JP3065430B2 - Method for hydroformylation of allyl alcohol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for hydroformylation of allyl alcohol. 2-Hydroxytetrahydrofuran obtained by the method of the present invention can be easily converted to 1,4-butanediol by hydrogen reduction. 1,4-butanediol is extremely useful as a raw material for polybutylene terephthalate and urethane resin, and as a raw material for tetrahydrofuran, which is an excellent solvent.

[0002]

2. Description of the Related Art Generally, carbon monoxide and hydrogen are obtained by using an olefinic compound as a catalyst with a Group IX metal complex compound such as a rhodium complex compound, or using triphenylphosphine (monodentate ligand) as a ligand. In the case of hydroformylation by reacting with olefinic compounds, depending on the type and amount of olefinic compounds, ligands, etc., the reaction rate, conversion of olefins, types and amounts of by-products, the desired linear or branched oxo compounds It is well known that selectivity and yield are greatly affected.

The same can be said for the hydroformylation reaction of allyl alcohol, and the formation of 1,4-, while suppressing the production of the main by-products 2-methyl-3-hydroxypropanal, propionaldehyde and n-propanol.
Many attempts have been made to obtain 2-hydroxytetrahydrofuran, a precursor of butanediol, with high selectivity. As a result, it has been found that the selectivity of the target substance can be greatly changed depending on the type of the ligand added to the reaction system.

[0004] For example, Japanese Patent Application Laid-Open No. 51-29412 discloses hydridecarbonyltris (triphenylphosphine) rhodium (I) industrially used in the hydroformylation reaction of propylene, and triphenylphosphine as a ligand. An example is described in which a catalyst system combining (monodentate ligand) is applied to allyl alcohol to obtain 2-hydroxytetrahydrofuran with a selectivity of 75 to 79%. The linear aldehyde formed by the hydroformylation reaction of allyl alcohol is 4-hydroxybutyraldehyde, which isomerized and exists as a more stable 2-hydroxytetrahydrofuran. [Journal of Organic Chemistry. 45, 2132 (1980)].

[0005] Also, the same report by See You Pitman Jr. [Journal of Organic Chemistry. 45, 2132 (1980)], when triphenylphosphine (monodentate ligand) is used as the ligand, the selectivity of 2-hydroxytetrahydrofuran is 67% (normal / iso ratio). Is 2.
0), when using tributylphosphine (monodentate ligand), 40% (many high-boiling products), and 1,1′-bis (diphenylphosphino) ferrocene (bidentate ligand) were used. In this case, it is 75% (normal / iso ratio is 3.3), and the reaction results are significantly different depending on the type of ligand. Therefore, in order to obtain a high linear selectivity, it is most suitable for allyl alcohol. The need to select a ligand is indicated.

JP-A-54-106407 discloses the above-mentioned catalyst system comprising a rhodium complex compound and triphenylphosphine (monodentate ligand), and further represented by 1,4-bis (diphenylphosphino) butane. It is disclosed that the use of a ternary catalyst to which a diphosphinoalkane (bidentate ligand) is added improves the catalyst life. However, the selectivity of 2-hydroxytetrahydrofuran is 75 to 79%, and the result of the improvement of the selectivity by addition of diphosphinoalkane has not been recognized. In addition, 2-methyl-3- which is an isomeric product
In addition to hydroxypropanal, undesired by-products such as propionaldehyde and n-propanol are produced at a selectivity of about 10%.

As still another example, Japanese Patent Application Laid-Open No. Sho 53-1217
No. 11 discloses that a hydroformylation reaction is carried out using a diphosphine compound having a structure in which two adjacent carbon atoms in a ring are substituted by two phosphinomethyl groups located in trans with each other as a ligand. It is reported that the linear selectivity is improved. Transformers 1-2
Although an example using -bis (diphenylphosphinomethyl) cyclobutane is shown, there is no example using allyl alcohol as a substrate.

