JPS60252438A - Production of alpha,omega-diol - Google Patents

Abstract

PURPOSE:To obtain the titled compound in high selectivity, by hydroformylating a compound such as tetrahydro-2-(3-methyl-3-butenoxy)-4-methyl-2H-pyrane producible easily from an unsaturated alcohol, and hydrogenating the hydroformylation product. CONSTITUTION:The compound of formula I (R is H or methyl; n is 1 or 2) is hydroformylated with H2 and CO at 60-150 deg.C under pressure in the presence of a rhodium carbonyl compound (preferably a compound unmodified with a ligand containing the group-V element of the periodic table), and the reaction product is hydrogenated under pressure at a high temperature in the presence of water and a hydrogenation catalyst to obtain the alpha,omega-diol of formula II (e.g. 3-methyl- 3-butan-1-ol). The compound of formula I can be produced e.g. by reacting a part of the hydroformylation product with the compound of formula III in the presence of an acid catalyst. USE:Raw material of polyesters, polyurethanes, lactones, etc.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing α,ω-diol, and more specifically, by hydroformylating a specific olefinic compound vIJ and hydrogenating the resulting product, α,ω-diol is produced. .

The present invention relates to a method for producing ω-diol.

The .alpha.,.omega.-diols produced by the method of the present invention are useful compounds as raw materials for producing, for example, polyesters, polyurethanes, and lactones.

[Conventional technology and its problems]

Conventionally, various methods have been proposed for producing α,ω-diols. One of the industrially advantageous methods for producing α,ω-diol is an unsaturated alcohol having a vinyl group or vinylidene group at the -10,000 end and a hydroxyl group at the other end.

For example, by hydroformylating allyl alcohol or 3-methyl-3-buten-1-ol and hydrogenating the resulting hydroformylation product, the corresponding α
, ω-diohel, for example, 1,4-butanediol or 3-methyl-1,5-bentanediol, is known. However, in this production method, when unsaturated alcohols are hydroformylated, the isomerization reaction of unsaturated alcohols accompanies the by-product of A/tehyde, so the yield of the hydroformylation reaction product is low. As a result, the yield of α,ω-diol was not necessarily satisfactory.Especially, when allyl alcohol or 3-diol was used as the raw material unsaturated alcohol,
When a substance having a structure in which a hydroxyl group and a carbon-carbon double bond are close to each other, such as methyl-3-buten-1-ol, is used, undesirable by-product aldehyde is significantly produced by the isomerization reaction, so it is not suitable. Even under such reaction conditions, there is a problem that by-product aldehydes such as propionaldehyde or invaleraldehyde are generated when the selected 7P is about 10% or more relative to the unsaturated alcohol. The object of the present invention is to provide a method for producing α,ω-diols with high selectivity on an industrial scale using derivatives easily derived from unsaturated alcohols.

[Seminarization of invention] The purpose of the above is to express the general formula (in the formula,
R represents hydrogen or a methyl group, and 11 represents an integer of 1 or 2. ) [Hereinafter, this will be referred to as compound (,l). ] In the presence of a rhodium carbonyl compound, 60~]
, the resulting hydroformylation reaction product is reacted under elevated pressure with hydrogen and carbon monoxide at a temperature of 50° C., and the resulting hydroformylation reaction product is reacted at elevated temperature and under elevated pressure in the presence of gold water and a hydrogenation catalyst. General formula % () characterized by hydrogenation [wherein 1R and 11 do not have the same meaning as those in general formula (1). ] The α,ω-diol represented by is hereinafter referred to as α,ω-di,4-l(n). ] is achieved by providing a manufacturing method.

