JPH1180068A - Method for producing tricyclodecanedialdehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable to suppress reaction inhibitions caused by by-products and dienes contained in a raw material as impurities and smoothly and profitably produce the subject compound useful in the field of a raw material for polyesters by allowing a dienophile to exist in the reaction system. SOLUTION: This method for producing 3(or 4), 8(or 9)-diformyl tricyclo[5.2.1.0<2> ,<6> ] decane comprises reacting (D) dicyclopentadiene with (E) hydrogen and (F) carbon monoxide in the presence of (A) a rhodium compound, (B) a monodentate tertiary organic phosphorus compound and (C) a dienophile (e. g. maleic anhydride, dimethyl maleate). The reaction is preferably carried out, after at least a part of the component C is preliminarily added to the component D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 3,8-diformyltricyclo [5.2.1.0 ^2,6 ] decane by hydroformylation of dicyclopentadiene, 3,9
-Diformyltricyclo [5.2.1.0 ^2,6 ] decane, 4,8-diformyltricyclo [5.2.1.0
^2,6 ] decane, 4,9-diformyltricyclo [5.
2.1.0 ^2,6 ] decane or a mixture thereof (hereinafter, referred to as "
"3 (or 4), 8 (or 9) -diformyltricyclo [5.2.1.0 ^2,6 ] decane" or "tricyclodecanedialdehyde"). . The tricyclodecanedialdehyde obtained by the present invention can be used as a raw material for a high molecular compound such as polyester by hydrogenation.
(Or 4), 8 (or 9) -dihydroxymethyltricyclo [5.2.1.0 ^2,6 ] decane (hereinafter sometimes abbreviated as TCDDM).

[0002]

2. Description of the Related Art A method for producing tricyclodecanedialdehyde by reacting dicyclopentadiene with hydrogen and carbon monoxide in the presence of a rhodium compound and a monodentate tertiary organic phosphorus compound is known. For example, JP-A-58-21638 discloses that in Example 1, 70-80 kg / cm ² (gauge pressure) in toluene.
The hydroformylation reaction of dicyclopentadiene was carried out at a pressure of 100 to 120 ° C., a rhodium concentration of 1.4 mmol / l and a triphenylphosphine concentration of 16 mmol / l, and the yield was 85%. It is stated that tricyclodecanedialdehyde was formed. Japanese Patent Application Laid-Open No. 6-501958 discloses, as Reference Example 4, 19-diisopropylbenzene.
An example is disclosed in which the hydroformylation reaction of dicyclopentadiene was carried out at a temperature of 95 ° C. to 125 ° C. under a pressure of kg / cm ² at a rhodium concentration of about 1.6 mmol / l and a tricyclohexylphosphine concentration of about 5 mmol / l. , 50% yield of tricyclodecanedialdehyde.

In the above, dicyclopentadiene used as a starting material is a compound obtained by dimerizing cyclopentadiene by a Diels-Alder reaction, and gives cyclopentadiene by thermal decomposition. Dicyclopentadiene is a compound having a melting point of 33.6 ° C., which can be easily handled by heating to a molten state. However, the higher the heating temperature, the longer the heating period. As the length increases, the rate of thermal decomposition increases. Particularly, in an atmosphere exceeding 40 ° C., thermal decomposition of dicyclopentadiene tends to be promoted. Cyclopentadiene, which is a raw material of dicyclopentadiene, is obtained from a C5 fraction which is a by-product of the thermal decomposition of naphtha, but may contain conjugated dienes such as isoprene and butadiene. Therefore, dicyclopentadiene which is a dimer of cyclopentadiene may also contain such a conjugated diene.

[0004]

SUMMARY OF THE INVENTION Cyclopentadiene,
It is known that conjugated dienes such as isoprene and butadiene form a stable complex with a rhodium compound under hydroformylation reaction conditions, and thus are less susceptible to hydroformylation reaction. Therefore, when producing dicyclodecanedialdehyde by reacting dicyclopentadiene with hydrogen and carbon monoxide, the carbon-
Tricyclodecanedialdehyde is produced via a monoaldehyde form in which one of the carbon double bonds is hydroformylated, but as described above, cyclopentadiene produced under the reaction conditions or mixed as an impurity in the raw material. It is important to solve the problem of reaction inhibition such as reduction of the reaction rate due to conjugated dienes such as isoprene and butadiene or, in extreme cases, termination of the reaction, in order to make the reaction proceed smoothly.

