JPH07309794A - Production of unsaturated alcohol - Google Patents

Abstract

PURPOSE:To produce an unsaturated alcohol useful as a precursor for isoprene, intermediate for pharmaceuticals, etc., under mild condition by reacting an olefin with an aldehyde in the presence of a specific metal salt. CONSTITUTION:This unsaturated alcohol of formula III is produced by reacting an olefin of formula I (R<1> to R<5> each is H, a 1-10C alkyl, etc.) with an aldehyde of formula II (R<6> is a 1-10C alkyl, an alkenyl, etc.) in the presence of a metal salt of formula M(SO3R<7>)3 (M is a metal of the group IIIA of the periodic table; R<7> is a perfluoroalkyl, perfluoroaryl, etc.) (preferably salt of scandium, yttrium or a lanthanoid series metal) preferably at 20-100 deg.C. In the case of using formaldehyde as the aldehyde of formula II, it is preferable to use scandium triflate as the metal salt to attain high selectivity of a gamma, delta-unsaturated alcohol.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing γ, δ-unsaturated alcohols. γ, δ-Unsaturated alcohols can be intermediates for many industrially important compounds, and 3-methyl-3-buten-1-ol is a precursor of isoprene which is a raw material of synthetic rubber. As
It is also a useful compound as an intermediate for medicines and fragrances.

[0002]

2. Description of the Related Art As a method for producing .gamma.,. Delta.-unsaturated alcohols, a method is known in which various olefins and aldehydes are heated and reacted in the presence of a catalyst or in the absence of a catalyst. As an example in the presence of a catalyst, a production method using a Lewis acid catalyst can be mentioned. Tin chloride, zinc chloride, etc. (US Pat. No. 2,308,192), alkylaluminum (J. Am. Chem. Soc.), 10
4, p. 555, 1982) and the like. Further, as an improved method for suppressing the formation of by-products, a gaseous form at a low temperature (20-80 ° C) in the presence of tin chloride, zinc chloride, etc. A method of reacting formaldehyde with isobutene is also known (British Patent No. 1205397).

As a method for obtaining a γ, δ-unsaturated alcohol in a high yield, a method using a metal salt of phosphoric acid as a catalyst has been disclosed (JP-A-51-70708 and JP-A-51-108006). Gazette). There is also known an example in which an acetic acid salt of a metal of Group Ib to Group VIII such as copper acetate or lead acetate and a hydrate thereof are used for the reaction in acetic acid (JP-A-51-70715). Gazette). A method for obtaining a desired γ, δ-unsaturated alcohol under relatively mild conditions using a crystalline aluminosilicate zeolite (JP-A-55)
No. 113732), a method of obtaining a γ, δ-unsaturated alcohol at a relatively low temperature using a catalyst containing a crystalline silicic acid compound as a main component is also known (JP-A-58-16453).
4 publication).

[0004]

In the method using a Lewis acid catalyst, it is necessary to use an anhydrous aldehyde because the catalyst is deactivated by hydrolysis in the presence of water. However, there is a problem that olefin polymerization is likely to occur under anhydrous conditions. Therefore, an inexpensive formaldehyde aqueous solution cannot be used as the formaldehyde raw material. Further, although it is necessary to use the Lewis acid in a stoichiometric amount or more with respect to the carbonyl compound, it is difficult to recover the Lewis acid after the reaction, and there is a problem in cost. In the method using a metal phosphate, alkyl-m which is difficult to separate from γ, δ-unsaturated alcohol in the coexistence of water.
-The production of dioxane is the main component, and a sufficient yield cannot be obtained for γ, δ-unsaturated alcohols. Moreover, the product has a drawback that it is a mixture of unsaturated alcohols having a double bond at the β-position or the γ-position.

Periodic table of Group Ib to Group 1 of copper acetate, lead acetate, etc.
In the method using a hydrate of a Group VIII metal acetate, since isobutene and formaldehyde are reacted in acetic acid, the main product is an acetic acid ester of 3-methyl-3-buten-1-ol, 3-Methyl-3-buten-1-ol cannot be obtained directly in high yield. In the method using crystalline aluminosilicate zeolite, high boiling by-products adhere to the surface of the catalyst and deactivation of the catalyst makes continuous operation difficult for a long time. In the method using a catalyst containing a crystalline silicic acid compound as a main component, the selectivity of formaldehyde standard is low, and the target γ, δ-unsaturated alcohol and a by-product of alkyl-m-dioxane that is difficult to separate are recognized.

[0006]

Means for Solving the Problems The present inventor has improved the drawbacks of the conventional method using a catalyst, and as a result of extensive studies on a method for producing γ, δ-unsaturated alcohol under mild conditions,
General formula (I)

[0007]

[Chemical 5]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ represents an alkyl group, an alkenyl group and an aryl group, each having 1 to 10 carbon atoms, which may be substituted with a hydrogen atom or a hydroxyl group. ) And the general formula (II)

[0009]

[Chemical 6]

(Wherein R ⁶ represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group or aryl group having 1 to 10 carbon atoms), and reacted with an aldehyde represented by the general formula (III )

[0011]

[Chemical 7]

In the production of the unsaturated alcohol represented by the formula (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above), the general formula (IV)

[0013]

[Chemical 8]

(In the formula, M represents at least one metal selected from Group IIIA metals of the periodic table, and R ⁷ represents a perfluoroalkyl group, a perfluoroaryl group or a trifluoromethylaryl group.) The present invention has been completed by finding a method for producing an unsaturated alcohol characterized by carrying out the reaction in the presence of the metal salt shown.