As the rhodium carbonyl compound to be present in the reaction system in the hydroformylation ff reaction of compound (I) according to the present invention, any rhodium carbonyl compound having catalytic ability for the hydroformylation reaction may be used. can dodecacarbonyltetrarhodium,
Hydrocarbonyl compound unmodified by a ligand containing an element of group V of the periodic table, such as hexadecarbonyl hexarhodium; ■
Lodiuno modified with a ligand containing elements of the group
Examples include carbonyl compounds. Such Periodic Table V
Modifiers that act as ligands containing elements of group 1 include 1-triphenylphosphine, 1-triazylphosphine, l-lyl-tolylphosphine, tri-0-tolylphosphine, tri-n-butylphosphine, trisoclohexylphosphine, Organic tertiary phosphines such as sodium diphenylphosphine benzene-m-sulfone-1; organic tertiary phosphites such as 1-IJ7, :nyl phosphite, tributyl phosphite; triphenylarsine, trioctele arunne, etc. Organic tertiary stibines such as triphenylstibine are exemplified. Among these, triphenylhonuphine is commonly used. Note that the above-mentioned rhodium carbonyl compound having hydroformylation catalytic ability may be added to the hydroformylation reaction system;
Rhodium compounds such as rhodium chloride, rhodium oxide, biscyclooctagenyl rhodium chloride, etc., which are converted into hydrorodium carbonyl compounds in the reaction system, may be added. In either case, the amount of rhodium carbonyl compound to be present in one reaction system is usually within the range of 0.001 to 1 milligram atom/l in terms of rhodium atoms relative to the reaction mixture. There is no particular restriction on the amount of the modifier used, but it is usually at most 250 mol, preferably at most 150 mol, per gram atom of rhodium. Compound (In the hydrophoration reaction, compound represented by the general formula 1, % and n have the same meanings as in the general formula (1).) [Hereinafter, this will be referred to as the compound (111 ) is mainly produced, but in addition, a formyl group (-ci+o) is formed at the 2M or tertiary carbon inside compound (1).
It also produces aldehydes that are not present in the casings in which they are introduced.

Compound (1) is tetrahydro-2-(2-globenoxy)furan or tetrahydro-2-(3-butenoxy)
-2H-bilane, that is, when R is a hydrogen atom in the general formula (2).

The desired hydroformylation reaction product compound (I
In order to increase the selectivity to II, I, it is preferable that a rhodium carbonyl compound modified with a ligand containing an element of group (I) of the periodic table be present in the hydroformylation reaction system. Moreover, compound (I) is detrahydride l:l-2
-(2-Methyl-2-globenoquine/)-4-methylfurampaketetrahydro-2-(3-methyl-3-butenoquine)-4-methyl-2H-bilane, that is, in the general formula (1) When R is a methyl group,
Since the selectivity to the compound (ill) in the hydroformylation reaction is very high regardless of the presence or absence of modification of the rhodium carbonyl compound present in the hydroformylation reaction system, the rhodium carbonylation adduct to be present in the hydroformylation reaction thread is as follows: Preferred are rhodium carbonyl compounds which have not been modified with a ligand containing an element from group 1 of the periodic table, giving a higher reaction rate.

The hydrogen and carbon monoxide used in the hydroformylation reaction preferably have a molar ratio of hydrogen to carbon oxide in the range of 3:1 to 1:3, particularly around 1:1. Regarding the reaction pressure, although the reaction can occur even if the total pressure is about 1 absolute atmosphere, in order to lower the rhodium concentration in the reaction system and obtain a high reaction rate, the total pressure must be increased to 2 to 300 Advantageously, it is within the range of absolute atmospheric pressure. When using a rhodium carbonyl compound that has not been modified with a ligand containing an element of group V of the periodic table as the rhodium carbonyl compound, the total pressure is preferably within the range of 80 to 300 absolute atmospheres. The reaction temperature is usually within the range of 60-150°C, preferably within the range of 80-130°C. The hydroformylation reaction can be carried out without using a solvent; however, if necessary, a solvent that is inert under the reaction conditions can also be used. Typical examples of solvents that can be used include saturated aliphatic hydrocarbons such as hexane, heptane, and octane; cycloaliphatic hydrocarbons such as cyclo-xane and methyl/chlorohexane; and aromatic hydrocarbons such as benzene, toluene, and kiln. Hydrogen; Examples include ethers such as tetrahydrofuran and dioxane. The hydroformylation reaction can be carried out so that the conversion rate of compound (1) is close to 100%, or it can be carried out so that the reaction does not go all the way. In the former case,
The rhodium carbonyl compound separated from the reaction mixture after the hydroformylation reaction can be subjected to the next elementary reaction. In the latter case, 1. Compounds (hydroformylation reaction products containing Misaki as a main component and unreacted compounds (1)) are extracted from the reaction mixture after the hydroformylation reaction.
are separated, the hydroformylation reaction product is subjected to the next hydrogenation reaction, and the unreacted compound (' ! >
can be reused in the hydroformylation reaction. Note that the rhodium carbonyl compound used in the reaction can be recycled and reused in the hydroformylation reaction, or can be recovered as rhodium metal reed or its compound.

