JPH1160567A - Production of 3-formyltetrahydrofuran - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for obtaining 3-formyltetrahydrofuran in a high selectivity and a high yield by using 2, 5 dihydrofuran and removing a very small amount of impurities giving an ill effect for hydroformylation reaction in the production of 3-formyltetrahydrofuran by the hydroformylation reaction of 2,5-dihydrofuran. SOLUTION: This method for producing 3-formyltetrahydrofuran is to perform a treatment for removing aldehydes which are inhibitory substances for hydroformylation reaction, to a reaction liquid containing 2,5-dihydrofuran and obtained through the production processes of the dehydrocyclization of cis-2-butene-1,4-diol with an acid catalyst or the rearrangement reaction of 3,4-epoxybutene, with a chemical reaction using a reducing agent or a condensing agent, and then effect hydrogen and carbon monoxide thereto in the presence of a metal compound selected from the elements of VIII group of the Periodic Table with an ester of phosphorous acid for producing 3-formyltetrahydrofuran.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a process for producing 3-formyltetrahydrofuran, which is an important intermediate in the fields of medicine and agricultural chemicals, particularly an important intermediate in the field of insecticides (JP-A-7-179448).

[0002]

BACKGROUND OF THE INVENTION The reaction of an olefin with hydrogen and carbon monoxide in the presence of a Group VIII metal compound to form an aldehyde is known as a hydroformylation reaction. Rhodium is known to be excellent in reactivity and selectivity among Group VIII metal compounds, but rhodium carbonyl is unstable and is generally used in a form modified with a ligand. As this ligand, a phosphorus compound such as trialkylphosphine, triarylphosphine or triarylphosphite, an arsenic compound or an antimony compound is generally used.

A method for producing 3-formyltetrahydrofuran by a hydroformylation reaction of 2,5-dihydrofuran is described in J. Am. C. . A report by Bayon et al. [Organome
talics, 11 (11), 3525-33 (1992); C. S. Chem. commu
n. , 600 (1990)] and U.S. Pat.
No. 208 and the like.

JP-A-57-123134 describes a method for hydroformylation of olefins with a rhodium catalyst modified with certain phosphites.

[0005] In addition to these methods, we have shown that the use of tris (2-tert-butyl-5-methylphenyl) phosphite as the ligand of the rhodium catalyst allows the selectivity to the 3-position of the hydroformylation reaction to be 90%. Thus, a method for obtaining 3-formyltetrahydrofuran in an efficient and satisfactory yield has been found.

[0006] 2,5-Dihydrofuran, which is a raw material of 3-formyltetrahydrofuran, is already a known compound,
A method is known in which cis-2-butene-1,4-diol is subjected to an acid-catalyzed dehydration cyclization reaction, or a method of producing cis-2-butene-1,4-diol by rearrangement of 3,4-epoxybutene. For example, as for the dehydration cyclization reaction of cis-2-butene-1,4-diol with an acid catalyst, a method of producing by adding a catalytic amount of sulfuric acid to cis-2-butene-1,4-diol and heating. (J. Org. Chem., 1963, 28, 1).
147) or cis-2-butene-1,4-diol by reacting with hydrogen bromide (J.O.
rg. Chem. , 1953, 18, 801) and cis-
Production method by adding a catalytic amount of iodine to 2-butene-1,4-diol and heating the mixture (J. Org. C)
hem. , 1981, 46, 3361). We also found that cis-
They have found a method for producing 2,5-dihydrofuran in high yield by subjecting 2-butene-1,4-diol to a dehydration cyclization reaction.

By rearrangement of 3,4-epoxybutene,
As a method for producing 2,5-dihydrofuran, a method has been reported in which 3,4-epoxybutene is rearranged in the presence of a catalyst containing iodide or a catalyst comprising one or more copper salts. (JP-A-3-77877, JP-A-8-59645, etc.)

[0008] As for the purification of 2,5-dihydrofuran, a method by distillation is known. (Japanese Patent Laid-Open No. 3-7
No. 7,877, J.P. Org. Chem. , 1981,
46, 3361 etc.) Org. Chem. , 1
953, 18, 801 include cis-2-butene-1,4
A method is described in which a reaction distillate containing 2,5-dihydrofuran produced by reacting hydrogen bromide with a diol is dried over potassium hydroxide and distilled.

