JPH06199730A - Production of hydroxybutyraldehyde compound - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing hydroxybutyraldehydes with a high selectivity while reducing the amount of the organic diphosphine compound used. [Structure] In the reaction of hydroformylating allyl alcohol in the presence of a rhodium complex catalyst having triphenylantimony as a ligand, the organic diphosphine compound is added in an amount of 0.4 to 1.2 equivalents per gram atom of rhodium. Add to the reaction system to produce hydroxybutyraldehydes.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing hydroxy buraldehydes.

The hydroxybutyraldehydes obtained in the present invention can be easily converted into butanediols by hydrogenation by a known method. Of these butanediols, 1,4-butanediol is a compound derived from tetrahydrofuran and is extremely useful as a raw material for polyester and polyurethane.

[0003]

2. Description of the Related Art It is known to produce hydroxybutyraldehyde using a rhodium complex catalyst having an organic phosphine compound as a ligand in a reaction for hydroformylating allyl alcohol (hereinafter referred to as AOH).
For example, this technique is disclosed in Japanese Patent Publication No. 53-19563, Japanese Patent Publication No. 56-5372, Japanese Patent Publication No. 62-54781, or Toyo Soda Research Report, 25 (1), 3 (19).
81) and the like. However, in the hydroformylation reaction of AOH, in the rhodium complex catalyst system having an organic phosphine compound as a ligand, other products such as hydroxybutyraldehyde, particularly 4-hydroxybutyraldehyde (hereinafter abbreviated as HBA), are produced. A by-product, that is, 2-methyl-3-hydroxypropionaldehyde (hereinafter abbreviated as MHP) which is an isomer of HBA, n-propyl alcohol (hereinafter abbreviated as PrOH) which is a hydride of AOH, and The generation of propionaldehyde (hereinafter abbreviated as Pald), which is an isomer of AOH, cannot be avoided.

For example, in the above-mentioned Toyo Soda research report,
In the hydroformylation reaction of AOH, influences of reaction pressure, ratio of hydrogen to carbon monoxide, reaction temperature and phosphine concentration and kind of rhodium phosphine complex catalyst on HBA selectivity are disclosed. According to this, the higher the hydrogen partial pressure and the higher the reaction temperature, the more the Pald and PrO.
H increases and HBA selectivity decreases. On the other hand, conversely, when the carbon monoxide partial pressure is increased, MHP increases, so that the target HBA selectivity is at most 7 even under the optimized conditions.
Only 9%.

Therefore, several attempts have been made to selectively obtain HBA in the hydroformylation reaction of AOH. U.S. Pat. No. 4,064,145 discloses a catalyst system comprising a combination of hexarhodium hexadecacarbonyl and triphenylphosphine, HB
A is obtained with a selectivity of 87%. However, in this method, the rhodium complex itself is unstable such as decomposition, and the amount thereof is usually as much as 50 times (as a rhodium metal) that is industrially used, which is economically advantageous. It becomes a problem.

Further, a method of using a special organic diphosphine compound as a ligand of a rhodium complex catalyst has been disclosed. For example, Charles Yu Pitman, Jr. et al. Obtained 1,1'-bis (diphenylphosphino) ferrocene to obtain HBA with a selectivity of 87% [Journ.
al of Organic Chemistry, 4
5, 2132 (1980)]. However, these methods have a slower reaction rate than monodentate ligands, and the absolute pressure is 22k.
A high pressure of g / cm ² or higher is required.

Further, in Japanese Patent Laid-Open No. 4-169579, trans-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane is used to select HBA at low pressure. An example of getting 87% is disclosed. However, this method requires at least 1.5 equivalents or more of the organic diphosphine compound having this special optical activity per gram atom of rhodium in order to obtain HBA with high selectivity. Furthermore, since these ligands are usually gradually deteriorated by a trace amount of oxygen contained in the raw material gas, an excess amount of the ligands is allowed to coexist in the reaction system, or the ligands are added as necessary. It is necessary to add them. Therefore, since a large amount of expensive ligands are required, it cannot be said that the economy is necessarily excellent.