The hydroformylation reaction product obtained in duplicate is converted into α,ω-diol (n) by hydrogenation in the presence of water and a hydrogenation catalyst. The water present in the hydrogenation reaction system is necessary for hydrolyzing the hydroformylation reaction product containing compound (III), but the amount of water is limited to the stoichiometrically necessary accumulation, that is, hydroformyl. The amount can be arbitrarily selected as long as the amount is equal to or more than the equimolar amount to the reaction product. Although water can also serve as a solvent, it is also possible to use solvents other than water. Typical examples of usable solvents include lower alcohols such as methanol, ethanol, and butyl alcohol; The same α, ω-7A-rule (example t,
Id+ 1.4-phthanediol, 3-methy/l/
Examples include -1,5-pencune diol; hydrocarbons such as hexane, cyclohexane, benzene, and toluene; and ethers such as tetrahydrofuran-2-dioxane. Hydrogenation catalysts used in the hydrogenation reaction according to the present invention include nickel, ruthenium, cobalt, copper-chromium oxides, etc. supported on a carrier such as Raney nickel, Raney cobalt, or quince alumina, or carbon. Examples include hydrogenation catalysts, with nickel thread catalysts being particularly preferred. In order to promote the hydrolysis reaction, an acid may be added to the hydrogenation reaction system according to the present invention in an amount of 5% by weight or less based on the reaction mixture, if necessary. Examples of such acids include organic acids such as acetic acid, globionic acid, isovaleric acid, and benzoic acid; polymeric compounds containing acidic groups such as cation exchange resins; inorganic acids such as hydrochloric acid, phosphoric acid, and boric acid; Examples include solid acids such as , /resilience, and alumina. The solid acid can also serve as a carrier in the hydrogenation catalyst.

The hydrogenation reaction is carried out at elevated temperature and elevated pressure. The reaction temperature is usually in the range of 50 to 250"C, preferably in the range of 80 to 180"C, and the reaction pressure is usually in the range of 2 to 200 absolute atmospheres as hydrogen pressure.
Preferably it is within the range of 5 to 150 absolute atmospheres.

The generated α,ω-diol Cn) can be isolated by any separation operation such as fractional distillation after removing the hydrogenation catalyst, hydrogen and solvent used in combination (if any) from the reaction mixture of the hydrogenation reaction system. can be obtained. 1,4-butanediol, 2-methyl-1,4-butanediol, 1,5-bentanediol'! As for fc, 3-mef-1,5-bentanediol is obtained.

The compound (1) used in the method of the present invention is, for example, 1.

An unsaturated alcohol represented by the general formula [wherein R and n have the same meanings as 2 in general formula (1)] [hereinafter referred to as unsaturated alcohol (PJ)]. ] can be easily manufactured from. For example, in the general formula obtained by hydroformylating unsaturated alcohol (IV), R and n have the same meanings as in general formula (1). ] A cyclic hemiacetal represented by [hereinafter referred to as a compound (
V). ] and an unsaturated alcohol (Yarito) in the presence of an acid catalyst F to form a compound (
1) 'jfc can be obtained (method 1).

Alternatively, a compound (In,) obtained by hydroformylation reaction of compound (1) according to the method of the present invention
A method is mentioned in which a part of the hydroformylation reaction product containing as the main component is reacted with an unsaturated alcohol (fV) in the presence of an acid catalyst (method 2). Method 2 is incorporated into the method of the present invention to use a portion of the hydroformylation reaction product of compound (1) for the production of compound (1), and the remainder to α
, when used for the production of ω-diol (AJ), the method of the present invention has general formula (I).

Taking as an example the case where R is a methyl group and n is 2 in (II), (■) and CI), the reaction is composed of the following three reactions.

(Li) Formation of compound (II) by hydroformylation reaction of compound (1) (11) α, by hydrogenation reaction of compound (IIl,),
Generation of ω-diol (n) (iii) Compound (ill) and unsaturated alcohol CJ
) Formation of compound (1) by acetal exchange reaction with 3-methyl-3-buten-1-ol, which is an unsaturated compound (1v) , ω-diol 3-me5-ru J
, is the same as producing 5-bentanediol. This corresponds to general formulas (I) and (n).