[0005] As a method for solving the reaction inhibition by the conjugated diene, i) purifying dicyclopentadiene by recrystallization to reduce the content of conjugated diene mixed as an impurity, and ii) diluting with a solvent. Iii) reducing the concentration of the conjugated diene in the reaction solution, and iii) increasing the amount of the rhodium compound or the monodentate tertiary organophosphorus compound. Therefore, this method is not advantageous for industrial implementation. Even if these methods are followed, it is difficult to eliminate cyclopentadiene produced under the reaction conditions. Here, when examining the hydroformylation reaction conditions of dicyclopentadiene described above or above, according to the method described in above, a rhodium compound and triphenylphosphine were each dissolved in a reaction solution at 1.4 mmol / liter, 16 Used at a relatively high concentration of mmol / L, 70-80 kg / cm ² (gauge pressure)
Under a pressure of 85% in a yield of 85%. However, in the method described in the above, the rhodium compound is used at a relatively high concentration of 1.6 mmol / liter. Tricyclohexylphosphine at a concentration of 5 mmol / liter,
When the reaction was carried out under a pressure of / cm ² , the yield of tricyclodecanedialdehyde remained at 50%. As described above, all of the above methods require not only high pressure as a reaction condition but also a high rhodium concentration, and it is difficult to say that the method is suitable for industrial implementation. Thus, the present invention provides a process capable of smoothly performing the hydroformylation reaction of dicyclopentadiene even under relatively low rhodium concentration reaction conditions, and thus industrially advantageously producing tricyclodecanedialdehyde. The task is to provide

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that dicyclopentadiene can be converted to hydrogen and monovalent in the presence of a rhodium compound and a monodentate tertiary organic phosphorus compound. When producing tricyclodecane dialdehyde by reacting with carbon oxide, cyclopentadiene produced under the reaction conditions by the presence of dienophile in the reaction system, and conjugated dienes such as isoprene and butadiene mixed as impurities in the raw material The present inventors have found that the reaction inhibition caused by the reaction can be suppressed, and completed the present invention.

That is, the present invention is characterized in that dicyclopentadiene is reacted with hydrogen and carbon monoxide in the presence of a rhodium compound, a monodentate tertiary organic phosphorus compound and a dienophile. ), 8 (or 9) -diformyltricyclo [5.2.1.
0 ^2,6 ] decane.

In the present invention, as the dicyclopentadiene, any one produced by any method may be used, but one containing about 100 to 2,000 ppm of a conjugated diene is industrially easily available. The dicyclopentadiene can be used in the form of a solution by adding a small amount of a solvent described below.

The conjugated diene mentioned above means an organic compound having a conjugated carbon-carbon double bond, such as butadiene, isoprene, 1,3-pentadiene, and cyclopentadiene.

As the rhodium compound used in the present invention, any rhodium compound which has a catalytic activity for hydroformylation or which changes to have catalytic activity for hydroformylation under hydroformylation reaction conditions can be used. , Rh ₄ (CO) ₁₂ , Rh ₆ (C
O) ₁₆ , Rh (acac) (CO) ₂ , rhodium oxide,
Rhodium chloride, rhodium acetylacetonate, rhodium acetate and the like can be mentioned. The rhodium compound is usually used in an amount of 0.001 to 1 mg atom, preferably 0.0%, in terms of rhodium atom per liter of the hydroformylation reaction solution.
It is used in a concentration range of from 0.5 to 0.5 milligram atoms.

The monodentate third compound used in the present invention
The typical organic phosphorus compounds are typically represented by the following formula (2): P (R ¹ ) (R ² ) (R ³ ) (2) (wherein R ¹ , R ² and R ³ are an aryl group, an aryl group, respectively) An oxy group, an alkyl group, an alkoxy group, a cycloalkyl group or an aralkyl group).

In the above formula (2), the aryl group represented by R ¹ , R ² and R ³ is, for example, a phenyl group,
The aryloxy group represented by R ¹ , R ² and R ³ includes, for example, a phenoxy group, an ot-butylphenoxy group and an o-ethylphenoxy group. And the like. Examples of the alkyl group represented by R ¹ , R ^2, and R ³ include a methyl group, an ethyl group, an n-butyl group, and an n-octyl group, and an alkoxy group represented by R ¹ , R ^2, and R ^3. Examples of the group include a methoxy group, an ethoxy group, n
-Butoxy group and the like. Furthermore, examples of the cycloalkyl group represented by R ¹ , R ² and R ³ include a cyclopentyl group and a cyclohexyl group,
The aralkyl group represented by R ¹ , R ² and R ³ includes, for example, a benzyl group. R ¹ , R ² and R ³
May have any substituent as long as it does not inhibit the hydroformylation reaction.