[0008]

Therefore, in the reaction for hydroformylating AOH in the presence of hydrogen and carbon monoxide, the amount of expensive organic diphosphine compound used is reduced, and MHP, PrOH and Pald are produced as by-products. Development of a method for obtaining HBA by suppressing and highly selective was expected. That is, an object of the present invention is to provide a highly selective method for producing HBA that reduces the amount of the organic diphosphine compound used.

[0009]

[Means for Solving the Problems] In view of such a current situation,
The present inventors diligently studied the hydroformylation reaction of AOH. As a result, when a rhodium complex catalyst having an antimony compound as a ligand is used, the amount of expensive organic diphosphine compound used can be reduced, and HBA
The inventors have found that the above can be obtained with high selectivity, and have completed the present invention.

That is, according to the present invention, in the reaction of hydroformylating allyl alcohol in the presence of a rhodium complex catalyst having an antimony compound as a ligand, the following general formula (1)

[0011]

[Chemical 5] (In the formula,

[0012]

[Chemical 6] Is a substituted or unsubstituted 3-5 ring structure in which the ring-forming element is carbon or carbon and oxygen;
¹ , R ² , R ³ and R ⁴ each independently represent an aryl group or an alkyl group) or the following general formula (2)

[0013]

[Chemical 7] (In the formula,

[0014]

[Chemical 8] Represents a substituted or unsubstituted five-membered ring structure elements forming a ring consisting of carbon and ^{nitrogen, R 1', R 2', R} 3'
And R ^4'are each independently ants - organic diphosphine compound represented by represents a group or an alkyl group), per rhodium 1 gram atom of rhodium complex catalyst 0.4
The present invention provides a highly selective method for producing HBA, which is characterized by adding 1.2 equivalents to a reaction system.

Next, the present invention will be described in more detail.

According to the present invention, in the reaction of hydroformylating allyl alcohol in the presence of a rhodium complex catalyst having an antimony compound as a ligand, the organic compound represented by the general formula (1) or (2) is used. The diphosphine compound is added to the reaction system.

Specific examples of the organic diphosphine compound include trans-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane,
Trans-4,5-bis (dibutylphosphinomethyl)
-2,2-Dimethyl-1,3-dioxolane, cis-N
-T-butoxycarbonyl-2- (diphenylphosphinomethyl) -4- (diphenylphosphino) pyrrolidine, cis-Nt-butoxycarbonyl-2- (diphenylphosphinomethyl) -4- (dicyclohexylphosphino) pyrrolidine , Cis-2- (diphenylphosphinomethyl) -4- (diphenylphosphino) pyrrolidine and the like.

Further, trans-1,2-bis (diphenylphosphinomethyl) cyclopropane, trans-1,
2-bis (diphenylphosphinomethyl) cyclobutane, trans-1,2-bis (diphenylphosphinomethyl) cyclopentane, or trans-2,3-bis (diphenylphosphinomethyl) -bicyclo [2.
2.1] Heptane and the like can be mentioned. Of these, trans-4,5-bis (diphenylphosphinomethyl)-
2,2-Dimethyl-1,3-dioxolane is easily available. The amount of the organic diphosphine compound used is rhodium 1
0.4 to 1.2 equivalents, preferably 0.5 to 1.1 equivalents, and more preferably 0.8 to gram atoms.
Is in the range of 1.0 equivalent.

In the present invention, a rhodium complex catalyst having an antimony compound as a ligand is used. Here, the rhodium complex catalyst having an antimony compound as a ligand can be easily prepared from an antimony compound and a rhodium compound by a known complex formation method. Alternatively, the antimony compound may be introduced into a hydroformylation reactor together with an appropriate rhodium compound to form a complex in the presence of a mixed gas of hydrogen and carbon monoxide for use. For example, Te
A method for forming the same is disclosed in trahedron, 40, 185 (1984) and the like.

