JPH0662464B2 - Method for producing 1,9-nonanediol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing 1,9-nonanediol.

1,9-Nonanediol is useful as a synthetic raw material for polyester, polyurethane, 1,9-nonanediamine and the like.

[Conventional technology]

JP-A-57-197238 discloses that 2,7-octadiene-1-ol is mixed with carbon monoxide and hydrogen in the presence of a rhodium catalyst and a monodentate tertiary organophosphorus compound in an organic solvent. Method for producing 1,9-nonanediol by hydrogenation of 1,9-nonanedial and / or 9-hydroxy-7-nonen-1-al by hydroformylating with gas Is listed. Further, Japanese Patent Laid-Open No. 64-26530 discloses that
A method for hydroformylating 7-octadiene-1-ol by a gas mixture of carbon monoxide and hydrogen in the presence of a rhodium compound and a specific tris (substituted aryl) phosphite is shown. JP 58-157739 A discloses 7-octen-1-al obtained by isomerizing 2,7-nectadien-1-ol in the presence of a copper-based or chromium-based catalyst. By hydroformylation in an aqueous sulfolane solution with a mixed gas of carbon monoxide and hydrogen in the presence of a rhodium complex compound and a sodium salt, potassium salt or lithium salt of diphenylphosphinobenzene-m-monosulfonic acid. , 9-nonanediol is obtained, and a method for producing 1,9-nonanediol by hydrogenating the 1,9-nonanediol is described. JP-A-58-201743 discloses that hydroformylation of 7-octen-1-al is carried out in a solution of an aromatic hydrocarbon containing a rhodium complex compound and a trisubstituted phosphine by a mixed gas of carbon monoxide and hydrogen. The method is shown.

[Problems to be Solved by the Invention]

Since the rhodium catalyst used in the hydroformylation reaction is expensive, it is necessary to recover the rhodium catalyst without loss and deactivation after the reaction and reuse it in the hydroformylation reaction in order to industrially carry out the hydroformylation reaction. Required. According to a study by the present inventors, Japanese Patent Laid-Open No. 57-197
Since 1,9-nonanedial and 9-hydroxy-7-nonen-1-al obtained by the method described in Japanese Patent No. 238 are high-boiling compounds, 1,9-nonanedial and / or 9-hydroxy- It has been found that a large decrease in the activity of the rhodium catalyst is unavoidable when 7-nonen-1-al is separated by distillation. Moreover, although it was possible to considerably prevent the thermal deterioration of the rhodium catalyst by allowing the disubstituted phosphine oxide to coexist in the reaction system in an appropriate amount, it is possible to completely suppress the decrease in the catalytic activity with the increase in the number of repetitions. could not. JP 64-26
In the method described in Japanese Patent No. 530, a diformylation product hydroformylated to the 2- and 3-positions of 2,7-octadiene-1-ol is by-produced, and the diformylation product is thermally extremely unstable. Therefore, a dehydration reaction is caused at the time of distillation separation, and as a result, a branched diol having 10 carbon atoms which can no longer be separated is mixed into 1,9-nonanediol, and the purity of 1,9-nonanediol is significantly lowered. In addition, since a large amount of 2-methyl-1,8-octanediol is by-produced by this method, it is not possible to selectively obtain 1,9-nonanediol.

Further, according to the methods described in JP-A-58-157739 and JP-A-58-201743, it is possible to obtain highly pure 1,9-nonanediol.
-Octadien-1-ol needs to be isomerized to 7-octen-1-al in the presence of a copper-based or chromium-based catalyst, and the number of steps increases, resulting in a total selectivity of 1,9-nonanediol. Will be lower.

An object of the present invention is to provide an industrially advantageous method for producing highly pure 1,9-nonanediol with high selectivity.