However, crotonaldehyde and the like, which are by-products, cannot be completely removed by mere distillation purification. To obtain 2,5-dihydrofuran containing no crotonaldehyde or the like, a considerable portion must be discarded. It was not a method that could be implemented industrially at all.

The inventors of the present invention have studied a process for producing 3-formyltetrahydrofuran, and have found that rhodium-catalyzed hydroformyl using 2,5-dihydrofuran as a ligand with tris (2-t-butyl-5-methylphenyl) phosphite as a ligand. The reaction was carried out. At that time, the 2,5-dihydrofuran obtained by distillation from the reaction solution containing 2,5-dihydrofuran obtained through the production process has a reduced reaction rate during the hydroformylation reaction, and in some cases, the reaction is stopped. Results were not obtained. The same results were obtained with 2,5-dihydrofuran produced by drying the crude 2,5-dihydrofuran obtained by the same reaction with potassium hydroxide and then distilling it. In addition, the present inventors have confirmed that when dried with an alkali metal hydroxide, there is a problem in operation due to the formation of colored or pasty insolubles.

[0011]

In a method for producing 3-formyltetrahydrofuran by a hydroformylation reaction of 2,5-dihydrofuran, a pretreatment is carried out so as not to affect the hydroformylation reaction, and 3-formyltetrahydrofuran is obtained in a high yield.
It is an object of the present invention to provide a method for producing formyltetrahydrofuran.

[0012]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the cause of the inhibition of the hydroformylation reaction is several kinds of existing in 2,5-dihydrofuran. Found to be inhibitors. further,
It has been found that aldehydes such as crotonaldehyde, which is a by-product always contained in 2,5-dihydrofuran obtained through the production process, significantly inhibit the reaction.

The inventors of the present invention have conducted intensive studies on a method for removing these inhibitors, and as a result, by chemically treating a reaction solution of 2,5-dihydrofuran obtained through the production process, an inhibitor mainly containing aldehydes has been obtained. It has been found that the substance can be removed, and in the subsequent hydroformylation reaction, a stable reaction rate and a stable yield can be obtained, thereby completing the present invention.

That is, the present invention relates to cis-2-butene-1,
A reaction solution containing 2,5-dihydrofuran obtained through a production process in which 4-diol is subjected to a dehydration cyclization reaction with an acid catalyst or 3,4-epoxybutene is rearranged in the presence of a catalyst, After performing a treatment for removing aldehydes, which are inhibitors of the hydroformylation reaction, by a chemical reaction using a reducing agent or a condensing agent, in the presence of a metal compound selected from Group VIII of the Periodic Table of the Elements and phosphites A method for producing 3-formyltetrahydrofuran, wherein hydrogen and carbon monoxide are allowed to act on the mixture.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The reaction solution containing 2,5-dihydrofuran used in the present invention is cis-2-butene-
The 1,4-diol is subjected to a dehydration cyclization reaction with an acid catalyst, and crude 2,5-dihydrofuran distilled out of the reaction system (J. Orr)
g. Chem. , 1963, 28, 1147). Since the reaction temperature is generally as high as the boiling point of 2,5-dihydrofuran, the reaction is carried out while distilling 2,5-dihydrofuran out of the reaction system. Distilled 2,5-
Dihydrofuran is obtained in two layers containing about 15 to 25% water.

Alternatively, the reaction solution containing 2,5-dihydrofuran used in the present invention may be used in the presence of a catalyst in the presence of 3,4
A reaction solution of 2,5-dihydrofuran in which a rearrangement reaction of epoxybutene has been carried out (method described in JP-A-3-77877).

Regardless of which method is used to produce a reaction solution containing 2,5-dihydrofuran, the reaction solution contains several types of hydroformylation-inhibitory substances, mainly crotonaldehyde as a by-product. doing.

In the method of the present invention, the reaction solution of 2,5-dihydrofuran is subjected to a chemical treatment and then subjected to a hydroformylation reaction.