In this case, suitable rhodium compounds are, for example, HRh (CO) (PPh ₃ ) ₃ and Rh (CO) ₂ (a
ch), Rh (acac) ₃ , [Rh (OAc) (C
O) ₂ ] ₂ , Rh (OAc) ₃ , Rh ₂ (OAc)
₂ (1,5-COD) ₂ , Rh ₄ (CO) ₁₂ , Rh ₆
(CO) ₁₆ , Rh (CO) (acac) (SbP
h ₃ ) ₃ (where acac represents acetylacetonate, Ac represents an acetyl group, and COD represents 1,5-cyclooctadiene) and the like, among which Rh (CO) ₂ (Acac) or HRh (C
O) (PPh ₃ ) ₃ is preferably used. These rhodium complexes can be synthesized by known methods from rhodium inorganic compounds such as rhodium nitrate, rhodium sulfate, rhodium trichloride, rhodium oxide, rhodium organic acid salts such as rhodium acetate, various salts of rhodium and carbonyl compounds.

Further, the antimony compound used in the above method is represented by the general formula SbR ⁵ R ⁶ R ⁷ (wherein R ⁵ , R ⁶ and R ⁷ are independently an aryl group, an arylalkyl group or an alkyl group). Group, which represents a group). Specific examples thereof include triphenyl antimony, tritolyl antimony, trichlorophenyl antimony, tribenzyl antimony, trinaphthyl antimony, diphenylmethyl antimony, diphenylethyl antimony, phenyldimethyl antimony, phenyl diethyl antimony, trimethyl antimony, triethyl antimony, tripropyl antimony. , Tributyl antimony, trioctyl antimony and the like, among which triphenyl antimony is more preferably used.

According to the present invention, the amount of the rhodium complex catalyst used is not particularly limited, but it is usually used at a concentration of 0.01 to 100 mmol, preferably 0.1 to 50 mmol per liter of the hydroformylation reaction liquid. To be done. When the catalyst concentration is lower than this, sufficient hydroformylation activity may not be obtained. On the contrary, when the catalyst concentration is higher than this, the reaction activity does not increase and it is not economical. On the other hand, the amount of the antimony compound used is in the range of 3 to 500 equivalents, preferably 5 to 100 equivalents, per gram atom of rhodium.

In the present invention, a solvent can be used if necessary. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, n-hexane and n.
-Saturated hydrocarbons such as heptane and cyclohexane; ethers such as diethyl ether and dipropyl ether; alcohols such as methanol, ethanol and butanol; ethers or ether glycols of polyhydric alcohols such as diethylene glycol diethyl ether and triethylene glycol monomethyl ether. Examples thereof include esters such as ethyl benzoate and dioctyl phthalate, and the like, with preference given to toluene, xylene and dioctyl phthalate.

The reaction temperature for the hydroformylation of the present invention is
The temperature is 0 to 150 ° C, preferably 10 to 100 ° C, more preferably 30 to 80 ° C. If the reaction temperature is low,
When the reaction temperature exceeds 150 ° C., the side reaction increases and the HBA selectivity tends to decrease.

The reaction pressure is 0 to 50 kg / cm in absolute pressure.
² , preferably 0.1 to 15 kg / cm ² . The composition of the oxo gas at this time, that is, the molar ratio of hydrogen to carbon monoxide is in the range of 0.1 to 30, preferably 0.5 to 20, and more preferably 0.8 to 1.
The range is 0. The oxo gas may contain a gas inert to the reaction, such as nitrogen, argon, helium, or the like.

This reaction can be carried out batchwise, semi-continuously or continuously. The HBA obtained by the reaction is separated from the reaction solution by a known method such as extraction with water or distillation, and 1,4 by a known hydrogenation method.
-Can be butanol

..

