JPH05331156A - Hydrofomylation of allyl alcohol - Google Patents

Abstract

PURPOSE:To carry out the hydroformylation of allyl alcohol by reacting allyl alcohol with carbon monoxide and hydrogen in the presence of a rhodium complex compound and a diphosphine compound. CONSTITUTION:Allyl alcohol is made to react with carbon monoxide and hydrogen in the presence of a rhodium compound and a diphosphine compound of formula (R<1> is alkyl or aryl; R<2> and R<3> are alkyl or H) in a solvent (e.g. toluene) at 40-100 deg.C under l-20 atm. pressure. 2-Hydroxytetrahydrofuran useful as a precursor for 1,4-butanediol can be produced by this process in high selectivity while suppressing the formation of by-products such as 2-methyl-3- hydroxypropanal, propionaldehyde and n-propanol. The compound of formula is e.g. trans-2,3-bis(diphenylphosphinomethyl)bicyclo-[2,2,1]-heptane.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for hydroformylating 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 resins, and as a raw material for tetrahydrofuran, which is an excellent solvent.

[0002]

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

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

For example, in JP-A-51-29412, hydridocarbonyltris (triphenylphosphine) rhodium (I), which is industrially used in the hydroformylation reaction of propylene, and triphenylphosphine as a ligand. An example is described in which a catalyst system in which a (monodentate ligand) is combined is applied to allyl alcohol to obtain 2-hydroxytetrahydrofuran with a selectivity of 75 to 79%. The straight-chain aldehyde produced by the hydroformylation reaction of allyl alcohol is 4-hydroxybutyraldehyde, which is isomerized and exists as more stable 2-hydroxytetrahydrofuran. Have been published by [Journal of Organic Chemistry. 45, 2132 (1980)].

In addition, the same C-You Pitman Jr. report [Journal of Organic Chemistry. , 45, 2132 (1980)], when triphenylphosphine (monodentate ligand) is used as a ligand, the selectivity of 2-hydroxytetrahydrofuran is 67% (normal / iso ratio). Is 2.
0), when using tributylphosphine (monodentate ligand), 40% (there are many high-boiling products), 1,1′-bis (diphenylphosphino) ferrocene (bidentate ligand) was used. In this case, the reaction result is 75% (normal / iso ratio is 3.3), and the reaction results greatly differ 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 has been demonstrated.

Japanese Unexamined Patent Publication (Kokai) No. 54-106407 discloses that the above catalyst system comprising a rhodium complex compound and triphenylphosphine (monodentate ligand) is further represented by 1,4-bis (diphenylphosphino) butane. It is disclosed that the catalyst life can be improved by using a ternary catalyst to which a diphosphinoalkane (bidentate ligand) is added. However, the selectivity of 2-hydroxytetrahydrofuran is 75 to 79%, and the result of improvement of the selectivity by the addition of diphosphinoalkane has not been recognized. Further, 2-methyl-3-, which is an isoform 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 Laid-Open No. 53-1217
No. 11 discloses a hydroformylation reaction using a diphosphine compound having a structure in which two adjacent carbon atoms in the ring are substituted with two phosphinomethyl groups located in trans with each other. It has been reported that the linear chain selectivity is improved. Transformer-1,2
An example using -bis (diphenylphosphinomethyl) cyclobutane is shown, but no example using allyl alcohol as a substrate.

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

[0009]

[Problems to be Solved by the Invention] As described above,
In the case of hydroformylation in which allyl alcohol is reacted with carbon monoxide and hydrogen in the presence of a rhodium complex compound, 2-hydroxy, which is useful as a precursor of 1,4-butanediol, has been investigated by examining various catalytic ligands. Attempts have been made to obtain tetrahydrofuran with good selectivity, but the effect of these catalytic ligands varies greatly depending on the type of reaction substrate, so the catalytic ligands used in the catalyst system for the hydroformylation reaction of allyl alcohol. Cannot be said to have a sufficient effect unless it is particularly suitable for allyl alcohol. In the reaction system using allyl alcohol as a substrate, the selectivity of a linear product that 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 the problem that n-propanol, which is a hydrogenation product of allyl alcohol, is by-produced, which is useful as a precursor of 1,4-butanediol.
No method has yet been found for obtaining hydroxytetrahydrofuran industrially with high selectivity without these by-products.

