogeneous. The concentration of 1.8-octanedial or 1.10-decanedial in the reaction mixture is preferably within the range of 0.5 to 3 mol/e from the viewpoint of catalytic activity and product separation. According to detailed studies by the present inventors, one reaction system includes, for example, a mixed solution of sodium dihydrogen phosphate (NaI(2PO4) and sodium phosphate-hydrogen (Na2HP04),
The catalytic activity can be increased by keeping the pH' of the reaction mixture in the range of 5 to 7 by coexisting an appropriate amount of a buffer solution represented by a mixed solution of potassium dihydrogen phosphate (KH2PO4) and potassium hydrogen phosphate (K2HPO4). was observed to become more stable.

1.5-hexadiene or 1. The reaction mixture obtained by hydroformylating octadiene is a saturated aliphatic primary alcohol having about 5 to 12 carbon atoms, or a carbonized saturated aliphatic alcohol having about 5 to 10 carbon atoms with the primary alcohol. It is subjected to an extraction operation using a mixture with hydrogen.

Saturated aliphatic primary alcohols having about 5 to 12 carbon atoms include n-pentanol, n-he-? ? Examples include /-l, 2-ethelhexanol, 3,5.5-)limethylhexanol, n-hebutanol, n-octatool, n-nonanol, n-decanol, n-undecanol, and n-dodecanol. I can do it.

Examples of saturated aliphatic hydrocarbons or saturated alicyclic hydrocarbons having about 5 to 10 carbon atoms include pentane, hex-13-thane, hebutane, octane, nonane, decane, cyclohexane, and methylcyclohexane. can. By using a mixture of the primary alcohol and the saturated aliphatic hydrocarbon or saturated alicyclic hydrocarbon, the amount of the reaction solvent and catalyst component into the extraction layer can be increased compared to when the primary alcohol is used alone. The elution rate can be reduced. In this case, the ratio of the saturated aliphatic primary alcohol having about 5 to 12 carbon atoms and the saturated aliphatic hydrocarbon or saturated alicyclic hydrocarbon having about 5 to IO carbon atoms (primary alcohol/hydrocarbon ) has a capacity ratio of 115 to 5/l
It is better to be within the range of Solubility of extractant in water, boiling point,
Physical properties such as melting point, 1.8-octanedial or 1. Considering various points such as the extraction rate of lO-decane dial, the elution rate of the reaction solvent and catalyst components, and the ease of obtaining it including the price, it is found that
- a primary alcohol selected from the group consisting of hebutanol, n-octatool and n-nonanol; and a saturated aliphatic hydrocarbon or saturated fat selected from the group consisting of hexane, heptane, octane, decane and cyclohexane. Most preferably, mixtures with cyclic hydrocarbons are used. The proportion of these primary alcohols or mixtures of primary alcohols and saturated aliphatic hydrocarbons or saturated alicyclic hydrocarbons in the reaction mixture is 1 by volume.
It is practical to choose from within the range of 15 to 5/1.

In addition, since the phase separation property, extraction rate of reaction products, elution rate of reaction solvent and catalyst components, etc. are strongly influenced by the extraction temperature, it is industrially recommended to select the extraction temperature within the range of 10 to 60°C. It's advantageous. As the extraction device, generally used stirring type extraction towers, RDC type extraction towers, perforated plate towers, etc. are applicable. The extraction operation is usually carried out under an atmosphere of an inert gas such as nitrogen, helium, argon or a hydrogen/carbon oxide mixture. By the extraction operation, the reaction product and unreacted 1°5-hexadiene or 1,7-octadiene are separated into an extraction layer (upper layer), and the catalyst component is separated into a raffinate layer (lower layer). A part of the raffinate layer is subjected to a known catalyst activation treatment if necessary, and then subjected to the process (
It is recycled and reused in the hydroformylation reaction step of 1).

From the extraction layer obtained in the extraction step (It), 1.8 to -4 dia or 1. lO-decandial is separated and obtained (step (■)). The extraction layer contains a small amount of reaction solvent and catalyst components in addition to the reaction product and unreacted 1.5-hexadiene or 1.7-octadiene. Therefore, after washing the extracted layer with water at a volume ratio of at least 0.25, the extracted layer is washed with water at a volume ratio of at least 0.25.
．． Preferably, 8-octanedial or 1,10-decanedial is separated. Although there is no upper limit in a strict sense regarding the amount of water used, it is usually used at a volume ratio of 3 or less per extraction layer. By washing the extraction layer with water, the reaction solvent and catalyst components contained in a small amount in the extraction layer can be transferred to the water/layer side, making it easy to separate and recover the reaction solvent and catalyst components from the extraction layer. Ru. The aqueous solution containing the reaction solvent and catalyst component obtained by this operation can be recycled to the hydroformylation reaction step (I) after water is distilled off from the aqueous solution. 1,8-octanedial or 1,1O-decanedial can be obtained by subjecting the extracted layer to a normal distillation operation.