[Means for Solving the Problems]

According to the present invention, the above object is to provide a rhodium complex compound of general formula (I) in an aqueous sulfolane solution. (In the formula, M represents lithium, sodium or potassium, and n represents an integer of 1 to 3.) and a water-soluble monodentate phosphine represented by the general formula (I
I) (In the formula, X ¹ , X ² , X ³ and X ⁴ each represent an aryl group which may have a lithium salt, a sodium salt or a potassium salt of a sulfonic acid group, provided that X ¹ , X ² , X ³ And X ⁴
At least one of which is a lithium salt of a sulfonic acid group,
It represents an aryl group having a sodium salt or a potassium salt, and R represents a linear alkylene group having 2 to 5 carbon atoms which may be substituted with a lower alkyl group. In the presence of a water-soluble bidentate phosphine represented by the formula (2), 2,7-octadiene-1-ol is hydroformylated with a mixed gas of carbon monoxide and hydrogen to obtain (2) step (1). 5 to 5 carbon atoms for the reaction mixture
9-Hydroxy-7-nonen-1-al is obtained from the reaction mixture by performing an extraction operation with a mixture of 11 saturated primary aliphatic alcohols and 5-10 saturated aliphatic hydrocarbons. Extraction, (3) process the raffinate containing the catalyst component obtained in step (2)
Feeding to the hydroformylation reaction step of (1), (4) 9-hydroxy-7-nonene-obtained in step (2)
The extract containing 1-are is subjected to a hydrogenation reaction, (5) the reaction mixture obtained in step (4) is washed with water if necessary, and then distilled to separate 1,9-nonanediol and sulfolane. (6) A method for producing 1,9-nonanediol, characterized in that the sulfolane recovered in step (5) is fed to the hydroformylation reaction step in step (1). .

As the rhodium complex compound used in the hydroformylation reaction of 2,7-octadiene-1-ol according to the method of the present invention, any rhodium complex compound having a hydroformylation ability under reaction conditions can be used. A large number of such rhodium complex compounds are already known, and for example, HRh (CO) (PA ₃ ) ₃ (wherein A represents an aryl group; the same applies hereinafter) Rh ₄ (CO) ₁₂ and Rh ₆ (CO ) ₁₆ , Rh (acac) (CO)
₂ (in the formula, acac represents an acetylacetonato group. The same applies hereinafter) and the like. Also, RhCl (P
_{A 3) 3, Rh (acac} ) 3, Rh (OAc) 3 ( wherein, OAc represents an acetoxyl group), _{[Rh (CO 2 (PA 3)} 2 ] _{2, RhC1 3 · 3H 2 O} , Rh 2 A rhodium compound such as O ₃ can also be used after being activated by a usual method in a catalyst preparation tank, among which Rh (acac) (C
When O) ₂ , Rh ₄ (CO) ₁₂ and Rh ₆ (CO) ₁₆ are used, 1,9
-Highly selective results for the nonanediol precursor are obtained. The rhodium complex compound is usually used in an amount in the range of 0.1 to 10 milligram atom in terms of rhodium atom per hydroformylation reaction solution.

The water-soluble monodentate phosphine represented by the general formula (I) is
Specifically, (C ₆ H ₅ ) ₂ P (C ₆ H ₄ -m-SO ₃ Li), (C ₆ H ₅ ) P (C ₆ H ₄ -m-SO ₃ Li) ₂ , P
_{(C 6 H 4 -m-SO} 3 Li) 3, (C 6 H 5) 2 P (C 6 H 4 -m-SO 3 Na), (C 6 H 5) P (C
₆ H ₄ -m-SO ₃ Na) ₂ , P (C ₆ H ₄ -m-SO ₃ Na) ₃ , (C ₆ H ₅ ) ₂ P (C ₆ H ₄ -mS
O ₃ K), a _{(C 6 H 5) P (} C 6 H 4 -m-SO 3 K) 2, P (C 6 H 4 -m-SO 3 K) 3. The water-soluble monodentate phosphine is used in an amount of 10 equivalents or more, preferably 40 equivalents per gram atom of rhodium.
It is used in an equivalent amount or more.