(1) and (fV) hold true even when R and n are other than the above. Therefore, α of the present invention,
ω-diol (hydroformylation reaction product whose main component is compound (III) obtained by hydroformylation of compound (1) by incorporating the method 2 above into the old production method to obtain raw material compound (1)) The compound (fV) is prepared by reacting a part of the compound with the compound (fV) in the presence of an acid catalyst.
It is preferable to convert it into I) and use it as a raw material for the hydroformylation reaction, while hydrogenating the remainder of the hydroformylation reaction product to produce α,ω-dimer (■).

Said method 1 and method 2 for producing compound (I)
In this case, either a protonic acid or a Lewis acid can be used as the acid catalyst. Examples of protonic acids include organic carboxylic acids such as acetic acid, propionic acid, 12-ethylhexanoic acid, 1-benzoic acid, and terephthalic acid; organic sulfonic acids such as benzenesulfonic acid and p-1 luenesulfonic acid; cation exchange resins, phenolic resins, etc. Polymer compounds having acidic groups; examples include inorganic protonic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydrogen sulfate, and sodium dihydrogen phosphate; examples of Lewis acids include copper sulfate, nickel chloride, calcium chloride, dichloride, etc. Examples include iron, zinc chloride, alumina, silica alumina, and activated clay. Among these, solid acids such as cation exchange resins and silica alumina are particularly preferred from the viewpoint of easy catalyst separation. The amount of the acid catalyst to be used is not particularly strictly limited, but is usually within the range of 0.0 to 10% by weight based on the 5 reaction materials. Also.

In the reaction according to Method 1 or Method 2, the ratio of the raw materials Compound (■) or Compound (Iil) and unsaturated alcohol (IV) used is preferably around the stoichiometric amount. That is, in method 1, the compound CV) and the unsaturated alcohol C■) are used in a molar ratio of about 1;
In addition, in method 2, the compound (■) and the unsaturated alcohol (IV
) in a molar ratio of about 1:2. However, there is no problem even if one of these components is used in excess. The reaction temperature is usually in the range of 20 to 150°C, preferably 20 to 150°C.
It is within the range of 100°C. Also, in these methods.

Although it is not necessary for a particular solvent to be present in the reaction system, any solvent can be used as long as it does not cause any actual damage to the reaction. As a usable solvent.

Saturated aliphatic hydrocarbons such as hexane, heptane, and octane; Saturated alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, and quincylene; methylene chloride, chloroform, tetracarbohydrate, dichloroethane halogenated hydrocarbons such as diethyl ether;

Examples include ethers such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, and ketones such as acetone, methyl ether ketone, and methyl imbutyl ketone. Among these, aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons are used. It is particularly preferred to carry out the reaction while distilling off the produced water by azeotropy. There is no particular limit on the amount of solvent used, but considering the solvent recovery after one reaction, it is usually 20 times the amount of the reaction raw material (weight: f
) The following is appropriate. Since the production reaction of compound (1) in Method 1 and Method 2 usually proceeds approximately quantitatively,
After such reaction, the reaction product solution from which the acid catalyst has been removed can be directly subjected to the hydroformylation reaction step according to the present invention, or the compound (1) can be isolated and purified from the reaction product solution and then subjected to the process according to the present invention. It can also be used in manufacturing methods.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (a) Tetrahydro-2-(3-methyl-3-butenoxy)-4-methyl-2H-bilane [Compound (1,) odor-(kl=ckis, n=2) (7) Synthesis;
Contents 300 m with stirrer, cooler and thermometer
1 flask containing tetrahydro-2-hydroxy-4-methyl-2H-bilane 70F (06 mol), 3-
Methyl-3-buten-1-ol 52.469 (0,
61 mol), He*-1,in 150M, and activated clay 32 were charged, and reacted at 60° C. for 1 hour with stirring. Analysis of the reaction mixture by gas chromatography revealed that tetrahydro-2-.(3-methyl-3-butenoxy)-
The yield of 4-methyl-2H-bilane was 98%. Activated clay was separated from the reactor mixture, and then hexane was distilled off. The remaining liquid was distilled under reduced pressure to obtain a boiling point of 89.5-90.
．． Tetrahydro-2=-(3-methyl-3-butenoxy)-4-methyl-211-bilane 1052 was obtained as a fraction at 0°C/10 mm Hy.