Here, specific examples of the monodentate tertiary organic phosphorus compound used in the present invention include triphenyl phosphite, tris (2-methylphenyl) phosphite, and tris (2-ethylphenyl). ) Phosphite, tris (2-isopropylphenyl) phosphite, tris (2-phenylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (2-t-butyl-5-methylphenyl) phosphite Phyte, bis (2-methylphenyl) (2-t-butylphenyl) phosphite, bis (2-t-butylphenyl)
(2-methylphenyl) phosphite, tris (2,4
Phosphites such as (-di-t-butylphenyl) phosphite; and phosphines such as triphenylphosphine, tolylphosphine, tricyclohexylphosphine, tri-n-butylphosphine, and tri-n-octylphosphine.

These monodentate tertiary organic phosphorus compounds may be used alone or in combination of two or more.

The amount of the monodentate tertiary organophosphorus compound used is usually 0.1 mmol or more, preferably 0.5 mmol or more per liter of the hydroformylation reaction solution. The upper limit of the amount of the monodentate tertiary organophosphorus compound is not particularly limited, but is generally about 20 mmol per liter of the hydroformylation reaction solution, and 10 mmol per liter of the hydroformylation reaction solution. It is preferred to be less than millimol. In some cases, the upper limit of the amount of the monodentate tertiary organic phosphorus compound used is determined by the solubility in the reaction solution.

In the present invention, bidentate coordination of 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, etc. The diphosphinoalkanes may be added at a rate of 0.2 to 2 moles per gram atom of rhodium.

The dienophile used in the present invention refers to a compound having a property of adding to a conjugated diene in a so-called Diels-Alder reaction, and includes a carbonyl group, a cyano group, a nitro group, a halogen atom, an acyloxy group and a phenyl group. And a compound having a carbon-carbon double bond or a carbon-carbon triple bond activated by an electron-withdrawing group such as a sulfonyl group, an alkoxy group, an amino group, and cyanomethyl. Examples of the dienophile usable in the present invention include, for example, maleic anhydride, dimethyl maleate, dimethyl fumarate, diethyl fumarate, acrylic acid, methyl acrylate, benzalacetone, diethyl ethylidenemalonate, N-methylmaleimide, acetylene Dimethyl carboxylate, acrolein, methyl vinyl ketone, p-benzoquinone, naphthoquinone, 2,7-octadienal, acrylonitrile, tetracyanoethylene, 2-nitropropene, styrene, cyclopropene, 4-phenyl-1,2,4- Examples include triazolinedione, methyl vinyl ether, vinyl acetate, phenyl vinyl sulfide, phenyl vinyl sulfone, tetrachloroethylene, 1,2-dibromoethane, and the like. One type of dienophile may be used, or two or more types may be used in combination.

The dienophile is preferably used in at least 0.5 times the molar number of the conjugated diene. However, for a conjugated diene having a plurality of conjugated diene structures in one molecule, 0.5 for each conjugated diene structure.
It is preferred to use more than twice as many moles of dienophile. There is no particular upper limit on the amount of dienophile to be used, but it is usually sufficient to use about 20 mmol per 1 mol of dicyclopentadiene.

In the present invention, dicyclopentadiene and dienophile may be separately added to the reaction system, but it is preferable to add at least a part of dienophile to dicyclopentadiene in advance. When dienophile is added in advance, it is preferable that dicyclopentadiene after the addition of dienophile is stored at a temperature of 80 ° C. or lower until the hydroformylation reaction is performed.

The hydroformylation reaction according to the invention is usually carried out at a temperature in the range from 60 to 160 ° C., preferably from 80 to 140 ° C.

The molar ratio of hydrogen to carbon monoxide used in the present invention is usually selected from the range of 1/5 to 5/1 as the composition of the gas entering the reaction system. The reaction system may contain a small amount of a gas inert to the hydroformylation reaction, for example, nitrogen or argon.

The hydroformylation reaction according to the present invention is generally carried out under normal pressure to 150 atm, depending on the reaction temperature. Further, the hydroformylation reaction according to the present invention can be carried out in a stirred type reaction vessel or a bubble column type reaction vessel in a continuous mode or a batch mode.

