JP2003055291A - Method for producing 3-hydroxyaldehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a 3-hydroxyaldehyde useful as a raw material for a 1,3-alkanediol used for uses such as polyester polyols, lubricants and plasticizers from the corresponding oxirane derivative at a high reaction rate and in a high yield. SOLUTION: This method for producing the 3-hydroxyaldehyde comprises bringing an oxirane derivative into contact with a metal carbonyl compound and an alkali metal or alkaline earth metal alkoxide in the presence of carbon monoxide and hydrogen to hydroformylate the oxirane derivative.

Description

Detailed Description of the Invention TECHNICAL FIELD OF THE INVENTION

The present invention relates to a method for hydroformylating an oxirane derivative with carbon monoxide and hydrogen to produce 3-hydroxyaldehyde.

[0002]

BACKGROUND OF THE INVENTION 3-Hydroxyaldehyde is useful as a raw material for 1,3-alkanediols, which are useful as raw materials for polyester polyols, lubricating oils, plasticizers and the like. 3-Hydroxyaldehyde can be prepared by contacting the corresponding oxirane derivative with a metal carbonyl compound and hydroformylating with carbon monoxide and hydrogen.

In the hydroformylation reaction, in order to improve the reaction rate and selectivity, improvement of the catalyst system by modification of a metal carbonyl compound and development of a hydroformylation accelerator have been carried out. For example, Tokuyohei 8-507
048 discloses a method of hydroformylating an oxirane derivative with carbon monoxide and hydrogen using a cobalt carbonyl compound modified with ditertiary phosphine as a catalyst and using an acid and a metal salt as a promoter. The derivative has a slow concentration rate and a low conversion rate.
Further, in Japanese Patent Publication No. 10-507165, a phosphine-coordinated or non-phosphine-coordinated cobalt carbonyl compound is used as a catalyst, and a lipophilic quaternary salt of a Group V element is used as an accelerator to convert an oxirane derivative into carbon monoxide and hydrogen. Discloses a method for hydroformylation. In this method, although the reaction rate is improved by the promoter, it is desired that the reaction rate and the selectivity are further improved. Also,
There is a drawback in using highly toxic compounds such as phosphonium salts as accelerators.

[0004]

An object of the present invention is to provide a method capable of producing 3-hydroxyaldehyde from an oxirane derivative with a high reaction rate and a high yield.

[0005]

The present invention has the general formula (I)

[0006]

[Chemical 5]

An oxirane derivative represented by the formula: wherein R ¹ represents a hydrogen atom or alkyl is prepared by reacting a metal carbonyl compound and a general formula (II) in the presence of carbon monoxide and hydrogen:

[0008]

[Chemical 6]

A method for producing 3-hydroxyaldehyde is provided, which comprises contacting with a compound represented by the formula: wherein R ² represents alkyl and X represents an alkali metal atom or an alkaline earth metal atom. To do.

Hereinafter, the oxirane derivative represented by the general formula (I) may be referred to as a compound (I) and the compound represented by the general formula (II) may be referred to as a compound (II).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the definition of each group in the general formulas (I) and (II), examples of alkyl include linear or branched alkyl having 1 to 20 carbon atoms,
Specific examples include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, decyl and eicosyl. Examples of alkali metal atoms include lithium, sodium,
Examples include atoms such as potassium, rubidium, and cesium,
Examples of alkaline earth metal atoms include beryllium, magnesium, calcium, strontium, barium, and other atoms.

In the compound (I), R ¹ is preferably a hydrogen atom or alkyl having 1 to 8 carbon atoms,
Furthermore, it is more preferable that R ¹ is a hydrogen atom. In the compound (II), ^{R 2} is alkyl of 1 to 8 carbon atoms, it is preferable for X is an alkali metal atom, in particular, ^{R 2} is tert- butyl, that X is potassium More preferable.