(b) Compound (1) (R=CHa, n=2) (
7) Human oformation reaction; Contents] 30 t (0,16
3 mol), 20rnl hexane and Rh, 1(Co)
After charging 120.14 m9 and sufficiently replacing the inside of the system with a mixed gas consisting of hydrogen and carbon monoxide (molar ratio of hydrogen/-carbon monoxide 1/1), the inside was heated to 250 absolute atmospheric pressure with the mixed gas. Pressure was applied. The temperature of the reaction mixture was raised to 100° C. over 30 minutes while stirring, and the hydroformylation reaction was continued for an additional 5 hours while maintaining the same temperature. During this time, the internal pressure of the reactor was always maintained at 250 absolute atmospheres with a pressure regulating valve, and 5 off gases were constantly drawn out of the reaction system at a flow rate of about 5 II/lir. After the reaction was completed, the inside of the reactor was cooled and returned to normal pressure, and then the reaction mixture was taken out. The reaction mixture was heated to 100° C. under a nitrogen atmosphere and then cooled.

The precipitated rhodium compound was removed with a filter.

By distilling off hexane from the effluent from the filter, 1 and the residual liquid 3 are obtained as hydroformylation reaction products.
I got 482. The main component of this residual liquid is 5-(tetrahydro-4-methyl-2i-1,-2-pyranoxy)-3-
It happened with methylpentanal.

(Hydrogenation of C1 hydroformylation reaction product; Content 30
Into a stainless steel electromagnetic stirring autoclave of o m, i, 10y of methanol, 50M of water, 10y of the hydroformylation reaction product obtained above, and 2v of the powdered nickel diatomaceous earth catalyst (Kickel content 50%) were charged to produce the hydropormylation reaction. The material was hydrogenated under stirring at 140° C. for 2 hours while maintaining the hydrogen pressure at 50 atmospheres absolute. As a result of gas chromatography analysis of the combined liquid in one reactor after the completion of the hydrogenation reaction, the hydrogenation rate of the hydroformylation product was 10.
The hydrogenation products were 97 mol% of 3-methyl-1,5-bentanediol, 2-improvil-1,3-
It turned out to be a mixture consisting of 2.5 moles of globandiol and 0.5 moles of isoamyl alcohol. After separating the catalyst from the reaction mixture and distilling off methanol and water, the residual liquid was distilled under reduced pressure to a boiling point of 114°C/'
3-Methyl-1,5-bentanediol (L5f) with a purity of 100% was obtained as a fraction of 4tm Hy.

(d) Compound from the hydroformylation reaction product (1
)(R=CH3,n22) Synthesis; hydropolmylation reaction product 10f, 3 to methyl was taken up in 20 m in a three-necked flask with a content of 100 m equipped with a condenser, a stirrer and a thermometer. 8.6 f (0.1 mol) of -3-buten-1-ol, 20 M of Hekijyo, and 11 oily clay were charged, and reacted at 05° C. for 1 hour with stirring. The obtained reaction mixture was analyzed by gas chromatography and the rate of change of the hydroformylation product was 1.
00%.

Tetrahydro-2-(3-methyl-3-butenoxy)-
The yield of 4-methyl-7,H-bilane was found to be over 96% based on the reacted 3-methyl-3-dian-1-ol.

Example 2 Tetrahydro-2-(3-methyl-3-furanoxy)-4-methyl-211-pyran 30y (0,163 mol, t□ #-c 720 ml) was placed in a 100σ stainless steel electromagnetic stirring autoclave. and HRh (
Co) [P(C6Ms)3] 35 mg was charged and a mixed gas consisting of hydrogen and carbon monoxide (hydrogen/'-
After sufficient replacement with oxidized carbon at a molar ratio of 1/1), the mixed gas was heated at 90% while stirring while maintaining the pressure at 100% absolute pressure.
The hydroformylation reaction was carried out at ℃ for 15 hours. After the reaction was completed, the reaction mixture was taken out, toluene was distilled off, and the remaining liquid was simply distilled under reduced pressure to a boiling point of 84.
5-(tetrahydro-4-methyl-
2H-2-pyranoxy)=3-methylpentanal 33
．． 6y was obtained (isolated yield 96 yen based on raw materials). Next, this distillate 10y1 methanol j00WLl! , water 5
0m1. Acetic acid 0.2f and Raney nickel catalyst 2y
Methyl 11i) was charged into the same hydrogenation apparatus as used in Example 1, and a hydrogenation reaction was carried out at a hydrogen pressure of 50 absolute atmospheres and 120° C. for 5 hours. After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and the product was found to be only 3-methyl-1,5-bentanediol.