In the present invention, the chemical treatment means a reduction reaction and a condensation reaction. Examples of the reducing agent used in the reduction reaction include bisulfites such as sodium bisulfite and potassium bisulfite; sulfites such as sodium sulfite and potassium sulfite; and metal hydride complexes such as sodium borohydride. .

The reducing agent is used as an aqueous solution or solid in the reaction solution. The amount of the reducing agent is from 1 to 10 mol%, preferably from 1 to 5 mol%, based on 2,5-dihydrofuran in the reaction solution.
５5 mol%. The temperature for the treatment can be from 0 ° C. to the reflux temperature, but usually, stirring may be performed at room temperature for 1 hour.

After the treatment, if an aqueous layer is present, the aqueous layer is separated by liquid separation. Generally, the mutual solubility of 2,5-dihydrofuran and water is high, and a solvent having low mutual solubility with water, such as toluene and xylene, is added to lower the mutual solubility of 2,5-dihydrofuran and water to carry out liquid separation. preferable. Also,
Even when the above-mentioned solvent is present at the time of mixing the reaction solution and the reducing agent, there is no problem in removing the inhibitor of the hydroformylation reaction.

Examples of the condensing agent used in the condensation reaction include amines. Examples of the amines include aliphatic primary amines such as methylamine and propylamine, and aromatic primary amines such as aniline, anisidine, toluidine, aminophenol, and naphthylamine.

The amount of amines added is 2,5-
It is 1 to 10 mol%, preferably 1 to 5 mol%, based on dihydrofuran. The temperature for the treatment can be from 0 ° C. to the reflux temperature, but the treatment may usually be carried out at room temperature for 1 hour. After the treatment, if an aqueous layer is present, the aqueous layer is separated by liquid separation. Even if a solvent having a low mutual solubility with water, such as toluene or xylene, is present during mixing, there is no problem in removing the inhibitor of the hydroformylation reaction.

After the reaction solution is mixed with a reducing agent or an amine, the separated oil layer is dried with a desiccant, if necessary. Absorbents such as molecular sieves as desiccants, alkali metal carbonates such as sodium carbonate and potassium carbonate,
Examples thereof include hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, and anhydrous sulfates such as anhydrous sodium sulfate and anhydrous magnesium sulfate. These desiccants can be used alone, but it is also possible to use a mixture of two or more kinds.

The oil layer containing desiccant-treated 2,5-dihydrofuran is subjected to solid-liquid separation such as filtration, and then distilled to produce high-purity 2,5-dihydrofuran. .

When a sulfite is used as a reducing agent, sulfur present in the reaction solution can be a substance inhibiting hydroformylation. Therefore, it is more preferable to bubble with an inert gas after distillation. Inert gases such as nitrogen, helium,
Any material that does not react with 2,5-dihydrofuran such as argon may be used. If the gas amount is large, the remaining inhibitors of the hydroformylation reaction can be quickly removed.
The loss of 5-dihydrofuran is also large, and the less it takes to remove the inhibitor. The gas amount is 0.05 to 1 m ³ with respect to 1 kg of 2,5-dihydrofuran,
Preferably it is a 0.1~0.3m ^3. The blowing speed is 0.01 to 1 Nm ³ , preferably 0.01 to 0.1 Nm ³ .
1 Nm ³ .

[0027] In the 2,5-dihydrofuran obtained through the above operation, there is no inhibitor of the hydroformylation reaction, and a stable hydroformylation reaction can be performed.

Next, the reaction of 2,5-dihydrofuran with hydrogen and carbon monoxide is carried out in the presence of a Group VIII metal compound and phosphite.

The group VIII metal compounds of the Periodic Table of the elements used as catalysts for the hydroformylation reaction include ruthenium, rhodium, cobalt, iridium and palladium, and among them, rhodium compounds are preferred. Specifically, Rh ₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , Rh (acac)
(CO) ₂ , RhH (CO) (PPh ₃ ) ₃ , Rh (ac
ac) (CO) (PPh ₃ ), rhodium oxide, rhodium chloride, rhodium acetyl acetate, rhodium acetate.