The hydroformylation reaction according to the present invention can be carried out in the absence of a solvent, but may be carried out in the presence of an inert solvent in the reaction system. Such solvents include, for example, saturated aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; methanol, ethanol, n-propanol, isopropanol, n-butanol, s- Alcohols such as butanol, t-butanol, and n-octanol; ethers such as diethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, and dioxane; esters such as methyl acetate, ethyl acetate, dioctyl phthalate, and dimethyl adipate; . These solvents may be used alone or in combination of two or more. In addition,
The amount of the solvent to be used is generally 50% by volume or less based on the reaction solution.

In the present invention, when the above alcohols are used as a solvent, acetals may be formed as a by-product because the reaction product is an aldehyde. However, by adding a basic substance to the reaction system, the acetals may be produced. Can be suppressed. Examples of the basic substance include amines such as triethylamine, tri-n-butylamine, tri-n-octylamine, and triethanolamine; and nitrogen-containing aromatic compounds such as pyridine and N, N-dimethylaminopyridine. Can be These basic compounds may be used alone or in combination of two or more. The amount of the basic compound used is usually in the range of 0.1 to 30 mmol per liter of the reaction solution.

The hydroformylation reaction solution obtained by the above method can be used as it is in the next reaction step such as a hydrogenation reaction, an oxidation reaction or an amination reaction. If desired, a fraction containing tricyclodecanedialdehyde obtained by evaporating the reaction solution under reduced pressure may be used in the next reaction step.

Further, if necessary, the above-mentioned fraction containing tricyclodecanedialdehyde can be purified by known means such as distillation and crystallization to isolate tricyclodecanedialdehyde. It is.

[0027]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by the examples.

Example 1 Internal volume 300 provided with gas inlet and sampling port
0.903 mg of dicarbonylacetylacetonatotrodium (0.035
Mmol), 364 mg (0.7 mmol) of tris (2-tert-butyl-5-methylphenyl) phosphite and 20 ml of toluene were mixed with air in a mixed gas atmosphere of hydrogen / carbon monoxide = 1/1 (molar ratio). And then charged inside the autoclave with hydrogen / carbon monoxide =
The pressure was adjusted to 90 atm (gauge pressure) with a mixed gas of 1/1 (molar ratio). The temperature in the autoclave was increased to 120 ° C., and a mixed gas of hydrogen / carbon monoxide = 1/1 (molar ratio) was supplied to maintain the internal pressure at 90 atm (gauge pressure). Of dicyclopentadiene (72 ml, 550 mmol, cyclopentadiene content: 500 ppm), 70 mg of maleic anhydride (0.71 mmol) and toluene 4
A mixture obtained by mixing 8 ml and stirring at room temperature for 10 hours under a nitrogen atmosphere was continuously fed to the autoclave at a rate of 20 ml / hr for 6 hours. After the completion of the feeding of the above mixed solution containing dicyclopentadiene, 1
The mixture was stirred at 20 ° C for 3 hours. When the obtained reaction solution was analyzed by gas chromatography [column: G-100 (trade name, manufactured by Chemical Inspection Association)], the conversion of dicyclopentadiene was 100%, and the yield of tricyclodecanedialdehyde was 100%. The rate was found to be 90%. In addition, the yield of the monoaldehyde form in which only one of the double bonds of dicyclopentadiene was hydroformylated (hereinafter, simply referred to as monoaldehyde form) was 10%.

Comparative Example 1 The procedure of Example 1 was repeated, except that 70 mg of maleic anhydride was not used. The resulting reaction solution was subjected to gas chromatography in the same manner as in Example 1. Analysis revealed that the conversion of dicyclopentadiene was 99%, the yield of tricyclodecanedialdehyde was 62%, and the yield of the monoaldehyde compound was 38%. When stirring at 120 ° C. was further continued for 6 hours, the conversion of dicyclopentadiene was 99%, and the yield of tricyclodecanedialdehyde was 74%.
% And the yield of the monoaldehyde compound was 26%.