Example 3 (a) Synthesis of tetrahydro-2-(2-propenoxy)furan [R=H, n=1 in compound (1)]; content 200 ml with stirrer, condenser and thermometer
Tetrahydro-2-hydroxy 7rane 44y (0.5 mol), 71J alcohol 30F (
0.52 mol), 100N of benzene, and 12% of sodium hydrogen sulfate were charged, and the mixture was reacted at 65°C for 1 hour with stirring. After the reaction mixture was separated and benzene was distilled off from the F solution, the remaining solution was distilled under reduced pressure to a boiling point of 87.5°C/10°C.
Tetrahydro-2-(2-propenoxy)furan 627 was obtained as a fraction of f1J.

(b) Hydroformylation reaction of compound (1) (R=H, n=1): Tetrahydro-2-(2-propenoxy) was placed in a 100 m, l stainless steel electromagnetic stirring autoclave.
Furan 12.8P (0.1 mol), toluene 2゜go,)
IRh(CO) CP(C6HFi)3. l],,9.
2~ and triphenylphosphine 262~ are prepared,
2P with a mixed gas consisting of hydrogen and carbon monoxide (hydrogen/-carbon monoxide ratio 3/1) at 60°C while maintaining counter pressure.
The hydroformylation reaction was carried out at ℃ for 3 hours with stirring.

During this time, off-gas was taken out of the reaction system at a flow rate of 3 J/br. After the reaction was completed, the inside of the autoclave was cooled and returned to normal pressure, and then the reaction mixture was taken out.

The reaction mixture was analyzed by gas chromatography, and the selectivity of the hydroformylation reaction product was found to be anti-KE, L
, ;/kofJ Lahydrau 2-(2-propenoxy)
Based on furan, 90 moles of 4-(tetrahydro-2-furanoxy)butanal and 3-(tetrahydro-2-furanoxy) and 2-
7 moles of furanoxy)-2-methylpropanal were received. After toluene was distilled off from the reaction mixture, the residual liquid was distilled under reduced pressure to obtain a mixture of the above aldehydes of 12.5f as a fraction with a boiling point of 67-77'C15mHy (isolated yield based on raw materials: 93). .

Hydrogenation of (Q) and DoI coformylation reaction product; Hydrogenation reaction was carried out in the same manner as in Example 1(C) except that the above aldehyde mixture was used as the hydroformylation reaction product. Analysis of the reaction mixture after the reaction by gas chromatography revealed that the hydrogenation rate was 100, and the water purple reaction produced ~methyl, 4 moles of 3-propanediol, and 1,4-butanediol. It turned out to be a mixture consisting of 95 ruti.

((1) Compounds from hydroformylation reaction products (
1) Synthesis of (R-H, n=1); In a 50-ml flask equipped with a magnetic stirrer, the hydroformylation reaction product 22 obtained above, allyl alcohol 1.6F (0,027 mol), hexane 1
0 m/ml and activated clay 0.32 kg were charged, and the mixture was reacted at 60°C for 1 hour with stirring. Analysis of the reaction mixture by gas chromatography revealed that 311 units of tetrahydro-2-(2-propenoxy)furan were produced.

Example 4 (a) Tetrahydro-2-(2-methyl-2-propenoxy)-4-methylfuran [Compound (1)
=CHs, n=1]; in Example 3(a), tetrahydro-2-hydroxy-4-
Methyl 7 run [J, Org.

Chem, 37.1835 (1972)) 51
F (0,5 mol) and 2-methyl-2-propene-1
The same reaction as in Example 3(a) was carried out except for using -ol 38F (0.52 mol). )-4-Methylfuran 75? I got it.

(b) Hydroformylation reaction of compound 1 (R=CHa, n=1); In Example 1(b), tetrahydro-2-
Example 1 (b
), and the hydroformylation reaction product was mainly 4-(tetrahydro-4
-Methyl-2-7ranoxy)-: 29.52% of a residual liquid consisting of methylbutanal was obtained.

(C) Hydrogenation of hydroformylation reaction product: Example 1 except that the hydroformylation reaction product 102 obtained above was used as the hydrogenation raw material in Example 1 (C)
After the same hydrogenation reaction as in (c), the reaction mixture was analyzed by gas chromatography, and the hydrogenation rate of the hydroformylation reaction product was 100%. Mol% is 2-methyl-1,4-
It turned out to be butanediol.