[0008] JP-A-56-26830 discloses that
Rhodium compounds and diphosphine compounds having a structure in which two adjacent carbon atoms on an alicyclic hydrocarbon ring having 3 to 6 carbon atoms are substituted by two phosphinomethyl groups located in trans with each other (bidentate coordination) It is disclosed that by performing a hydroformylation reaction with a ternary catalyst using a trisubstituted phosphine (monodentate ligand) and a trisubstituted phosphine (monodentate ligand), the catalyst life can be improved. Although examples using trans-1,2-bis (diphenylphosphinomethyl) cyclobutane and trans-1,2-bis (diphenylphosphinomethyl) cyclopentane are shown, there is no example of allyl alcohol, and There is no clear description of the effect on chain selectivity.

[0009]

As described above, as described above,
In the case where allyl alcohol is subjected to hydroformylation by reacting with carbon monoxide and hydrogen in the presence of a rhodium complex compound, investigation of various catalyst ligands has revealed that 2-hydroxy is useful as a precursor of 1,4-butanediol. Attempts have been made to obtain tetrahydrofuran with good selectivity, but the effects of these catalytic ligands vary greatly depending on the type of reaction substrate. Cannot be said to have a sufficient effect unless it is particularly suitable for allyl alcohol. In a reaction system using allyl alcohol as a substrate, the selectivity of a linear product which is industrially desirable is lower than that in the case of hydroformylation of a simple olefin, and propionaldehyde which is an isomerization product of allyl alcohol is used. And n-propanol, which is a hydrogenation product of allyl alcohol, is by-produced.
A method for obtaining hydroxytetrahydrofuran without these by-products and with high industrial selectivity has not yet been found.

It is an object of the present invention to reduce the selectivity of these by-products and to increase the selectivity when allyl alcohol is reacted with carbon monoxide and hydrogen in the presence of a rhodium complex compound to effect hydroformylation. To provide a method for obtaining 2-hydroxytetrahydrofuran at a high rate.

[0011]

The present inventors have studied the effect of adding a large number of organophosphorus ligands to solve the above problems, and as a result, have found that a diphosphine compound having a specific structure (bidentate) Ligand) significantly reduced the selectivity of by-products of propionaldehyde and n-propanol and significantly improved the selectivity of linear products, thereby completing the present invention.

That is, according to the first aspect of the present invention, allyl alcohol is reacted under the pressure of carbon monoxide and hydrogen in the presence of a rhodium compound and a diphosphine compound represented by the general formula (I). This is a method for hydroformylation of allyl alcohol. In the formula, R ¹ is an alkyl group or a substituted or unsubstituted aryl group, structural formula (Formula 4) is an alkyl-substituted or unsubstituted norbornane or norbornene ring, and R ² and R ³ are
Represents an alkyl group or a hydrogen atom.

[0013]

Embedded image

[0014]

Embedded image

The invention of claim 2 of the present invention relates to a compound of the general formula (I)
Is trans-2,3-bis (diphenylphosphinomethyl) bicyclo- [2,2,1] -heptane and / or trans-2,3-bis (diphenylphosphinomethyl) bicyclo- [2 , 2,1] -hept-5-ene.

The invention according to claim 3 of the present invention is the method according to claim 1, wherein a phosphine compound represented by the general formula (II) is further added to the reaction system. PR ⁴ R ⁵ R ⁶ (II) In the formula, R ⁴ , R ⁵ and R ⁶ represent an alkyl group or a substituted or unsubstituted aryl group.

Conventionally, in the hydroformylation reaction of allyl alcohol, there has been a problem that the selectivity of an industrially desirable linear product is low as described above, but the method of the present invention solves these problems. By the hydroformylation reaction of allyl alcohol, 1,4-
It is possible to obtain 2-hydroxytetrahydrofuran, a precursor of butanediol, with an extremely high selectivity.