Further, according to detailed studies by the present inventors, in the extraction operation in step (It), a primary alcohol selected from the group consisting of In-hexanol, n-hebutanol, n-octatool, n-nonanol, and n-decanol or when carried out using a mixture of said primary alcohol and a saturated aliphatic hydrocarbon or saturated alicyclic hydrocarbon selected from the group consisting of hexane, heptane, octane, decane, cyclohexane and methylcyclohexane. When the extracted layer obtained by the operation is maintained at an appropriate temperature depending on the type of primary alcohol used in the extraction operation, the corresponding primary alcohol of 1,8-octanedial or 1,10-decanedial dihemiacetal [see general formula (A) above] precipitates as crystals,
It has been found that such crystals do not precipitate for branched dials and monoaldehydes, which are by-products of the hydroformylation reaction. Therefore, if this property is used, especially high-purity 1.
, 8-octanedial or 1,10-decanedial can be obtained. Namely.

After washing the extracted layer with water, it is kept at a temperature of 0 to 50°C to precipitate crystals, and the precipitated crystals are separated by an operation such as filtration or centrifugation, and the resulting crystals are separated as necessary. After washing with a small amount of water, the same primary alcohol used in step (■), saturated aliphatic hydrocarbon or saturated alicyclic hydrocarbon, or a mixture thereof, perform fractional distillation. This makes it possible to obtain extremely high purity 1,8-octanedial or 1,10-decanedial. ``If the extraction layer after crystal separation or a part thereof is subjected to a fractional distillation operation, unreacted raw material 1 monoaldehydes and branched dials can be separated. In addition, the extractant obtained at this time is used in the step (It
) and can be recycled and reused.

Hereinafter, the present invention will be explained more specifically with reference to Examples. explain.

Example 1 Thermometer 1 Stainless steel autoclave K with contents 11 equipped with an electromagnetic stirrer, a gas inlet and a gas outlet
Rh4(CO) 120.25 mmol.

After charging 150 ml of sulfolane and thoroughly replacing the inside of the autoclave with hydrogen/carbon oxide mixed gas (molar ratio 3/l), the mixed gas of this composition was used to maintain the pressure inside the autoclave at 10 atm and keep the internal temperature constant at 80°C. The mixture was heated until it became , and stirring was continued for an additional 30 minutes. The autoclave was connected to a gas reservoir filled with a hydrogen/carbon oxide mixed gas at a molar ratio of 3/1 through a pressure control valve so that a constant pressure was always maintained during one reaction.

Then, with vigorous stirring, 1,5-hexadiene 401
(8 mmol of 4B) was continuously added into the autoclave using a metering pump over 3 hours. After the addition of O, stirring was continued for another 1 hour. After a total of 4 hours of reaction, a very small amount of the reaction mixture was taken out and subjected to gas chromatography. Analysis revealed that 352.1 mmol of unresolved alcohol was produced. Other products include 2-methyl-
1,7-heptanedial, 2,5-dimethyl-1,6
-hexane dial and 6-hebuten-1-al were 83.5 mmol, 9.3 mmol and 8.3 mmol, respectively.
9 mmol was produced. Next, the reaction mixture was pumped into a three-necked flask with contents 21, which had been sufficiently replaced with a hydrogen/carbon oxide mixed gas (molar ratio 1/1), without coming into contact with air, and 150 d of n-hexanol and 35 d of hexane were added.
0 ml was added thereto, and the mixture was stirred for 20 minutes under a mixed gas atmosphere having the above composition while maintaining the internal temperature at 30°C. As soon as stirring was stopped, the mixture separated into two layers. After standing for 10 minutes, the lower layer (yellow) and the upper layer (colorless) were separated and analyzed by gas chromatography.
-octanedial, 2-methyl-1,7-hebutanedial, 2,5-dimethyl-1,6-hexanedial and 6--butene-1-al are each 89 units,
93%, 9! It was found that jφ and 99% were extracted into the extraction layer.

Next, remove the lower layer (raffinate layer) without exposing it to air.
was transferred to an autoclave, and 5 tLl of sulfolane was added. 1,5- of 4Or under the same reaction conditions as the first time.
Hegisadier was added continuously over a period of 3 hours, and stirring was continued for an additional hour. Analysis of the reaction mixture revealed that the remaining amount of 1.5-hexadiene in the second reaction was 25.8.
i 'J mole, 1,8-octanedial, 2
-Methyl-1,7-heptane dial, 2,5-dimethyl-1,6-hexane dial and 6-hebutene-1
It was found that 351.3 mmol, 81.4 mmol, 9.0 mmol, and 11.3 mmol of -R were produced, respectively. After performing an extraction operation using the same operating method and conditions as the first extraction, the raffinate layer was placed in an autoclave, and 5 rnl of sulfolane was added again.