The phosphites include tris (2-
t-butylphenyl) phosphite, tris (2-t-
Butyl-5-methylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2-phenylphenyl) phosphite, tris (2-methylphenyl) phosphite, tris (2,5-dimethylphenyl) phosphite, Tris (2-t-butyl-4-methylphenyl) phosphite is exemplified. Generally, the molar ratio of catalyst to 2,5-dihydrofuran is from 1: 100 to 1: 5.
00000, preferably 1: 1000 to 1: 10000
0.

The molar ratio of the Group VIII metal to the phosphite in the Periodic Table of the elements of the catalyst is from 1: 1 to 1: 1000, preferably from 1:10 to 1: 500, more preferably 1:20.
１ ： 1: 100.

In the hydroformylation reaction, it is desirable to use 2,5-dihydrofuran as a raw material and a solvent, but the reaction may be carried out in the presence of an inert solvent for recovering the catalyst. The inert solvent used here includes alcohols such as methanol, ethanol, propanol and diglyme; halogenated hydrocarbons such as dichloromethane, trichloromethane and dichloroethane; and aromatic hydrocarbons such as benzene, toluene and xylene. And aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and N, N-dimethylimidazolidinone.

The reaction temperature is suitably from 20 to 150 ° C, more preferably from 50 to 60 ° C.

The reaction pressure is suitably in the range of 0 to 150 atm. If the pressure is higher than this, the reaction apparatus becomes large, which is disadvantageous in terms of equipment. More preferably, the reaction is carried out at 10 to 80 atm.

The mixing ratio of hydrogen / carbon monoxide is 1/5 to 10
/ 1 is desirable. Preferably it is 1/2 to 2/1.

After completion of the reaction, 3-formyltetrahydrofuran is distilled off from the reaction mixture and optionally further purified by fractional distillation.

[0037]

The present invention will be described in more detail with reference to the following examples. The detection limit of crotonaldehyde described in the following examples is 200 ppm. The analysis conditions by gas chromatography are as follows. Filler 10% OV-17 2m × 3mmφ Detection method FID

Reference Example 1 Water (76.8) was added to sodium hydrogensulfate monohydrate (651.3 g).
g and 1,3-dimethyl-2-imidazolidinone 213
1.7 g was charged and the temperature was raised to 115 ° C. Then cis
2147.8 g of 2-butene-1,4-diol (2
4.4 mol) was added dropwise, and the distillation of 2,5-dihydrofuran started almost simultaneously with the start of the addition. 2,5-
The distillate containing dihydrofuran was subjected to Dean-Star
The mixture was distilled using a k-tube and stored in a receiver. The reaction was terminated when the dropping was completed and the distillation of 2,5-dihydrofuran stopped. 1733.7 g of distillate (oil layer 14
When 53 g and the aqueous layer (280 g) were analyzed by gas chromatography, 2,5-dihydrofuran was found to be contained in the oil layer in an amount of 8%.
1.2%, 27.8% contained in the aqueous layer. (Yield 7
4%). Crotonaldehyde was contained in the oil layer at 3.5%.

Reference Example 2 12 g of sulfuric acid was charged into 300 g of 1,3-dimethyl-2-imidazolidinone, and the temperature was raised to 115 ° C. Then cis
300 g (4.3 mol) of -2-butene-1,4-diol was added dropwise, and the dropping was started at about the same time as 2,5.
Distillation of dihydrofuran started. The distillate containing 2,5-dihydrofuran was distilled using a Dean-Stark tube and stored in a receiver. After dripping,
The reaction was terminated when the distillation of 5-dihydrofuran stopped. 210 g of distillate (182 g of oil layer, 28 g of water layer)
Was analyzed by gas chromatography to find that 2,5-
Dihydrofuran is 80.3% in the oil phase and 26.25% in the aqueous phase.
5% was included. (Yield 64%). Crotonaldehyde was contained at 5.1% in the oil layer.