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

[0011]

As a result of investigating the effect of adding a large number of organic phosphorus ligands in order to solve the above-mentioned problems, the present inventors have found that a diphosphine compound having a certain specific structure (bidentate It was found that the ligand) significantly reduces the selectivity of by-products of propionaldehyde and n-propanol and significantly improves the selectivity of the linear product, and has completed 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). And a method for hydroformylating allyl alcohol. In the formula, R ¹ is an alkyl group or a substituted or unsubstituted aryl group, the structural formula (Formula 4) is an alkyl group-substituted or unsubstituted norbornane or norbornene ring, and R ² and R ³ are
Represents an alkyl group or a hydrogen atom.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

The invention of claim 2 of the present invention is represented by the general formula (I)
Is a 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 industrially desirable linear product selectivity is low as described above, but the method of the present invention solves these problems. The hydroformylation reaction of allyl alcohol produces 1,4-
2-Hydroxytetrahydrofuran, a precursor of butanediol, can be obtained with extremely high selectivity.

As an example of the diphosphine compound (bidentate ligand) used in the present invention, trans-2,3-bis (diphenylphosphinomethyl) bicyclo- [2,2
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 can be mentioned. Among them, reDPMNr and DPMNr are particularly preferable in order to achieve the object of the present invention more effectively.

The amount of diphosphine used in the present invention is 0.5 to 50 mol, preferably 1.5 to 10 mol per 1 gram atom of rhodium in order to increase the selectivity of 2-hydroxytetrahydrofuran. Is desirable. When the amount of diphosphine used 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 will decrease, which is economically disadvantageous.

In the present invention, in addition to the above phosphine compound (bidentate ligand), a tri-substituted 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,
Examples thereof include diethylphenylphosphine. The amount used is preferably 2 to 500 mol per 1 gram atom of rhodium.

The rhodium compound used in the present invention may be one used in a conventional olefin hydroformylation catalyst, and specifically, RhO and Rh ₂ O.
₃ , RhO ₂ and other rhodium oxides, rhodium nitrate, rhodium sulfate, rhodium chloride, rhodium bromide, rhodium iodide, rhodium acetate and other rhodium salts and acetylacetonate dicarbonyl rhodium, acetylacetonatocarbonyl (triphenylphosphine) Rhodium, hydridocarbonyltris (triphenylphosphine) rhodium, and other rhodium complex compounds and Rh ₄ (C
Examples thereof include rhodium carbonyl clusters such as O) ₁₂ and Rh ₆ (CO) ₁₆ .

The amount of the catalyst used in the present invention is not particularly limited, but the amount of rhodium in the catalyst is in the range of 1 × 10 ^-2 to 1 × 10 ^-4 gram atom per 1 mol of allyl alcohol. It is suitable to use.

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

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

The molar ratio of the carbon monoxide / hydrogen mixed gas which is the raw material gas used in the present invention is from 1/10 to 10/1.
Is preferred. 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 The method of the present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples without departing from the gist of the present invention. [Example 1] 2.0 g of allyl alcohol (34.4) was placed in an autoclave having a content of 50 ml equipped with a thermometer and a stirrer.
mmol), Rh (acac) (CO) ₂ 5.16 mg (20
μmol), reDPMNr 19.7 mg (40 μmol) and toluene 16 ml. After stirring was started and the inside of the autoclave was sufficiently replaced with nitrogen gas and then CO / H ₂ mixed gas, the liquid temperature was raised to a constant temperature of 65 ° C. Then, a mixed gas of CO / H ₂ = 1/1 (molar ratio) was introduced so that the pressure in the autoclave became 6.0 atm to start the reaction. During the reaction, the pressure in the system was 6.0 atm
A mixed gas of CO / H ₂ = 1/1 was added so that Thus, the hydroformylation reaction of allyl alcohol was carried out 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 reaction rate of allyl alcohol was 97.9%.
Hydroxytetrahydrofuran is 2.59 g (29.4
mmol) and 0.32 g (4.11 mmol) of 2-methyl-3-hydroxypropanal were produced. The selectivity of 2-hydroxytetrahydrofuran is 87.2 mol%
(Hereinafter, abbreviated as%). Also, 2-methyl-3-
Hydroxypropanal, propionaldehyde, n-
The propanol selectivities are 12.2% and 0.1, respectively.
It was 4% and 0.13%.

[Example 2] 39.4 mg of reDPMNr
(80 μmol), reaction pressure 9 atm, reaction temperature 5
The hydroformylation reaction of allyl alcohol was carried out in the same manner as in Example 1 except that the temperature was 5 ° C. The reaction rate of allyl alcohol 6 hours after starting the reaction is 94.3.
%, And the reaction resulted in 2.54 g (28.8 mmol) of 2-hydroxytetrahydrofuran, 2-methyl-
0.303 g of 3-hydroxypropanal (3.44
mmol) had been produced. The selectivity of 2-hydroxytetrahydrofuran was 88.8%. Also, 2-methyl-
3-hydroxypropanal, propionaldehyde,
The selectivity of n-propanol is 10.6%,
It was 0.17% and 0.15%.