Example 2 Internal volume 300 ml provided with gas inlet and sampling port
1.754 mg (0.0068 mmol) of dicarbonylacetylacetonatotrodium in a magnetic stirring type autoclave of Tris (2,4-di-t-butylphenyl)
440 mg (0.68 mmol) of phosphite, 29 μl (0.21 mmol) of triethylamine, toluene 4
ml and 16 ml of 2-propanol were charged in a mixed gas atmosphere of hydrogen / carbon monoxide = 1/1 (molar ratio) without touching air, and then hydrogen / carbon monoxide = 1/1 ( (Atmolar ratio) and 90 atm (gauge pressure). Set the temperature in the autoclave to 12
The temperature was raised to 0 ° C., and a mixed gas of hydrogen / carbon monoxide = 1/1 (molar ratio) was supplied to maintain the internal pressure at 90 atm (gauge pressure), and 120 g of dicyclopentadiene containing 60 mg of cyclopentadiene (120 ml, 0.91 mol, cyclopentadiene content: 500 ppm), 133 mg (1.36 mmol) of maleic anhydride, 216 μl (1.56 mmol) of triethylamine and 30 ml of 2-propanol were mixed and stirred at room temperature under a nitrogen atmosphere for 10 hours. (Hereinafter, this is abbreviated as mixture 1)
Was fed to the autoclave at a rate of 10 ml / hr / h for 8 hours. When the feed of the mixture 1 was completed, the reaction solution was sampled and analyzed by gas chromatography in the same manner as in Example 1. As a result, the conversion of dicyclopentadiene was 100%, and the yield of tricyclodecanedialdehyde was 100%. Rate is 93% and the yield of the monoaldehyde compound is 7
%. The reaction solution after the completion of the feeding of the mixture 1 was left as it was for 1 hour.

400 g (400 ml, 3.03 mol, content of cyclopentadiene: 500 ppm) of dicyclopentadiene containing 200 mg of cyclopentadiene, 445 mg of maleic anhydride (4.54 mmol), 720 μl of triethylamine (5.2 mmol) and 2 Mixed with 100 ml of propanol and mixed at room temperature under a nitrogen atmosphere.
After stirring for an hour, 8.77 mg (0.034 mmol) of dicarbonylacetylacetonatotrodium and 2.2 g (3.4 mmol) of tris (2,4-di-t-butylphenyl) phosphite are added. The prepared mixture (hereinafter, abbreviated as mixture 2) is
The reaction mixture obtained above (one hour after the completion of feeding of the mixture 1) was continuously fed to the autoclave at a rate of 10 ml / hr / hour. During this time, a mixed gas of hydrogen / carbon monoxide = 1/1 (molar ratio) was supplied to the reaction vessel to maintain the internal pressure at 90 atm (gauge pressure).
Further, the reaction liquid was continuously withdrawn so that the liquid amount in the autoclave was kept constant at the same time as the start of the feed of the mixed liquid 2. The reaction liquid (withdrawn liquid) at the point when 20 hours had elapsed since the start of the feed of the mixed liquid 2 was analyzed by gas chromatography in the same manner as in Example 1.
It was found that the conversion of dicyclopentadiene was 100%, the yield of tricyclodecanedialdehyde was 88%, and the yield of the monoaldehyde compound was 12%.

Comparative Example 2 The same operation as in Example 2 was carried out except that maleic anhydride was not used, and the obtained reaction liquid (withdrawn liquid) was treated in the same manner as in Example 1 with gas. Analysis by chromatography revealed that the conversion of dicyclopentadiene was 99%, the yield of tricyclodecanedialdehyde was 38%, and the yield of the monoaldehyde form was 62%.

Example 3 Internal Volume 100 with Gas Inlet and Sampling Port
5.16 mg (0.02 mmol) of dicarbonylacetylacetonatotrodium and 65.5 mg (0.25 mg) of triphenylphosphine were placed in a 2.5 ml electromagnetically stirred autoclave.
5 mmol), 20 ml of toluene and 30 g of dicyclopentadiene containing 11 mg of cyclopentadiene (3 g).
0 ml, 0.23 mol, content of cyclopentadiene:
370 ppm) and maleic anhydride 25 mg (0.2
6 mmol) and stirred under a nitrogen atmosphere at room temperature for 10 hours, and charged under a mixed gas atmosphere of hydrogen / carbon monoxide = 1/1 (molar ratio) so as not to come into contact with air. Hydrogen / carbon monoxide = 1/1 in the autoclave
(Molar ratio) with a mixed gas of 90 atm (gauge pressure), the temperature in the autoclave was raised to 120 ° C, and hydrogen /
The reaction was carried out at the same temperature for 5 hours while supplying a mixed gas of carbon monoxide = 1/1 (molar ratio) and maintaining the pressure in the autoclave at 90 atm (gauge pressure). When the obtained reaction solution was analyzed by gas chromatography in the same manner as in Example 1, the conversion of dicyclopentadiene was 100%, the yield of tricyclodecanedialdehyde was 84%,
The yield of the monoaldehyde was found to be 16%.