Reference Example 3 4.5 g of potassium iodide, 8.7 g of zinc iodide and 7.2 g of 18-crown-6 were charged into a 1 L autoclave,
Heated to 150 ° C. under a nitrogen atmosphere. In this mixture,
Under stirring, 300 g of 3,4-epoxybutene was charged over 4 hours. 150 after charging 3,4-epoxybutene
C. for 1 hour. After cooling to room temperature, the contents were transferred, 100 g of xylene was added, and the mixture was distilled.
g was obtained. This fraction contained 167 g of 2,5-dihydrofuran. (Yield 70%). Crotonaldehyde was contained in the fraction at 2.5%.

Example 1 A distillate 173 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 1
3.7 g was transferred to a separating funnel, and 877.7 g of toluene and 132.8 g (1.3 mol) of sodium bisulfite were added and shaken at room temperature for 1 hour. After standing, the lower aqueous layer was separated and removed to obtain 2299.6 g of an oily layer. After adding 300 g of sodium hydrogen carbonate to the oil layer and drying, the residue was removed by filtration. The filtrate is distilled under normal pressure, and 64 to 65 ° C
Thus, 1,000 g of 2,5-dihydrofuran was obtained. (2,5
-Dihydrofuran purity 99.9%). Crotonaldehyde was not detected. This 2,5-dihydrofuran 10
Was transferred to a flask equipped with a condenser and a blowing tube, and was bubbled with nitrogen at 0.03 Nm ³ / hr for 9 hours.
990 g of 5-dihydrofuran were obtained. Then 300ml
A stainless steel autoclave was charged with 105.0 g of the obtained 2,5-dihydrofuran, and 100 m of monocarbonyltris (triphenylphosphine) rhodium was added thereto.
g, 2.50 g of tris (t-butyl-4-methylphenyl) phosphite. Next, a 1: 1 mixed gas of carbon monoxide and hydrogen was charged to 60 atm and heated to 55 ° C. Absorption of the mixed gas, which indicates that a reaction was taking place, started, and gas absorption ceased in 10 hours. The autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography. As a result, the conversion of the raw materials was 100%, and the yield of 3-formyltetrahydrofuran was 93%.

Example 2 A distillate 181 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 2
1.6 g was transferred to a separating funnel, and 877.7 g of toluene and 15.1 g (0.4 mol) of sodium borohydride were added and shaken at room temperature for 1 hour. After standing, the lower aqueous layer was separated and removed, and 1204.9 g of 2,5-dihydrofuran was used.
2299.6 g of an oil layer containing (17.2 mol) was obtained.
After adding 300 g of sodium hydrogen carbonate to the oil layer and drying, the residue was removed by filtration. The filtrate is distilled and 2,5-
1000 g of dihydrofuran were obtained. Crotonaldehyde was not detected. This 2,5-dihydrofuran 100
0 g was transferred to a flask equipped with a condenser and a blowing tube, and bubbled with nitrogen at 0.03 Nm ³ / hr for 9 hours.
990 g of dihydrofuran were obtained. When 105.0 g of this 2,5-dihydrofuran was partially used for hydroformylation in the same manner as in Example 1, gas absorption was lost in 10 hours. The autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography.
00%, the yield of 3-formyltetrahydrofuran is 92
%Met.

Example 3 A distillate 175 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 1
4.5 g was transferred to a separating funnel, and 877.7 g of toluene and 47.1 g (0.5 mol) of aniline were added and shaken at room temperature for 1 hour. After liquid separation, the lower aqueous layer was removed, and 2,5-dihydrogen was removed. 2307.5 g of an oil layer containing 1191.9 g (17.0 mol) of furan was obtained. After 410 g of sodium bicarbonate was added to the oil layer and dried, the residue was removed by filtration, and the filtrate was distilled to obtain 1,000 g of 2,5-dihydrofuran. Crotonaldehyde was not detected. This 2.5
- dihydrofuran 1000g condenser, transferred into a flask equipped with a blowing tube was bubbled 0.03 nm ³ / hr, 9 hours with nitrogen, to give a 2,5-dihydrofuran 990 g. As in Example 1, 105.0 g of a portion of this 2,5-dihydrofuran was used for hydroformylation.
Gas absorption ceased over time. The autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography. As a result, the conversion of the starting material was 100%, and the yield of 3-formyltetrahydrofuran was 90%.