Examples of the diphosphine compound (bidentate ligand) used in the present invention include trans-2,3-bis (diphenylphosphinomethyl) bicyclo- [2,
2,1] -heptane (hereinafter abbreviated as reDPMNr), trans-2,3-bis (diphenylphosphinomethyl)
Bicyclo- [2,2,1] -hept-5-ene (hereinafter D
PMNr), trans-2,3-bis (diphenylphosphinomethyl) -2-methyl-bicyclo- [2,
2,1] -heptane, trans-2,3-bis (diphenylphosphinomethyl) -2-methyl-bicyclo-
[2,2,1] -hept-5-ene, trans-2,3
-Bis (diphenylphosphinomethyl) -1,4,5
6,7-pentamethyl-bicyclo- [2,2,1] -heptane, trans-2,3-bis (diphenylphosphinomethyl) -1,4,5,6,7-pentamethyl-bicyclo- [2,2 , 1] -hept-5-ene, trans-
2,3-bis (diphenylphosphinomethyl) -1,
2,4,5,6,7-hexamethyl-bicyclo- [2,
2,1] -heptane, trans-2,3-bis (diphenylphosphinomethyl) -1,2,4,5,6,7-hexamethyl-bicyclo- [2,2,1] -hept-5-
En and the like. Among them, reDPMNr and DPMNr are particularly preferable in order to more effectively achieve the object of the present invention.

The amount of diphosphine used in the present invention is from 0.5 to 50 mol, preferably from 1.5 to 10 mol, per gram atom of rhodium in order to increase the selectivity of 2-hydroxytetrahydrofuran. It is desirable. When the use amount of diphosphine is 0.5 mol or less, the selectivity of the linear product is lowered, which is not preferable. If it is used in an amount of 50 mol or more, the reaction rate decreases, which is economically disadvantageous.

In the present invention, in addition to the phosphine compound (bidentate ligand), a trisubstituted phosphine (monodentate ligand) can be further added. Examples of the phosphine compound that can be used at this time include triphenylphosphine, tri-p-tolylphosphine, and tri-m
-Tolylphosphine, tris (p-methoxyphenyl)
Phosphine, tris (m-methoxyphenyl) phosphine, tris (p-chlorophenyl) phosphine, tris (m-chlorophenyl) phosphine, tris (p-fluorophenyl) phosphine, tris (m-fluorophenyl) phosphine, tris (p -Trifluoromethylphenyl) phosphine, triethylphosphine, triisopropylphosphine, tributylphosphine, tricyclohexylphosphine, ethyldiphenylphosphine,
Diethylphenylphosphine and the like. It is desirable to use 2 to 500 moles per 1 gram atom of rhodium.

The rhodium compound used in the present invention may be any of those used in conventional olefin hydroformylation catalysts, and specifically, RhO, Rh ₂ O
₃ , rhodium oxides such as RhO ₂ , rhodium nitrate, rhodium sulfate, rhodium salts such as rhodium chloride, rhodium bromide, rhodium iodide, rhodium acetate and acetylacetonatodicarbonylrhodium, acetylacetonatocarbonyl (triphenylphosphine) Rhodium complex compounds such as rhodium, hydride carbonyl tris (triphenylphosphine) rhodium, and Rh ₄ (C
O) _12, such as rhodium carbonyl clusters such as Rh ₆ (CO) ₁₆ and the like.

In the present invention, the amount of the catalyst used is not particularly limited, but is such an amount that rhodium in the catalyst is in the range of 1 × 10 ^-2 to 1 × 10 ^-4 gram atom per mole of allyl alcohol. It is appropriate to use.

The solvent used in the present invention is preferably one which is inert to the starting material allyl alcohol and the product. Specific examples include benzene, toluene, xylene, ethylbenzene, aromatic hydrocarbons such as dodecylbenzene, n-hexane, heptane, cyclohexane, saturated hydrocarbons such as methylcyclohexane,
Diethyl ether, ethers such as diphenyl ether, methyl acetate, ethyl acetate, diethyl phthalate, dibutyl phthalate, carboxylic acid esters such as dioctyl phthalate and the like, among these, benzene, toluene, xylene, ethylbenzene, dodecylbenzene, Aromatic compounds such as diethyl phthalate, dibutyl phthalate and dioctyl phthalate are particularly preferred. The amount of the solvent used is not particularly limited, but is suitably 2 to 50 times (volume) with respect to allyl alcohol.