The 321st hydroformylation reaction was carried out under the same reaction conditions and reaction operations as in the first reaction. After the reaction has stopped,
Analysis of the reaction mixture revealed that the remaining amount of 1,5-hexadiene and the amount of each product produced were almost the same as in the second reaction.

After washing the extract obtained from the three reactions and extraction operations described above with the same volume of water, the organic layer was left at a temperature of about 5° C. to precipitate crystals.

The crystals were separated in a furnace, washed with hexane, and then dried under vacuum at room temperature to obtain about 3301 crystals.

A part of this crystal was dissolved in tetrahydrofuran and analyzed by gas chromatography.
It was found that n-hexanol was contained in an amount of 2 moles relative to -octanedial and 1.8-octanedial. When the infrared absorption spectrum of this crystal was measured using the KBr tablet method, no absorption indicating the presence of aldehyde groups was observed. Absorption indicating the presence of Salles, hydroxyl groups, and acetal bonds were observed at 3400 and 1000 to 1200 m-', respectively. Observed. Furthermore, the LH-NMR spectrum of the CDα3-solution of this crystal was measured. 1,8-diol).

After melting the crystals, the boiling point is 69% by normal vacuum distillation operation.
~70℃/1.5 w Hf (1') as fraction
, 8-octanedial was obtained. Analysis by gas chromatography confirmed that this product had a purity of 98.6% or higher.

Example 2 Rhg (CO)160 was added to the reactor used in Example 1.
．． 15 Water 300 Go and 1,4-butanediol 200
After charging ml of gold and sufficiently replacing the inside of the autoclave with hydrogen/carbon oxide mixed gas (molar ratio 3/1), the pressure inside the autoclave was maintained at 8 atm and the exit gas flow rate was maintained at 1071/hour using the mixed gas of this composition. Internal temperature under stirring is 8
The mixture was heated to a constant temperature of 0° C., and stirring was continued for an additional 30 minutes. Then, with vigorous stirring, 1,7-octadiene 50
F (455 mol) was continuously added into the autoclave using a metering pump over 3 hours, and immediately after the addition was completed, 1
Stirring was continued for an hour. After reacting for a total of 4 hours, the reaction mixture was analyzed by gas chromatography and found that unreacted 1
．． The remaining amount of 7-octadiene is 18.2 mmol, 1.10-decandial and 2-methyl-1,9
- 336.4 mmol and 74.2 mmol of nonane dial were produced, respectively, and a small amount of 2,7-dimethyl-1,8-octanedial and 8-nonen-1-al were produced. I understand. Next, in the same manner as in Example 1, the reaction mixture was transferred to a flask with a content of 21, and an n-octatool 160 m was heated under a nitrogen gas atmosphere.
An extraction operation was performed at 30°C using a mixed solution of 1 and 250 mg of octane. After liquid separation, the raffinate layer was analyzed by gas chromatography and then transferred to the autoclave again.1.
Hydroformylation of 1,7-octadiene was repeated under the same reaction conditions as in the first reaction, with 101 additional portions of 4-butanediol. After the reaction, the reaction mixture was analyzed and the remaining amount of 1,7-octadiene in the second reaction was 20
．． 1 mmol, and the amounts of 1.10-decanedial and 2-methyl-1,9-nonanedial were found to be 332.8<IJ mol and 73.6:l mol, respectively. Next, an extraction operation was performed using the same operating method and conditions as the first time.

The extract obtained from the above two reactions and operations was washed with the same volume of water and then left at a temperature of about 10°C to precipitate crystals. The crystals were separated, washed with octane, and then subjected to vacuum distillation to achieve a boiling point of 89 to 9.
Approximately 84f of 1,10-decandial was obtained as a fraction at 0°C/0.5yHy. Analysis by gas chromatography showed that this product had a purity of 98.9% or more.

25- Example 3 h(CO)(PPhs) used as catalyst in Example 2
300d water and sulfolane 2 as solvent.
1.7 in the same manner as in Example 2 except that 00d was used.
- Hydroformylation reaction of octadiene was carried out for 4 hours. After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and it was found that the remaining amount of 1.7-octadiene was 25.4 mmol, 1.10-decandial, 2methyl-1°9-nonanedial, and 2.7-octadiene.
3 each of 5-dimethyl-1,8-octanedial
It was found that 28.5 mmol, 68.3 mmol and 8.5 mmol were produced. Then, in the same manner as in Example 2, 40° was added using 300 d of 2-ethylhexanol.
A C-t' extraction operation was performed. After separating the layers, the upper layer was washed with an equal volume of water and then subjected to vacuum distillation.
about 592 1.10-decandial, 2-methyl-1
A mixture of , 9-nonanedial and 2,5-dimethy26-1,8-octanedial was obtained.