The compound (I) is preferably contacted with the metal carbonyl compound and the compound (II) in the presence of a solvent. Examples of the solvent include aliphatic hydrocarbon solvents such as hexane and isooctane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, methanol, ethanol, tert-butyl alcohol,
Alcohol-based solvents such as propanol, ethyl cellosolve, butyl cellosolve, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc., aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, butylbenzene, tetralin, etc. Examples of the solvent include ether solvents such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, crown ether, and ethylene glycol dimethyl ether, and mixed solvents of these solvents. Among them, aromatic hydrocarbon solvents are particularly preferable. A mixed solvent of a solvent and an ether solvent is preferable, and a more preferable solvent is a mixed solvent of toluene or xylene and tetrahydrofuran or dioxane. Ri, most preferred solvent is a mixed solvent of toluene and tetrahydrofuran. If necessary, water may be added to the reaction system, and the amount used is preferably 0.5 to 5% by weight based on the reaction liquid.

When a mixed solvent of an aromatic hydrocarbon solvent and an ether solvent is used, the ratio of ether solvent: aromatic hydrocarbon solvent is preferably 1: 0.5 to 20 (weight). , 1: 1 to 20 (weight) is more preferable, and 1: 1 to 5 (weight) is the most preferable. The solvent is preferably used in a 5-fold amount (weight) to a large excess amount with respect to the compound (I), and 5 to 100.
More preferably, a double amount (weight) is used.

The metal carbonyl compound is preferably a carbonyl compound of a metal belonging to Group 9 of the periodic table (cobalt, rhodium, iridium, etc.), and more preferably a cobalt carbonyl compound. Specific preferred examples of the cobalt carbonyl compound include hydrocobalt tetracarbonyl and dicobalt octacarbonyl. In addition, the metal carbonyl compound is
It may be modified with a phosphorus compound such as o (CO) ₃ P (C ₆ H ₅ ) ₃ and HCo (CO) ₃ P (C ₄ H ₉ ) ₃ .

The metal carbonyl compound can be purchased as a commercial product, or can be produced by a known method. For example, the cobalt carbonyl compound can be obtained by dispersing fine particle cobalt salt or metallic cobalt powder in a solvent and contacting with carbon monoxide in a reactor in which oxygen is blocked. At this time, the reaction temperature is preferably 100 to 150 ° C., and the partial pressure of carbon monoxide is preferably 3.0 MPa or more. The amount of the metal carbonyl compound used is not particularly limited, but is preferably 0.01 to 15% by weight, more preferably 0.05 to 10% by weight, based on the compound (I).

The compound (II) is preferably used in an amount of 0.01 to 0.50 equivalent (molar ratio), and preferably 0.10 to 0.35 equivalent (molar ratio) with respect to the metal carbonyl compound. More preferable. The concentration of the compound (I) in the reaction solution is preferably 1 to 30% by weight, 5 to 2
It is more preferably 5% by weight.

Hydrogen and carbon monoxide are preferably used in an amount of 2 equivalents (molar ratio) to a large excess relative to compound (I). The ratio of hydrogen to carbon monoxide is preferably 1: 2 to 1: 0.2 (molar ratio), more preferably 1: 1.5 to 1: 0.5 (molar ratio). .

The contact of the compound (I) with the metal carbonyl compound and the compound (II) is preferably carried out at a temperature of 120 ° C or lower, more preferably 60 to 100 ° C.
Most preferably, it is performed at 70 to 90 ° C. The contact of the compound (I) with the metal carbonyl compound and the compound (II) is preferably carried out at a pressure of 5.0 to 25.0 MPa, more preferably 8.0 to 20.0 MPa. Compound (I) with metal carbonyl compound and compound (I
The method of contacting with I) may be a batch method or a continuous method. Further, as a mode of bringing the compound (I) into contact with the metal carbonyl compound and the compound (II), for example, the metal carbonyl compound and the compound (II) are packed in a column reactor and the compound (I) is passed through the column. Although the method of making it tower | column may be used, you may carry out by a batch type.