Examples of the water-soluble bidentate phosphine represented by the general formula (II) include (C ₆ H ₄ -m-SO ₃ Na) ₂ PCH ₂ CH ₂ CH ₂ CH ₂ P (C ₆ H ₄ -m -SO ₃ Na) ₂ , (C ₆ H ₄ -m-SO ₃ Li) ₂ PCH ₂ CH ₂ CH ₂ CH ₂ P (C ₆ H ₄ -m-SO ₃ Li) ₂ , (C ₆ H ₄ -m -SO ₃ K) ₂ PCH ₂ CH ₂ CH ₂ CH ₂ P (C ₆ H ₄ -m-SO ₃ K) ₂ , (C ₆ H ₄ -m-SO ₃ Na) (C ₆ H ₅ ) PCH ₂ CH ₂ CH ₂ CH ₂ P (C ₆ H ₅ ) (C ₆ H ₄ -m-SO
₃ Na), (C ₆ H ₄ -m-SO ₃ Li) (C ₆ H ₅ ) PCH ₂ CH ₂ CH ₂ CH ₂ P (C ₆ H ₅ ) (C ₆ H ₄ -m-SO
₃ Li), (C ₆ H ₅ ) ₂ PCH ₂ CH ₂ CH ₂ CH ₂ P (C ₆ H ₅ ) (C ₆ H ₄ -m-SO ₃ Na), (C ₆ H ₅ ) ₂ PCH ₂ CH _{2 CH 2 CH 2 P (C 6} H 5) (C 6 H 4 -m-SO 3 Li) , and the like. When the water-soluble bidentate phosphine was not used, the catalytic activity of the rhodium complex compound decreased as the reaction was repeated. On the other hand, when the water-soluble bidentate phosphine was used, deterioration of the catalytic activity of the rhodium complex compound was not observed, and the general formula
It was found that the water-soluble monodentate phosphine represented by (I) is inhibited from being oxidized by oxygen. The decrease in the catalytic activity is caused by dehydration reaction of 2,7-octadien-1-ol to the 2-position of the resulting hydroformylated α, β-unsaturated aldehyde or 2,7-unsaturated aldehyde. It is considered that the coordination of rhodium to the allyl alcohol portion of octadien-1-ol is the cause. General formula (I
The water-soluble bidentate phosphine represented by I) is presumed to have an action of suppressing the coordination of these compounds with rhodium. Rhodium 1 is a water-soluble bidentate phosphine
Used in amounts ranging from 0.3 to 2 equivalents per gram atom. If it is less than 0.3 equivalent, the above-mentioned effect is small, and if it exceeds 2 equivalent, the reaction rate is significantly decreased.

The hydroformylation reaction of 2,7-octadien-1-ol according to the method of the present invention is carried out in an aqueous sulfolane solution. The weight ratio of sulfolane and water is 10:90 to 75:25.
Is preferred. If the concentration of sulfolane in the aqueous solution is less than 15% by weight, the solubility of 2,7-octadiene-1-ol in the aqueous solution is decreased, the reaction rate is lowered, and the layer separation property in the step (2) is reduced. It is not preferable because it worsens. When the concentration of sulfolane in the aqueous solution exceeds 75%, the selectivity to the 1,9-nonanediol precursor decreases, and the amount of the solvent and catalyst components eluted into the extraction layer in step (2) is large. Therefore, it is not preferable. A particularly preferred concentration of the sulfolane aqueous solution is in the range of 20:80 to 60:40 by weight ratio of sulfolane and water.

The hydroformylation reaction is usually carried out at a temperature in the range of 40 to 110 ° C, preferably in the range of 60 to 90 ° C. The molar ratio of hydrogen and carbon monoxide in the mixed gas of hydrogen and carbon monoxide used in the reaction is usually 1 to 2 to 5 to 1 as the gas composition. The reaction pressure is generally in the range of 1 to 30 absolute atmospheric pressure. The hydroformylation reaction can be carried out continuously or batchwise in a stirred reactor or a bubble column reactor. 2,7-octadiene-into the reaction mixture under the reaction conditions
Since the solubility of 1-ol is relatively low, it is desirable to adjust the feed rate of 2,7-octadiene-1-ol according to the reaction rate, which can prevent the reaction system from becoming non-uniform. . The concentration of 9-hydroxy-7-nonen-1-al in the reaction mixture is 0.3 to 3 mol /
It is desirable that it is within the range from the viewpoint of contact activity and stability of the product.