INDUSTRIAL APPLICABILITY According to the present invention, in the hydroformylation reaction of AOH, the amount of the organic diphosphine compound used can be reduced, and by-products of MHP, Pald and PrOH can be suppressed, and HBA can be obtained highly selectively. .

[0028]

The present invention will be described in more detail below with reference to examples, but these examples show the outline of the present invention, and the present invention is not limited to these examples. .

Example 1 A pressure resistant reaction vessel made of stainless steel having an internal volume of 300 ml equipped with a thermometer, a stirrer, and a gas blowing port was used, and rhodium-hydride (carbonyl) tri (triphenylphosphine) [HRh (CO) ( PPh ₃ ) ₃ ] 82.
6 mg (0.090 mmol) of trans-4,5-bis (diphenylphosphinomethyl)-was used as a ligand.
2,2-Dimethyl-1,3-dioxolane (hereinafter, DI
Abbreviated as OP) 44.9 mg (0.090 mmol)
And triphenylantimony 0.318g (0.90m
mol) and 150 ml of toluene as a solvent.

After the inside of the reaction vessel was sufficiently replaced with nitrogen gas and then with a mixed gas of hydrogen / carbon monoxide = 4.0 (molar ratio), the absolute pressure in the reaction vessel was 3 kg / cm ² , and the flow rate of the incoming gas was It was adjusted to 75.0 NL / hr, and the stirring speed was maintained at 1000 rpm and the temperature at 65 ° C. Under sufficient stirring under the mixed gas stream, 141 mmol of AOH was continuously added over 48 minutes to carry out the reaction. AOH
After the addition was completed, the reaction conditions were maintained for an additional 24 minutes to complete the reaction. The discharged gas is led to a trap in a dry ice / ethanol bath and entrained AOH, Pol and PrOH
Was collected in the trap.

The unreacted AOH and products entrained in the reaction solution and in the unreacted gas were analyzed by gas chromatography. As a result, the conversion rate of the raw material AOH was 98.9 m.
ol%, hydroxybutyraldehyde 85.1
mol%, 2-methylhydroxypropionaldehyde 13.9 mol% and propionaldehyde 0.4.
mol% was produced.

Example 2 22.5 mg (0.045 mm) of DIOP was used as a ligand.
ol) and 0.318 g of triphenylantimony
The reaction was performed in the same manner as in Example 1 except that (0.90 mmol) was used. The results are shown in Table 1.

Example 3 53.9 mg (0.108 mm) of DIOP was used as a ligand.
ol) and 0.318 g of triphenylantimony
The reaction was performed in the same manner as in Example 1 except that (0.90 mmol) was used. The results are shown in Table 1.

[0034]

[Table 1] Comparative Example 1 22.5 mg (0.045
mmol) was used, and the reaction was performed in the same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 2 and 3 In Comparative Example 2, only 44.9 mg of DIOP was used as the ligand.
(0.090 mmol), and Comparative Example 3
Is 67.4 mg (0.135 mmol) of DIOP only
The reaction was performed in the same manner as in Example 1 except that it was used. The results are shown in Table 2.

[0036]

[Table 2]

Claims (1)

[Claims] 1. In a reaction for hydroformylating allyl alcohol in the presence of a rhodium complex catalyst having an antimony compound as a ligand, the following general formula (1): (In the formula, Is a substituted or unsubstituted 3-5 ring structure in which the ring-forming element is carbon or carbon and oxygen;
¹ , R ² , R ³ and R ⁴ each independently represent an aryl group or an alkyl group) or the following general formula (2): (In the formula, Represents a substituted or unsubstituted five-membered ring structure elements forming a ring consisting of carbon and ^{nitrogen, R 1', R 2', R} 3'
And R ^4'are each independently ants - organic diphosphine compound represented by represents a group or an alkyl group), per rhodium 1 gram atom of rhodium complex catalyst 0.4
A method for producing hydroxybutyraldehydes, which comprises adding 1.2 equivalents to a reaction system.