In the production method of the present invention, 1,3-alkanediol may be co-produced in addition to 3-hydroxyaldehyde. The 3-hydroxyaldehyde obtained by the production method of the present invention can be converted to a 1,3-alkanediol by subjecting it to a hydrogenation reaction by a known method. In the hydrogenation, the reaction solution after the reaction in the above-mentioned 3-hydroxyaldehyde production may be subjected to the hydrogenation reaction as it is, but the 3-hydroxyaldehyde is extracted from the reaction solution with an aqueous solvent to obtain a metal carbonyl compound. Hydrogenation may be performed after separating the above. Further, the isolated 3-hydroxyaldehyde may be subjected to a hydrogenation reaction. Further, the metal carbonyl compound separated by the extraction can be reused.

Hydrogenation is carried out, for example, on 3-hydroxyaldehyde by hydrogenation catalyst (copper-chromium catalyst, Raney nickel catalyst, palladium on aluminum oxide or activated carbon, or platinum on aluminum oxide or activated carbon). In the presence of a catalyst, or a catalyst formed by mixing these active ingredients with other components), preferably 50 ° C. or higher, more preferably 60 to 10
At a temperature of 0 ° C., preferably a hydrogen pressure of 1.0 MPa or more,
More preferably, the hydrogen pressure is 3.0 MPa or more.
For example, when using a tower reactor, the liquid hourly space velocity LHSV of 3-hydroxyaldehyde [hydrogenation catalyst (cm ³ ).
The flow rate of 3-hydroxyaldehyde (cm ³ / hour)] is preferably 0.1 to 5.0 (/ hour), and more preferably 0.2 to 2.0 (/ hour). Furthermore, by distillation or the like from the hydrogenated reaction solution,
The 1,3-alkanediol can be separated.

According to the present invention, from the oxirane derivative,
The reaction rate is fast, and 3-hydroxyaldehyde can be produced in high yield. The compound (II) used in the production method of the present invention has low toxicity. Further, by hydrogenating 3-hydroxyaldehyde produced by the production method of the present invention, a polyester polyol,
It is also possible to produce 1,3-alkanediols that are useful in applications such as lubricating oils and plasticizers.

[0023]

Example 1 In a 500 ml autoclave, 263 g of a mixed solvent of toluene-tetrahydrofuran (THF) in a weight ratio of 2: 1 was used as a reaction solvent, and dicobalt octacarbonyl 1.45.
g (0.0085 mol), deionized water 3 g, and potassium tert-butoxide 0.24 g were added. H
_The internal gas replacement was performed twice with a mixed gas having a ₂ / CO mixing ratio of 1.1: 1. Then, the autoclave was filled with hydrogen and pressurized to 3 MPa, and then the H ₂ / CO mixing ratio was 1.
It was filled with 1: 1 synthesis gas and pressurized to 10 MPa.
After preheating this mixed solution at 80 ° C. for 1 hour, 20 g (0.45 mol) of ethylene oxide (EO) was added to start the hydroformylation reaction. The reaction was followed by gas chromatography while sequentially supplying the H ₂ / CO mixed gas consumed by the reaction. By performing the reaction for 1 hour, 3-hydroxypropionaldehyde was obtained. The conversion rate of ethylene oxide determined by gas chromatography analysis was 80%. The yield was 70% when gas chromatography analysis was performed after treating the reaction solution by the method described below.

Gas Chromatographic Analysis Conditions for Determining the Conversion of Ethylene Oxide: The reaction liquid was analyzed under the following gas chromatography analysis conditions. Column: Petrocall DH Capillary (Supelco)
(Diameter 0.25 mm x length 100 m) Temperature condition: Temperature rising from 40 ° C to 300 ° C at 10 ° C / min Detector: Hydrogen flame ionization detector

Pretreatment for Gas Chromatographic Analysis for Obtaining Yield and Its Conditions: (Preparation of Analytical Sample) After completion of the reaction, the reaction solution was cooled to 25 ° C., 40 g of water was added, and the reaction was continued for 15 minutes. After stirring, the aqueous layer was separated. Furthermore, 40g is taken from the water layer and TH
40 g of F was added. This solution was subjected to a hydrogenation reaction for 2 hours at 5 MPa and 80 ° C. using 5% by weight of Raney nickel to obtain a sample for analysis by gas chromatography.