The content of 1,10-decandial in this mixture is 8
It was 6.1'%.

Further, when the hydroformylation reaction of 1,7-octadiene was repeated using the above raffinate layer, almost the same reaction results as the first reaction were obtained.

Example 4 Water 250 as the hydroformylation solvent in Example 1
+rtll and 1,6-hexanediol 250d
1 in the same manner as in Example 1 except that a mixed solution of
．． A hydroformylation reaction of 5-hexadiene was carried out. After the reaction was stopped and analyzed by gas chromatography, the mixture was extracted with an extractant consisting of 150 tug of n-hexanol and 250 ml of cyclohexane under a nitrogen gas atmosphere.
The extraction operation was performed twice at 0°C. The extracted layer obtained by the two extractions is washed with 300 d of water and left at a temperature of about 5°C, and the obtained crystals are dried under vacuum to obtain about 1002 crystals, which are distilled under reduced pressure. by about 3
62 1,8-octanedials were obtained.

27-

Claims (1)

[Claims] 1. (I) Sulfolane, 1,4-butanediol or 1,6-hexanediol and water in a weight ratio of 15/85 to
(a) rhodium complex compound and (b) diphenylphosphinobenzene in 75/25 sulfolane, 1,4-butanediol or 1,6-hexanediol aqueous solution
1,5-hexadiene or 1.5-hexadiene in the presence of sodium, potassium or lithium salts of m-monosulfonic acid.
7-octadiene is hydroformylated with a mixed gas of hydrogen and carbon monoxide, and (II) a saturated aliphatic primary alcohol having about 5 to 12 carbon atoms is added to the reaction mixture obtained in step (1), or 1.8-octanedi is extracted from the reaction mixture by forming an extraction layer with a mixture of the primary alcohol and a saturated aliphatic hydrocarbon or saturated alicyclic hydrocarbon having about 5 to 10 carbon atoms. Earl or 1. Extract lO-decandial,
The raffinate layer containing the catalyst component is recycled to the hydroformylation reaction step of step (1), and from the extraction layer containing 1,8-octanedial or 1,10-decanedial obtained in step ('It). 1,8-octanedial or 1.10-decanedial is obtained, characterized in that 1,i-octanedial or 1.
A method for producing 10'-decandial. 2. Hydroformylation reaction of 1,5-hexadiene or 1,7-octadiene in step (I). The method according to claim 1, which is carried out in an aqueous sulfolane solution having a weight ratio of sulfolane to water of 25/75 to 60'/40. 3. In step (1), a rhodium complex compound is used in the reaction mixture IJi7t at a concentration of 0.05 to 10 milligram atoms in terms of rhodium warabi, and the sodium salt of diphenylphosphine benzene-m-monosulfonic acid is prepared. 2. A method according to claim 1, wherein the potassium salt or lithium salt is used in an amount of at least 10 equivalents per gram of rhodium. 4. In step (TI), the extraction operation is performed using a primary alcohol selected from the group consisting of n-hexanol, n-heptatool, n-octatool, n-nonanol, and n-decanol, and hexane, heptane, octane, decane, The method according to claim 1, which is carried out at a temperature of 10 to 60°C using a mixture of saturated aliphatic hydrocarbons or saturated alicyclic hydrocarbons selected from the group consisting of cyclohexane and methylcyclohexane. 5. In step (nl), after washing the extract layer obtained in step (n) with water, 1.8-
A method according to claim 1 for obtaining octanedial or 1,10-decanedial. 6. In step (n), the extraction operation is performed with a primary alcohol selected from the group consisting of n-hexanol, n-heptatool, n-octatool, n-nonanol, and n-decanol, or with the primary alcohol. hexane,
It is carried out at a temperature of 10 to 60°C using a mixture of saturated aliphatic hydrocarbons or saturated alicyclic hydrocarbons selected from the group consisting of hebutane, octane, decane, cyclohexane and methylcyclohexane, and the obtained n The extracted layer is washed with water and then maintained at a temperature of 0 to 50°C to precipitate crystals of dihemiacecool of 1.8-octanedial or 1.10-decanedial and the primary alcohol. After separating the crystals from the extraction layer, distillation was performed to obtain 1.8
A process according to claim 1 for obtaining -octanedial or 1°10-decanedial.