The reaction mixture obtained by hydroformylating 2,7-octadien-1-ol has a carbon number of 5 to 1
It is subjected to an extraction apparatus using a mixture of 1 saturated aliphatic primary alcohol and 5 to 10 saturated aliphatic hydrocarbons. Examples of the saturated aliphatic primary alcohol having 5 to 11 carbon atoms include n-pentanol, n-hexanol, 2-ethylhexanol, 3,5,5-trimethylihexanol, n-heptanol, n-octanol, and n. -Nonanol, n-decanol, n-undecanol, etc. can be illustrated. Further, as the saturated aliphatic hydrocarbon having 5 to 10 carbon atoms, n-pentane, n-hexane, n
-Heptane, n-octane, n-nonane, n-decane and the like can be exemplified. By mixing and using the saturated aliphatic primary alcohol and the saturated aliphatic hydrocarbon, the elution rate of the reaction solvent and the catalyst component in the extract is reduced as compared with the case where the saturated aliphatic primary alcohol is used alone. be able to. In this case, the ratio of the saturated aliphatic primary alcohol and the saturated aliphatic hydrocarbon used is 1 to 5 by volume.
It is preferably within the range of 5: 1. The ratio of the mixture of the saturated aliphatic primary alcohol and the saturated aliphatic hydrocarbon used to the reaction mixture is practically selected from the range of 1: 5 to 3: 1 by volume. Further, in view of the layer separation property, the extraction rate, the elution rate of the catalyst component, the stability of the catalyst and the stability of the product, a temperature in the range of 10 to 70 ° C is adopted as the extraction temperature, and a range of 30 to 70 ° C. It is desirable to adopt the temperature of. As the extraction device, a stirring type extractor, an RDC type extraction tower,
A perforated plate tower or the like can be applied. The extraction operation is usually performed in an atmosphere of an inert gas such as nitrogen, helium, or argon, or a mixed gas of hydrogen and carbon monoxide. By the extraction operation, the products containing 2,7-octadiene-1-ol and 9-hydroxy-7-nonen-1-al as raw materials as main components are separated into the upper layer (extract), and the catalyst is separated into the lower layer (extraction). It is separated into residual liquid). A part of the raffinate is subjected to a known catalyst activation treatment, if necessary, and then recycled to the hydroformylation reaction step of step (1).

9-Hydroxy-7-nonene-1-obtained in step (2)
The extract containing Earle contains a small amount of a reaction solvent and a catalyst component in addition to the starting compound 2,7-octadiene-1-ol. Therefore, it is preferred to wash the extract with water in a volume ratio thereof of at least 0.015. There is no strict upper limit on the amount of water used,
It is usually used in a volume ratio of 0.15 or less with respect to the extract. By washing the extract with water, the reaction solvent and the catalyst component contained in the extract in a small amount can be transferred to the water layer side, so that the reaction solvent and the catalyst component can be easily separated and recovered from the extract. The aqueous solution containing the reaction solvent and the catalyst component obtained by this operation can be recycled and reused in the hydroformylation reaction step of step (1). The extract after washing with water is subjected to a hydrogenation reaction as it is or after distillation to separate saturated aliphatic primary alcohol and saturated aliphatic hydrocarbon and a part or all of the raw materials by distillation.

As the catalyst used in the hydrogenation reaction of 9-hydroxy-7-nonen-1-al, known catalysts having the ability to hydrogenate olefins and aldehydes can be used. Among them, nickel-based catalysts and ruthenium-based catalysts can be used. Use is preferred. Specifically, Raney-Nickel catalyst, modified Raney-Nickel catalyst, supported Nickel catalyst, supported ruthenium catalyst and the like can be mentioned. The hydrogenation reaction can be carried out in a stirred type or bubble column type reactor in a state where the catalyst is suspended in a liquid phase, and when a supported nickel catalyst or a supported ruthenium catalyst is used as the catalyst, these are It can also be carried out in a packed fixed bed reactor.