The sample treated as described above is
The analysis was performed under the following gas chromatography analysis conditions. Column: CP-Wax 58CB (FFAP) (Varian, Inc.) (diameter 0.25 mm x length 25 m) Temperature condition: Temperature rising from 40 ° C to 220 ° C at 5 ° C / min Detector: Hydrogen flame ionization detector

The yield was calculated by the following formula.

[0028]

[Equation 1]

Further, the reaction rate in Example 1 was calculated by the following formula, and was 43 (/ hour).

[0030]

[Equation 2]

[0031]

INDUSTRIAL APPLICABILITY The present invention provides a method capable of producing 3-hydroxyaldehyde from an oxirane derivative with a high reaction rate and a high yield.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 31/20 C07C 31/20 B Z 47/19 47/19 (72) Inventor Toshihiko Yamaguchi Ichihara City, Chiba Prefecture Goi Minami Kaigan 11-1 Kyowa Yuka Co., Ltd., Chiba Plant (72) Inventor Takayuki Suzuki Ichihara, Chiba Prefecture Goi Minami Kaigan 11-1 Kyowa Yuka Co., Ltd., Chiba Plant (72) Inventor Kenji Harada Ichihara, Chiba Prefecture Goi Minamikaigan 11-1 Kyowa Yuka Co., Ltd., Chiba Factory (72) Inventor Masumi Iwasawa Ichihara, Chiba Prefecture Goi Minamikaigan 11-1 Kyowa Yuka Co., Ltd., Chiba Factory (72) Inventor Takao Yamada Ichihara, Chiba Chiharadai 4-78-8 (72) Inventor Ryoichi Nakajima 5-6-14 Tokokubunjidai, Ichihara-shi, Chiba F-term (reference) 4G069 AA06 AA08 BA21A BA21B BC01A BC03A BC03B BC08A BC67A BC67B BC71A BC74 A BE06A BE06B BE42A BE42B CB51 DA02 4H006 AA02 AC41 AC45 BA02 BA20 BA32 BB11 BB15 BE20 BE40 4H039 CA60 CA62 CH70 CL45

Claims (9)

[Claims] 1. A compound represented by the general formula (I): [In the formula, R ¹ represents a hydrogen atom or alkyl], an oxirane derivative represented by the formula (II) with a metal carbonyl compound in the presence of carbon monoxide and hydrogen: [In the formula, R ² represents alkyl, X represents an alkali metal atom or an alkaline earth metal atom], a method for producing a 3-hydroxyaldehyde, which comprises contacting the compound. 2. The method according to claim 1, wherein the metal of the metal carbonyl compound is a metal belonging to Group 9 of the periodic table. 3. The method according to claim 2, wherein the metal belonging to Group 9 of the periodic table is cobalt. 4. X in the compound represented by formula (II)
Is an alkali metal atom, The manufacturing method in any one of Claims 1-3. 5. The method according to claim 4, wherein the alkali metal atom is potassium. 6. The production method according to claim 1, wherein 1,3-alkanediol is also produced. 7. A oxirane derivative represented by the general formula (I) is contacted with a metal carbonyl compound and a compound represented by the general formula (II) in a mixed solvent of an ether solvent and an aromatic hydrocarbon solvent. The manufacturing method according to any one of claims 1 to 6. 8. A compound represented by the general formula (I): [Wherein R ¹ has the same meaning as defined above], and an oxirane derivative represented by the formula (II) with a metal carbonyl compound in the presence of carbon monoxide and hydrogen: [In the formula, R ² and X are as defined above]
A method for producing a 1,3-alkanediol, which comprises a step of producing a 3-hydroxyaldehyde by contacting the compound represented by 9. The production method according to claim 8, comprising a step of subjecting 3-hydroxyaldehyde to a hydrogenation reaction.