(d) Compound (I) from the hydroformylation reaction product
) (R=CHs, n=1); In a flask with a content of 5 Qml equipped with a magnetic colander, add the hydroformylation reaction product 52.2-methyl-2 obtained above.
-propene) 71-ol 3.92 (54 mmol),
Hexane lQi/and sulfonic acid type ion exchange resin (
Manufactured by Rohm & Co., Ltd. (trade name: Amberlis)
15) 0.52 was charged and reacted at room temperature for 1 hour with stirring.

When the reaction mixture after the reaction was analyzed by gas chromatography, it was found that tetrahydro-2-(2-methyl-2-propenoxy)-4-methylfuran was 81? It was generating.

Example 5 (a) Tetrahydro-2-(3-butenoxy)-2H
-Biran [Compound (1) with OiteR-H, n=2]
Synthesis of tetrahydro-2-hydroxy-2)1-bilane 50 r(0,49
The reaction was carried out in the same manner as in Example 3 (a), except that 31' (mol) and 3-buten-1-ol 31' (0.5 mol) were used. The resulting reaction mixture was distilled under reduced pressure and the boiling point was 88-9.
Tetrahydro-2-(
72.52 of 3-butenoxy)-2H-bilane was obtained.

(b) Hydroformylation reaction of compound (1) (R=H, n=2); Tetrahydro-2 as a raw material in (b) of Example 3
-(3-butenoxy)-2H-bilane 15.6F(0,
The same reaction as in Example 5 (b) was carried out except that 1 mol) was used. When the obtained reaction mixture was analyzed by gas chromatography, the conversion rate of the raw material was 95%. )-pentanal 9 di(tetrahydro-2h-2-pyranoxy)-2-methylbutanal was diluted with 8 mol of rice cake. After toluene was distilled off from the reaction mixture under reduced pressure, the residual liquid was distilled under reduced pressure to reduce the boiling point to 11.
2-115℃/l 17.3 as a fraction of OwtHy
The above aldehyde mixture of F was obtained.

(e) Hydrogenation of hydroformylation reaction product; Hydrogenation reaction was carried out in the same manner as in fe) of Example 1 except that the aldehyde mixture obtained above was used as the hydroformylation reaction product. When the reaction mixture after the reaction was analyzed by gas chromatography, the hydrogenation rate was 100%, and the hydrogenation reaction products were 2-methyl-1,4-butanediol and 1,5-bentanediol. 95
It turned out to be a mixture of seven ruchi.

〔Effect of the invention〕

The conventionally known α method involves hydroformylating an unsaturated alcohol (■) and then hydrogenating the product.

In the method for producing ω-diol (n), a major problem was the loss due to isomerization of the unsaturated alcohol in the hydroformylation reaction step.

According to the method of the present invention, compound (I) which can be easily produced from unsaturated alcohol (fV) is hydroformylated,
11 by hydrogenation of the product.

By significantly suppressing side reactions such as isomerization, it is possible to obtain industrially advantageous target α,ω-diols (II, I) with high selectivity. Patent applicant Rira Co., Ltd. Ken Shihonda

Claims (1)

[Claims] 1. A compound represented by the general formula (wherein R represents hydrogen or a methyl group, and n represents an integer of 1 or 2) is heated at 160 to 150°C in the presence of a rhodium carbonyl compound. reacting hydrogen and carbon monoxide at elevated pressure at elevated temperature and hydrogenating the resulting hydroformylation reaction product at elevated temperature and elevated pressure in the presence of water and a hydrogenation catalyst. Characteristic General Formula %Formula %() [wherein R and n have the same meanings as in the general formula (I). ] A method for producing an α,ω-diol shown in the following. 2. A portion of the hydroformylation reaction product is reacted with a compound represented by the general formula (wherein R represents hydrogen or a methyl group, and n represents an integer of 1'' or 2) in the presence of an acid catalyst. The general formula (1
) The manufacturing method according to claim 1, wherein the compound is converted into a compound represented by the following formula and used as a raw material for the hydroformylation reaction. 3. The compound represented by general formula (1) is tetrahuman rJ
-2-(3-methyl-3-butenoxy)-4-methyl-
The manufacturing method according to claim 1 or 2, which is 2H-bilane. 4. The manufacturing method according to claim 3, wherein the rhodium carbonyl compound is a rhodium carbonyl compound that has not been modified with a ligand containing an element of group (I) of the periodic table.