Example 4 A distillate 178 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 1
9.3 g was transferred to a separatory funnel, 877.7 g of toluene and 15.5 g (0.5 mol) of methylamine were added, and the mixture was shaken at room temperature for 1 hour. After liquid separation, the lower aqueous layer was removed to remove 2,5.
-2169.7 g of an oil layer containing 1211.8 g (17.3 mol) of dihydrofuran was obtained. After adding 410 g of sodium hydrogen carbonate to the oil layer and drying, the residue was removed by filtration and the filtrate was distilled to give 1,000 g of 2,5-dihydrofuran.
I got Crotonaldehyde was not detected. 1000 g of this 2.5-dihydrofuran was transferred to a flask equipped with a condenser and a blowing tube, and was charged with nitrogen at 0.03 Nm ³ / h.
r, bubbling for 9 hours to give 2,5-dihydrofuran 99
0 g was obtained. When 105.0 g of this 2,5-dihydrofuran was partially used for hydroformylation in the same manner as in Example 1, gas absorption was lost in 10 hours. The autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography. As a result, the conversion of the starting material was 100%, and the yield of 3-formyltetrahydrofuran was 90%.

Example 5 A distillate 168 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 3
9.1 g was transferred to a separating funnel, and 877.7 g of toluene and 132.8 g (1.3 mol) of sodium bisulfite were added and shaken at room temperature for 1 hour. After standing, the lower aqueous layer was separated and removed, and 1168.6 g of 2,5-dihydrofuran was used.
2365.1 g of an oil layer containing (16.7 mol) was obtained.
After 300 g of molecular sieves were added to the oil layer and dried, the residue was removed by filtration. The filtrate is distilled and 2,5-
1000 g of dihydrofuran were obtained. Crotonaldehyde was not detected. This 2.5-dihydrofuran 100
0 g was transferred to a flask equipped with a condenser and a blowing tube, and bubbled with nitrogen at 0.03 Nm ³ / hr for 9 hours.
990 g of dihydrofuran were obtained. When 105.0 g of this 2,5-dihydrofuran was partially used for hydroformylation in the same manner as in Example 1, gas absorption was lost in 10 hours. The autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography.
00%, the yield of 3-formyltetrahydrofuran is 93
%Met.

Example 6 A distillate 201 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 1.
3.7 g was transferred to a separating funnel, and 877.7 g of toluene and 132.8 g (1.3 mol) of sodium bisulfite were added and shaken at room temperature for 1 hour. After standing, the lower aqueous layer was separated and removed, and 1198.8 g of 2,5-dihydrofuran was removed.
2510.0 g of an oil layer containing (17.1 mol) was obtained.
After 360 g of sodium sulfate was added to the oil layer and dried, the residue was removed by filtration. The filtrate was distilled to obtain 1000 g of 2,5-dihydrofuran. Crotonaldehyde was not detected. Transfer 1000 g of this 2.5-dihydrofuran to a flask equipped with a condenser and a blow-in tube, and add 0.1 g of nitrogen to the flask.
Bubbling was performed at 03 Nm ³ / hr for 9 hours to obtain 990 g of 2,5-dihydrofuran. As in the first embodiment,
When 105.0 g of a part of 5-dihydrofuran was used for hydroformylation, gas absorption was lost in 10 hours. The autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography.
%, And the yield of 3-formyltetrahydrofuran was 90%.

Example 7 105.0 g of 2,5-dihydrofuran obtained by chemical treatment and distillation bubbling according to Reference Example 1 and Example 1 was added to 3
The mixture was charged into a 00 ml stainless steel autoclave, and 100 mg of monocarbonyltris (triphenylphosphine) rhodium and 2.59 g of tris (2-phenylphenyl) phosphite were added thereto. Next, a 1: 1 mixed gas of carbon monoxide and hydrogen was charged to 60 atm and heated to 55 ° C. Since the gas absorption was completed in 10 hours, the autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography. As a result, the conversion of the raw materials was 100%, and the yield of 3-formyltetrahydrofuran was 89%.