The reaction mixture after the hydrogenation reaction obtained in the step (4) is washed with water if necessary and then subjected to a distillation operation to obtain 1,9-nonanediol. A part of the sulfolane used in the step (1) is mixed in the reaction mixture, and it is recovered as an aqueous solution by washing with water. In addition, sulfolane is
It is recovered as a compound having a lower boiling point than 9-nonanediol. Recovered sulfolane or its aqueous solution is processed
It is recycled to the hydroformylation step (1).

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these.

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 Rh.
(CO) ₂ (acac) 0.75 mmol, diphenylphosphinobenzene-m-monosulfonate sodium 50 mmol, bidentate phosphine (C ₆ H ₄ -m-SO ₃ Na) ₂ PCH ₂ CH ₂ CH ₂ C
H ₂ P (C ₆ H ₄ -m-SO ₃ Na) ₂ 0.75 mmol, 400 ml of water and 100 ml of sulfolane were charged, and the inside of the autoclave was sufficiently replaced with a mixed gas of hydrogen and carbon monoxide (molar ratio 1: 1). Then, while maintaining the internal pressure of the autoclave at 5 atm with the mixed gas of this composition and the flow rate of the discharged gas at 10 / hour, the mixture was heated until the internal temperature became constant at 75 ° C., and further stirred for 30 minutes. Continued. Then, 43 ml of 2,7-octadiene-1-ol (296 ml) was vigorously stirred.
(Mmol) was continuously added into the autoclave by a metering pump over 2 hours. 0.5 more after addition
Stirring was continued for hours. After reacting for a total of 2.5 hours, stirring was stopped, and the reaction mixture was fully replaced with a mixed gas of hydrogen and carbon monoxide (molar ratio 1: 1) in advance so that the autoclave of content 1 was not exposed to air. Then, 400 ml of hexane and 170 ml of n-octanol were added, and the mixture was stirred for 15 minutes while maintaining the pressure in the autoclave at 5 atm and the internal temperature at 60 ° C. Immediately after stirring was stopped, two layers were separated. After standing for 10 minutes, the upper layer (colorless) was analyzed by gas chromatography. As a result, the residual amount of 2,7-octadiene-1-ol was 83 mmol (conversion rate 72%), and 9-hydroxy-7-nonene was found. -1-R (Hereafter, this is HN
It was found that 147 mmol and 3 mmol of 1,9-nonanedial (hereinafter abbreviated as EL) and 1,9-nonanedial (hereinafter abbreviated as NL) were extracted, respectively. Next, the lower layer (the extraction layer, yellow) was transferred to an autoclave without touching the air again, and 7 ml of sulfolane was added. 43 ml of 2,7-octadiene-1-ol was continuously added into the autoclave over 2 hours under the same conditions as the above-mentioned first time, and stirring was continued for further 0.5 hour to carry out the second hydroformylation reaction. I went. After performing the extraction operation by the same operation method and conditions as the first time, the extract was analyzed by gas chromatography and found to be 2,7
The residual amount of -octadien-1-ol was 87 mmol, and it was found that HNEL and NL were extracted by 192 mmol and 4.5 mmol, respectively. The remaining amount of the extract was transferred to the autoclave again, and 10 ml of sulfolane was added. The third hydroformylation reaction was carried out under the same conditions and operations as those of the first time, and then the extraction operation was carried out by the same method and conditions. Then, the extract was analyzed and the 2,7-octadien-1-ol remained. The amount is 83
And HNEL and NL are each 201
It was found that the millimoles and the 4.2 millimoles had been extracted. A part (1 ml) of this extract was taken and hydrogenated at room temperature and atmospheric pressure using Raney-Nickel as a catalyst. After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find that 1,9-nonanediol (hereinafter, abbreviated as ND) as a normal product and 2-methyl-1 as an iso product. The production ratio of 8,8-octanediol (hereinafter abbreviated as MOD) was 97: 3.
No formation of a branched triol having 10 carbon atoms derived from a diformyl body hydroformylated to the 2- and 3-positions of 2,7-octadien-1-ol was observed. The raffinate layer was transferred to the autoclave again, 10 ml of sulfolane was added, the hydroformylation reaction was performed under the same conditions and operations as the first time, and then extraction was performed by the same method and conditions, repeating 15 times in total. Ivy. The analysis results of the extracts of the reaction mixture obtained by the third, fifth, tenth and fifteenth hydroformylation reactions and a part of the extracts were subjected to a hydrogenation reaction in the same manner as above, Table 1 shows the production ratios obtained by gas chromatographic analysis of the obtained ND and MOD. After 15 repeated reactions, no decrease in catalytic activity was observed, and the amount of HNEL produced was almost constant.