The reaction temperature of the hydroformylation in the present invention is preferably in the range of 40 to 100 ° C., particularly preferably 50 to 80 ° C. When the reaction temperature is lower than 40 ° C., the reaction rate becomes extremely low, and when it exceeds 100 ° C., the selectivity of 2-hydroxytetrahydrofuran decreases and the stability of the catalyst is impaired.

The molar ratio of the carbon monoxide / hydrogen mixed gas as the raw material gas used in the present invention is from 1/10 to 10/1.
Is preferable. The reaction pressure is not particularly limited, but it is practically preferable to carry out the reaction in the range of 1 to 20 atm.

[0026]

EXAMPLES Hereinafter, the method of the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto without departing from the gist of the present invention. Example 1 2.0 g of allyl alcohol (34.4 g) was placed in a 50 ml autoclave equipped with a thermometer and a stirrer.
mmol), 5.16 mg of Rh (acac) (CO) ₂ (20
μmol), 19.7 mg (40 μmol) of reDPMNr and 16 ml of toluene. After the stirring was started and the inside of the autoclave was sufficiently replaced with nitrogen gas and then CO / H ₂ mixed gas, the solution was heated until the liquid temperature became a constant temperature of 65 ° C. Thereafter, a mixed gas of CO / H ₂ = 1/1 (molar ratio) was introduced so that the pressure in the autoclave became 6.0 atm, and the reaction was started. During the reaction, the pressure in the system was 6.0 atm
, A mixed gas of CO / H ₂ = 1/1 was added. Thus, the hydroformylation reaction of allyl alcohol was performed under a constant pressure and a constant temperature. The reaction products were quantitatively analyzed by gas chromatography, and all the products were isolated and identified by ¹ H- and ¹³ C-NMR.

After 3 hours from the start of the reaction, the conversion of allyl alcohol was 97.9%.
2.59 g of hydroxytetrahydrofuran (29.4 g)
mmol), and 0.362 g (4.11 mmol) of 2-methyl-3-hydroxypropanal was produced. The selectivity for 2-hydroxytetrahydrofuran is 87.2 mol%
(Hereinafter abbreviated as%). Also, 2-methyl-3-
Hydroxypropanal, propionaldehyde, n-
The selectivity of propanol was 12.2% and 0.1%, respectively.
4% and 0.13%.

Example 2 39.4 mg of reDPMNr
(80 μmol), the reaction pressure was 9 atm, and the reaction temperature was 5 atm.
An allyl alcohol hydroformylation reaction was carried out in the same manner as in Example 1 except that the temperature was changed to 5 ° C. Six hours after the start of the reaction, the conversion of allyl alcohol was 94.3.
%, And the reaction gave 2.54 g (28.8 mmol) of 2-hydroxytetrahydrofuran and 2-methyl-
0.303 g (3.44 g) of 3-hydroxypropanal
mmol). The selectivity for 2-hydroxytetrahydrofuran was 88.8%. Also, 2-methyl-
3-hydroxypropanal, propionaldehyde,
The selectivity of n-propanol was 10.6%,
0.17% and 0.15%.

[Embodiment 3] Instead of reDPMNr, D
The hydroformylation reaction of allyl alcohol was carried out in the same manner as in Example 1 except that 19.7 mg (40 μmol) of PMNr was added. As a result, the reaction rate of allyl alcohol after 3 hours was 99.9%, and this reaction resulted in 2.58 g of 2-hydroxytetrahydrofuran (2
9.3 mmol) and 0.423 g (4.82 mmol) of 2-methyl-3-hydroxypropanal were produced. 2-
The selectivity for hydroxytetrahydrofuran was 85.1%. The selectivities of 2-methyl-3-hydroxypropanal, propionaldehyde, and n-propanol were 14.0%, 0.15%, and 0.13%, respectively.