[Embodiment 3] D instead of reDPMNr
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 2.58 g (2
9.3 mmol) and 0.423 g (4.82 mmol) of 2-methyl-3-hydroxypropanal were produced. 2-
The selectivity of 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 The hydroformylation reaction of allyl alcohol was carried out in the same manner as in Example 1 except that 262 mg (1.0 mmol) of triphenylphosphine was added in addition to reDPMNr. The reaction rate of allyl alcohol after 3 hours from the start of the reaction was 90.5%, and by this reaction, 2.40 g (27.3 mmol) of 2-hydroxytetrahydrofuran and 2-methyl-3-
Hydroxypropanal 0.330g (3.75mmo
l) was generated. The selectivity of 2-hydroxytetrahydrofuran was 87.5%. Also, 2-methyl-3
-Hydroxypropanal, propionaldehyde, n
-Propanol selectivity is 12.0%, 0.
It was 16% and 0.13%.

[Example 5] In addition to reDPMNr, 316 tris (p-fluorophenyl) phosphine was further added.
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. The reaction rate of allyl alcohol was 94.1% 4.5 hours after the reaction was started, and 2.53 g (28.7 mm) of 2-hydroxytetrahydrofuran was obtained by this reaction.
ol), 2-methyl-3-hydroxypropanal is 0.
313 g (3.56 mmol) had been produced. The selectivity of 2-hydroxytetrahydrofuran was 88.8%.
Moreover, the selectivity of 2-methyl-3-hydroxypropanal is 11.0%, and the propionaldehyde, n-
No propanol was detected.

Example 6 As a Rh compound, Rh (a
Cac) (CO) ₂ instead of Rh ₆ (CO) ₁₆ .
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 in. The reaction rate of allyl alcohol after 3 hours from the start of the reaction was 91.5%.
2.41 g (27.4 g) of hydroxytetrahydrofuran
mmol), and 0.310 g (3.52 mmol) of 2-methyl-3-hydroxypropanal was produced. The selectivity of 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 The 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. The reaction rate of allyl alcohol was 100% after 3 hours from the start of the reaction, and 1.87 g (21.2 mmol) of 2-hydroxytetrahydrofuran and 1.14 g of 2-methyl-3-hydroxypropanal were obtained by this reaction. (12.9 mmol) had been produced. The selectivity of 2-hydroxytetrahydrofuran was 61.6%. In addition, 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 in place 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 reaction rate of allyl alcohol was 97.9%, and the reaction resulted in 1.91 g (21.7 mmo) of 2-hydroxytetrahydrofuran.
l), 2-methyl-3-hydroxypropanal is 0.
866 g (9.83 mmol) had been produced. The selectivity of 2-hydroxytetrahydrofuran was 65.7%.
Further, 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) instead of reDPMNr
The hydroformylation reaction 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 reaction rate of allyl alcohol was 90.2%, and the reaction resulted in 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%. In addition, the selectivities of 2-methyl-3-hydroxypropanal, propionaldehyde, and n-propanol are 17.3%, 2.10%, and 0.
It was 09%.

[Comparative Example 4] trans-1,2-bis (diphenylphosphinomethyl) 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 had a reaction rate of 2.3%.
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
It was 8.2%. The selectivity of 2-methyl-3-hydroxypropanal, propionaldehyde, and n-propanol are 20.0%, 0.41%, and 0.
It was 19%.

Comparative Example 5 Trans-1,2-bis (diphenylphosphinomethyl) instead of reDPMNr
The hydroformylation reaction of allyl alcohol was carried out in the same manner as in Example 1 except that 19.3 mg (40 μmol) of cyclohexane was added. The reaction rate of allyl alcohol after 5 hours from the start of the reaction was 51.5%.
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
It was 2.7%. In addition, 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 for hydroformylation, a diphosphine ligand having a specific structure By using a (dentate ligand), allyl alcohol can be highly selectively converted into 2-hydroxytetrahydrofuran which is a precursor of 1,4-butanediol.

Claims (3)

[Claims] 1. Hydroformylation of allyl alcohol characterized by reacting allyl alcohol 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. [Chemical 1] [Chemical 2] 2. A 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.