The hydrogenation reaction of the extract obtained as described above was performed as follows. That is, 20 g of Raney-Nickel was charged into a stainless steel autoclave having a thermometer, an electromagnetic stirrer, a gas inlet and a gas outlet, and 20 g of Raney-Neckel was sufficiently replaced with hydrogen gas, and then the pressure in the autoclave was adjusted to 10 atm. While maintaining the flow rate of the discharged gas at 5 / hour, warm the inner temperature until it became constant at 100 ° C, and then vigorously agitate the extract solution 5 obtained after the third and subsequent repetitions for 2 hours using a metering pump. Was continuously added to the inside. After the addition was completed, stirring was continued for another 2 hours. After reacting for a total of 4 hours, stirring was stopped. A very small amount of the reaction mixture was sampled and analyzed by gas chromatography.
The NEL conversion was found to be 100%. Hexane was distilled off from the reaction mixture, and the residue was further subjected to vacuum distillation to recover sulfolane contained in the extract, which had a boiling point of 120 to 123 ° C. under a reduced pressure of about 0.5 mmHg. ND is a high-purity fraction (MOD
And mixed amount: about 3%) about 270 g was obtained.

Comparative Example 1 The hydroformylation reaction was repeated under the same conditions and operations as in Example 1 except that the water-soluble bidentate phosphine was not added, and an extraction operation was performed. Three
The analysis results of the extracts of the reaction mixture obtained by the 5th, 5th, 10th and 15th hydroformylation reactions and a part of the extracts were subjected to a hydrogenation reaction to obtain ND and MOD. Table 2 shows the production ratio obtained by gas chromatography analysis. In the reaction repeated 15 times, the production amount of HNEL gradually decreased, and deterioration of the catalyst activity was observed.

Example 2 The same autoclave used in Example 1 was charged with Rh ₄ (CO) ₁₂ 0.
1875 mmol, diphenylphosphinobenzene-m-
Lithium monosulfonate 50 mmol, water-soluble bidentate phosphine (C ₆ H ₄ -m-SO ₃ Na) ₂ PCH ₂ CH ₂ CH ₂ CH ₂ P (C ₆ H ₄ -mS
After charging 0.75 mmol of O ₃ Na) ₂ , 400 ml of water and 100 ml of sulfolane, the inside of the autoclave was sufficiently replaced with a mixed gas of hydrogen and carbon monoxide (molar ratio 1: 1),
With the mixed gas of this composition, the pressure inside the autoclave was maintained at 5 atm, and the flow rate of the discharged gas was kept at 10 / hour, while heating was continued until the internal temperature became constant at 75 ° C. under stirring, and stirring was continued for further 30 minutes. After a while, stirring vigorously for 2,7
-Octadien-1-ol 43 ml (296 mmol)
Was continuously added into the autoclave by a metering pump over 2 hours. After the addition was completed, stirring was continued for another 0.5 hour. After reacting for a total of 2.5 hours, stirring was stopped, and the autoclave of Content 15 in which the reaction mixture was sufficiently replaced with a mixed gas of hydrogen and carbon monoxide (molar ratio 1: 1) beforehand was kept out of contact with air. Then, 400 ml of hexane and 170 ml of n-octanol were added, and the mixture was stirred for 15 minutes while maintaining the pressure in the autoclave at 5 atm and the internal temperature at 60 ° C. Immediately after stirring was stopped, two layers were separated. After standing for 10 minutes,
When the upper layer (colorless) was analyzed by gas chromatography, the residual amount of 2,7-octadiene-1-ol was 83 mmol (conversion rate 72%), and HNEL and NL were extracted by 147 and 3 mmol, respectively. I found out that A part (1 ml) of this extract was taken and hydrogenated at room temperature and atmospheric pressure using Raney-Nitzkel as a catalyst. After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and the production ratio of ND and MOD was 9
It was 7 to 3.