Example 4 Apart from reDPMNr, the allyl alcohol hydroformylation reaction was carried out in the same manner as in Example 1 except that 262 mg (1.0 mmol) of triphenylphosphine was further added. After 3 hours from the start of the reaction, the conversion of allyl alcohol was 90.5%. By this reaction, 2.40 g (27.3 mmol) of 2-hydroxytetrahydrofuran and 2-methyl-3-
0.330 g of hydroxypropanal (3.75 mmo
l) had generated. The selectivity for 2-hydroxytetrahydrofuran was 87.5%. Also, 2-methyl-3
-Hydroxypropanal, propionaldehyde, n
-Selectivity for propanol is 12.0%, 0.
16% and 0.13%.

Example 5 In addition to reDPMNr, tris (p-fluorophenyl) phosphine was further added to 316
The hydroformylation reaction of allyl alcohol was carried out in the same manner as in Example 1 except that mg (1.0 mmol) was added. 4.5 hours after the start of the reaction, the conversion of allyl alcohol was 94.1%, and this reaction resulted in 2.53 g (28.7 mm) of 2-hydroxytetrahydrofuran.
ol), 2-methyl-3-hydroxypropanal is 0.1%.
313 g (3.56 mmol) had been produced. The selectivity for 2-hydroxytetrahydrofuran was 88.8%.
The selectivity of 2-methyl-3-hydroxypropanal is 11.0%, and propionaldehyde, n-
No propanol was detected.

Example 6 As a Rh compound, Rh (a
2. cac) Rh ₆ (CO) ₁₆ instead of (CO) ₂ .
Example 1 except that 53 mg (3.33 μmol) was used.
The hydroformylation reaction of allyl alcohol was carried out in the same manner as described above. After 3 hours from the start of the reaction, the conversion of allyl alcohol was 91.5%.
2.41 g of hydroxytetrahydrofuran (27.4 g)
mmol) and 0.310 g (3.52 mmol) of 2-methyl-3-hydroxypropanal. The selectivity for 2-hydroxytetrahydrofuran was 86.9%. Also, 2-methyl-3-hydroxypropanal,
The selectivity of propionaldehyde and n-propanol is
They were 11.2%, 1.08% and 0.29%, respectively.

Comparative Example 1 A hydroformylation reaction of allyl alcohol was carried out in the same manner as in Example 1 except that 21.0 mg (80 μmol) of triphenylphosphine was added instead of reDPMNr. After 3 hours from the start of the reaction, the conversion of allyl alcohol was 100%, and this reaction resulted in 1.87 g (21.2 mmol) of 2-hydroxytetrahydrofuran and 1.14 g of 2-methyl-3-hydroxypropanal. (12.9 mmol) had been formed. The selectivity for 2-hydroxytetrahydrofuran was 61.6%. The selectivities of 2-methyl-3-hydroxypropanal and propionaldehyde were 37.5% and 0.85%, respectively, and n-propanol was not detected.

Comparative Example 2 1,4-bis (diphenylphosphino) butane was used instead of reDPMNr.
The hydroformylation reaction of allyl alcohol was carried out in the same manner as in Example 1 except that 1 mg (40 μmol) was added. After 3 hours from the start of the reaction, the conversion of allyl alcohol was 97.9%, and this reaction resulted in 1.91 g (21.7 mmol) of 2-hydroxytetrahydrofuran.
l), 2-methyl-3-hydroxypropanal is 0.1%.
866 g (9.83 mmol) was produced. The selectivity for 2-hydroxytetrahydrofuran was 65.7%.
The selectivities of 2-methyl-3-hydroxypropanal, propionaldehyde, and n-propanol were 29.8%, 1.75%, and 0.65%, respectively.