Comparative Example 3 The same operation as in Example 3 was carried out except that 25 mg of maleic anhydride was not used, and the resulting reaction solution was subjected to gas chromatography in the same manner as in Example 1. As a result of the analysis, the conversion of dicyclopentadiene was 99%, the yield of tricyclodecanedialdehyde was 49%, and the yield of the monoaldehyde compound was 51%.

Example 4 Internal Volume 100 with Gas Inlet and Sampling Port
1.29 mg (0.005 mmol) of dicarbonylacetylacetonatotrodium, 130 mg (0.25 mmol) of tris (2-methyl-5-t-butylphenyl) phosphite, 30 ml of toluene, And 20 g of dicyclopentadiene containing 26 mg of cyclopentadiene (20 ml, 0.15
Mol, content of cyclopentadiene: 1300 ppm)
And dimethyl fumarate 85mg (0.59mmol)
And a mixture obtained by stirring at room temperature for 40 hours in a nitrogen atmosphere is charged in a mixed gas atmosphere of hydrogen / carbon monoxide = 1/1 (molar ratio) so as not to come into contact with air, and the inside of the autoclave is charged. After the pressure in the autoclave was raised to 110 ° C. after the pressure in the autoclave was increased to 50 atm (gauge pressure) with a mixed gas of hydrogen / carbon monoxide = 1/1 (molar ratio), hydrogen / carbon monoxide = 1.
While maintaining the pressure in the autoclave at 50 atm (gauge pressure) by supplying a mixed gas of / 1 (molar ratio), the reaction was carried out at the same temperature for 2.5 hours. When the obtained reaction solution was analyzed by gas chromatography in the same manner as in Example 1,
It was found that the conversion of dicyclopentadiene was 100%, the yield of tricyclodecanedialdehyde was 88%, and the yield of the monoaldehyde compound was 12%.

Comparative Example 4 The procedure of Example 4 was repeated, except that 85 mg of dimethyl fumarate was not used. The resulting reaction solution was subjected to gas chromatography in the same manner as in Example 1. As a result of the analysis, the conversion of dicyclopentadiene was 99%, the yield of tricyclodecanedialdehyde was 42%, and the yield of the monoaldehyde compound was 58%.

REFERENCE EXAMPLE Internal volume of 300 ml provided with a hydrogen inlet and a hydrogen outlet
Of the reaction solution obtained in Example 1 [27 g of tricyclodecanedialdehyde
(0.14 mol)], isopropanol 50
ml and Raney nickel [Degussa Japan, B
-113W (trade name), moisture content: about 50% by weight]
4.0 g was charged, and the inside of the autoclave was replaced with hydrogen. Next, the temperature in the autoclave was set to 100 under stirring.
° C, while continuously supplying hydrogen so that the pressure in the autoclave is maintained at 8 atm (gauge pressure).
After reacting for an hour, the internal temperature was further increased to 120 ° C.
The reaction was performed for 5 hours while maintaining the pressure (gauge pressure). After the reaction was completed, the reaction mixture was cooled to room temperature, and the reaction mixture was taken out and Raney nickel was filtered off. As a result of analyzing the obtained filtrate by gas chromatography, no unreacted raw material (tricyclodecanedialdehyde) was detected. By distilling the filtrate obtained above under reduced pressure, TCDDM (b.
p. 188 ° C./2 mmHg).

[0038]

According to the present invention, the hydroformylation reaction of dicyclopentadiene can be carried out smoothly, and as a result, tricyclodecanedialdehyde can be industrially advantageously produced.

Claims (3)

[Claims] 1. A method of reacting dicyclopentadiene with hydrogen and carbon monoxide in the presence of a rhodium compound, a monodentate tertiary organophosphorus compound and dienophile, wherein 3 (or 4), 8 ( Or 9) A method for producing diformyltricyclo [5.2.1.0 ^2,6 ] decane. 2. The method according to claim 1, wherein at least a part of the dienophile is previously mixed with dicyclopentadiene and then reacted with hydrogen and carbon monoxide.
(Or 9) -diformyltricyclo [5.2.1.0
^2,6 ] Method for producing decane. 3. The reaction pressure is 150 atm or less, the concentration of the monodentate tertiary organophosphorus compound is 10 mmol or less per liter of the reaction solution, and the concentration of the rhodium compound is rhodium atom conversion per liter of the reaction solution. 3 (or 4), 8 (or 9) -diformyltricyclo [5.
2.1.0 ^2,6 ] method for producing decane.