Examples 3 to 9 The rhodium complex compound shown in Table 3 in Example 2, the water-soluble monodentate phosphine, the water-soluble bidentate phosphine and the extractant were used, and the reaction pressures shown in Table 3 ( The reaction and extraction operations were performed in the same manner except that the CO / H ₂ pressure) and the extraction temperature were adopted. Table 3 shows the obtained results.
Shown in.

EFFECT OF THE INVENTION According to the present invention, 1,9-nonanediol can be continuously produced with high selectivity and high purity.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display area C07B 61/00 300 C08G 18/32 NDS 8620-4J

Claims (6)

[Claims] 1. A rhodium complex compound of the formula (I) in an aqueous sulfolane solution. (In the formula, M represents lithium, sodium or potassium, and n represents an integer of 1 to 3.) and a water-soluble monodentate phosphine represented by the general formula (I
I) (In the formula, X ¹ , X ² , X ³ and X ⁴ each represent an aryl group which may have a lithium salt, a sodium salt or a potassium salt of a sulfonic acid group, provided that X ¹ , X ² , X 4
^At least one of ³ and X ⁴ represents an aryl group having a lithium salt, a sodium salt or a potassium salt of a sulfonic acid group, and R is a straight chain having 2 to 5 carbon atoms which may be substituted with a lower alkyl group. Represents an organic alkylene group. 2,7-in the presence of a water-soluble bidentate phosphine represented by
Octadiene-1-ol is hydroformylated with a mixed gas of carbon monoxide and hydrogen, and (2) the reaction mixture obtained in step (1) has 5 to 5 carbon atoms.
9-Hydroxy-7-nonen-1-al is obtained from the reaction mixture by performing an extraction operation with a mixture of 11 saturated primary aliphatic alcohols and 5-10 saturated aliphatic hydrocarbons. Extraction, (3) process the raffinate containing the catalyst component obtained in step (2)
Feeding to the hydroformylation reaction step of (1), (4) 9-hydroxy-7-nonene-obtained in step (2)
The extract containing 1-are is subjected to a hydrogenation reaction, (5) the reaction mixture obtained in step (4) is washed with water if necessary, and then distilled to separate 1,9-nonanediol and sulfolane. (6) A method for producing 1,9-nonanediol, characterized in that the sulfolane recovered in step (5) is fed to the hydroformylation reaction step of step (1). 2. In the step (1), the rhodium complex compound is used in an amount of 0.1 to 10 milligram atom in terms of rhodium atom per reaction solution, and the water-soluble monodentate phosphine represented by the general formula (I) is used as rhodium. The use according to claim 1, which is used in an amount of 10 equivalents or more per gram atom, and the water-soluble bidentate phosphine represented by the general formula (II) is used in an amount of 0.3 to 2 equivalents per gram atom of rhodium. Production method. 3. A 2,7-octadiene-in the step (1)
The method according to claim 1 or 2, wherein the hydroformylation reaction of 1-ol is carried out in an aqueous sulfolane solution having a weight ratio of sulfolane and water of 10:90 to 75:25. 4. The extraction operation in step (2) is carried out with n-hexanol, n-heptanol, n-octanol and n-octanol.
Using a mixture of a saturated aliphatic primary alcohol selected from the group consisting of nonanol and a saturated aliphatic hydrocarbon selected from the group consisting of hexane, heptane and octane, 1
The manufacturing method according to any one of claims 1 to 3, which is carried out at a temperature of 0 to 70 ° C. 5. The step (4), wherein the extract obtained in the step (2) is washed with water and then subjected to a hydrogenation reaction in the presence of a nickel catalyst or a ruthenium catalyst. The manufacturing method according to one. 6. The production method according to claim 1, wherein sulfolane is recovered in step (5) by washing the reaction mixture obtained in step (4) with water.