Comparative Example 3 trans-1,2-bis (diphenylphosphinomethyl) was used instead of reDPMNr
Hydroformylation of allyl alcohol was carried out in the same manner as in Example 1 except that 18.1 mg (40 μmol) of cyclobutane was added. After 6 hours from the start of the reaction, the conversion of allyl alcohol was 90.2%, and this reaction gave 2.7% of 2-hydroxytetrahydrofuran.
9 g (24.5 mmol) and 0.610 g (5.37 mmol) of 2-methyl-3-hydroxypropanal were produced. The selectivity of 2-hydroxytetrahydrofuran is 7
It was 9.0%. The selectivities of 2-methyl-3-hydroxypropanal, propionaldehyde and n-propanol were 17.3%, 2.10% and 0.1%, respectively.
09%.

Comparative Example 4 trans-1,2-bis (diphenylphosphinomethyl) was used instead of reDPMNr
The hydroformylation reaction of allyl alcohol was carried out in the same manner as in Example 1 except that 18.7 mg (40 μmol) of cyclopentane was added. The reaction rate of allyl alcohol 4 hours after the start of the reaction was 93.3%, and 2-hydroxytetrahydrofuran was converted to 2.3.3% by this reaction.
85 g (25.1 mmol) and 0.729 g (6.42 mmol) of 2-methyl-3-hydroxypropanal were produced. The selectivity of 2-hydroxytetrahydrofuran is 7
8.2%. The selectivities of 2-methyl-3-hydroxypropanal, propionaldehyde, and n-propanol were 20.0%, 0.41%, and 0.4%, respectively.
19%.

Comparative Example 5 trans-1,2-bis (diphenylphosphinomethyl) was used instead of reDPMNr
The hydroformylation reaction of allyl alcohol was performed in the same manner as in Example 1 except that 19.3 mg (40 μmol) of cyclohexane was added. Five hours after the start of the reaction, the conversion of allyl alcohol was 51.5%, and this reaction reduced the amount of 2-hydroxytetrahydrofuran to 0.1%.
51 g (5.80 mmol) and 1.00 g (11.4 mmol) of 2-methyl-3-hydroxypropanal were produced. The selectivity of 2-hydroxytetrahydrofuran is 3
2.7%. The selectivities of 2-methyl-3-hydroxypropanal and propionaldehyde were 64.4% and 1.70%, respectively, and n-propanol was not detected.

[0038]

As described above, according to the present invention, when allyl alcohol is reacted with carbon monoxide and hydrogen in the presence of a rhodium complex compound to effect hydroformylation, a diphosphine ligand having a specific structure (dithiophene) is used. Allyl alcohol can be converted to 2-hydroxytetrahydrofuran, which is a precursor of 1,4-butanediol, with high selectivity by using a (dentate ligand).

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-261775 (JP, A) JP-A-56-166185 (JP, A) UK Patent Application Publication 1528697 (GB, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 307/20 B01J 31/24 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. Hydroformylation of allyl alcohol, wherein allyl alcohol is reacted under the pressure of carbon monoxide and hydrogen in the presence of a rhodium compound and a diphosphine compound represented by the general formula (I). Method. In the formula, R ¹ represents an alkyl group or a substituted or unsubstituted aryl group, structural formula (Formula 2) represents an alkyl group-substituted or unsubstituted norbornane or norbornene ring, and R ² and R ³ represent an alkyl group or a hydrogen atom Represents Embedded image Embedded image 2. The compound represented by the general formula (I) is trans-2,3-bis (diphenylphosphinomethyl) bicyclo- [2,2,1] -heptane and / or trans-2,3-bis The method according to claim 1, which is (diphenylphosphinomethyl) bicyclo- [2,2,1] -hept-5-ene. 3. The method according to claim 1, wherein a phosphine compound represented by the general formula (II) is further added to the reaction system. PR ⁴ R ⁵ R ⁶ (II) In the formula, R ⁴ , R ⁵ and R ⁶ represent an alkyl group or a substituted or unsubstituted aryl group.