Comparative Example 1 A distillate 188 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 1.
1.0 g was transferred to a separatory funnel, and 877.7 g of toluene was added and shaken. After separation, the lower aqueous layer was removed, and the oil layer 21 was removed.
69.5 g were obtained. The oil layer was distilled to obtain 1,000 g of 2,5-dihydrofuran. 2.5% crotonaldehyde
Was included. When 105.0 g of this 2,5-dihydrofuran was partially used for hydroformylation in the same manner as in Example 1, no gas absorption was observed.

Comparative Example 2 A distillate 165 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 1
1.6 g was transferred to a separating funnel, and 877.7 g of toluene was added and shaken at room temperature for 1 hour. After standing, the lower aqueous layer was separated by liquid separation to obtain 2504.3 g of an oil layer. After 410 g of sodium hydrogen carbonate was added to the oil layer and dried, the residue was removed by filtration and the filtrate was distilled to give 2,5-dihydrofuran 1
000 g were obtained. Crotonaldehyde was contained in 1.7%. 1000 g of this 2,5-dihydrofuran was transferred to a flask equipped with a condenser and a blowing tube, and charged with nitrogen for 0.03 g.
Nm ³ / hr was bubbled for 9 hours to obtain 990 g of 2,5-dihydrofuran. As in Example 1, this 2,5-
When 105.0 g of a portion of dihydrofuran was used for hydroformylation, gas absorption was lost in 5 hours. The autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography. As a result, the conversion of the raw material was 10%, and the yield of 3-formyltetrahydrofuran was 9%.

Comparative Example 3 A distillate 169 containing 1254.6 g (17.9 mol) of 2,5-dihydrofuran obtained in the same manner as in Reference Example 1.
9.3 g was transferred to a separating funnel, and 877.7 g of toluene was added and shaken at room temperature for 1 hour. After standing, the lower aqueous layer was separated and removed to obtain 2306.0 g of an oil layer. The oil layer was distilled to obtain 1,000 g of 2,5-dihydrofuran. Crotonaldehyde was contained at 2.5%. 1000 g of this 2,5-dihydrofuran was transferred to a flask equipped with a condenser and a blowing tube, and was bubbled with nitrogen at 0.03 Nm ³ / hr for 9 hours to obtain 990 g of 2,5-dihydrofuran.
In the same manner as in Example 1, part 1 of this 2,5-dihydrofuran
When 55.0 g was used for hydroformylation, gas absorption ceased in 5 hours. The autoclave was allowed to cool, and the reaction product was analyzed by gas chromatography.
The conversion of the raw material was 10%, and the yield of 3-formyltetrahydrofuran was 9%.

[0051]

According to the present invention, the reaction rate of the hydroformylation reaction to 3-formyltetrahydrofuran by removing the reaction-inhibiting components contained in the raw material 2,5-dihydrofuran as is clear from the examples and comparative examples. Can be avoided, and 3-formyltetrahydrofuran can be stably produced at a high yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shuji Ozawa 1144 Togo, Mogo-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Tatsuo Kaiho 1900 Togo, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co. 72) Inventor Hiroshi Sonoda 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Mitsuhiko Miyamoto 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A process according to claim 1, wherein the cis-2-butene-1,4-diol is subjected to a dehydration cyclization reaction with an acid catalyst or a rearrangement reaction of 3,4-epoxybutene in the presence of a catalyst. After subjecting the reaction solution containing 5-dihydrofuran to a treatment for removing aldehydes, which are inhibitors of the hydroformylation reaction, by a chemical reaction using a reducing agent or a condensing agent, a group VIII of the periodic table of elements is used. Reacting hydrogen and carbon monoxide in the presence of a metal compound and phosphites selected from
A method for producing formyltetrahydrofuran. 2. The process according to claim 1, wherein in the treatment for removing the inhibitory substance by a chemical reaction, after the reaction, an oil layer is separated, treated with a desiccant, and distilled. 3. The method according to claim 1, wherein in the treatment for removing the inhibitory substance by a chemical reaction, after the reaction, a step of separating an oil layer and bubbling with an inert gas is performed. 4. The phosphite according to claim 1, wherein the phosphite is tris (2-t-butyl-5-methylphenyl) phosphite.
The described method.