According to the present invention, the desired γ, δ-unsaturated alcohol can be produced under mild conditions in the presence of a catalytic amount of metal salt (IV). Furthermore, R of metal salt
^Since it is possible to control and prepare a water-soluble catalyst or a fat-soluble catalyst by changing ⁷ , it is possible to use a fat-soluble catalyst in a reaction to obtain a water-soluble target substance, and then to divide it into the organic layer by phase separation or the like. In a reaction for easily separating and recovering a fat-soluble target substance, a water-soluble catalyst is used, and after separation into a water phase by phase separation or the like, separation and recovery can be easily performed.

The olefin used in the present invention has the general formula (I)

[0017]

[Chemical 9]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is as defined above. ) Is an olefin having a structure represented by Specifically, R ⁴ and R ⁵ are hydrogen atoms, and R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, alkenyl groups or alkyl groups. Examples of α-olefins are propylene, isobutene and 2- Methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, 2-methyl-1-octene 2,3-dimethyl-1-butene, α-methyl Styrene, α-ethylstyrene; methylene norbornane and the like are examples of those in which the alkyl group of R ^{3 and} the alkyl group of R ¹ or R ² are included in part of the same cyclic structure. At least one of R ^{4 and} R ⁵ is an alkyl group,
Examples of the internal olefin that is an alkenyl group or an aryl group include 2-butene, 2-pentene, 2-methyl-2-butene, 2-hexene, cyclohexene, norbornene,
3-phenyl-2-propene etc. are mentioned. Also,
As an example in which a hydroxyalkyl group is substituted, 3-methyl-
3-buten-1-ol, 7-octen-1-ol and the like can be mentioned. As the olefin, not only a single compound but also a mixture of the above exemplified compounds may be used.

The amount of the olefin used is preferably 0.5 to 50 mole times, and particularly preferably 2 to 20 mole times the aldehyde. When the amount of olefin used is small, the selectivity of the target γ, δ-unsaturated alcohol decreases, and when the amount used is large, the reaction rate decreases and the utility required for the recovery of olefin becomes large, which is an industrial problem. Value decreases.

The aldehyde used in the present invention has the general formula (II)

[0021]

[Chemical 10]

An aldehyde having a structure represented by the formula (wherein R ⁶ is as defined above) and may be any of an aldehyde monomer, an aldehyde multimer and an aldehyde aqueous solution. Specifically, formaldehyde in which R ⁶ is a hydrogen atom, or paraformaldehyde which is a multimer thereof, trioxane; acetaldehyde, propionaldehyde as an aldehyde in which R ⁶ is a substituted or unsubstituted alkyl group, alkenyl group or aryl group, Trichloroacetaldehyde, pivalaldehyde,
Benzaldehyde, p-chlorobenzaldehyde; and citronellal as an example in which an olefin and an aldehyde group are present in the same molecule. Aldehydes having a low carbon number such as formaldehyde and acetaldehyde are well miscible with water to form an aldehyde aqueous solution. These aldehyde aqueous solutions can also be used for this reaction. When a formaldehyde aqueous solution is used, a 10 to 70% aqueous solution can be used. It is also possible to use anhydrous formaldehyde, paraform, trioxane, methylal and their mixtures with water.

The present invention has the general formula (IV)

[0024]

[Chemical 11]

(Wherein M represents at least one metal selected from Group IIIA metals of the periodic table, and R ⁷ represents a perfluoroalkyl group, a perfluoroaryl group or a trifluoromethylaryl group). By carrying out in the presence of the metal salt shown, the reaction of the olefin and the carbonyl compound proceeds under mild conditions. Periodic Table III A
Examples of the group metal include scandium (Sc), yttrium (Y), lanthanoid series and actinoid series metals, and preferably scandium, yttrium and lanthanoid series metals. The metal salt that can be used in this reaction, scandium triflate, yttrium triflate, lanthanum triflate, cerium triflate, praseodymium triflate, neodymium triflate, promethium triflate, samarium triflate, europium triflate, gadolinium triflate, Terbium triflate, dysprosium triflate, holmium triflate, erbium triflate, thulium triflate, ytteribium triflate, lutetium triflate, scandium tris (nonafluorobutane sulfonate), scandium tris (heptadecafluorooctane sulfonate), scandium Tris (pentafluorobenzene sulfonate), scandium tris (m-trifluorome Such as Le benzenesulfonate) and the like, but not limited thereto. Particularly, in the reaction using formaldehyde, scandium triflate is preferable because it has excellent selectivity for γ, δ-unsaturated alcohol. The amount of the metal salt used is 1 mol% to 50 mol% with respect to 1 mol of the carbonyl compound. The metal salt used in this reaction is listed in Periodic Table II.
Group IA metal oxides and general formula (V)

[0026]

[Chemical 12]

It is easily prepared by mixing sulfonic acid represented by the formula (wherein R ⁷ is as defined above) and heating (Tetrahedron Lett.), 34, p. 3755, 1993).

The reaction temperature is preferably in the range of 0 to 150 ° C, particularly preferably in the range of 20 to 100 ° C. When the temperature is 0 ° C or lower, the reaction rate is low and the reaction takes a long time. When the temperature is 150 ° C or higher, the decomposition reaction of formaldehyde and the γ, δ-unsaturated alcohol produced is promoted, and the yield of the target unsaturated alcohol decreases. Bring The reaction time is appropriately determined depending on the difference in reaction rate, but under the above reaction conditions, the reaction is completed within a range of 10 minutes to 48 hours.

A solvent may be used in carrying out the reaction. Solvents that can be used in this reaction include alcohols, ethers, hydrocarbons, halogenated hydrocarbons, nitrile compounds, nitro compounds, amide compounds, etc. Any solvent can be used, but a solvent that can be uniformly dissolved with the raw materials is preferable. Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and tert-butyl alcohol, ethers such as tetrahydrofuran and dioxane, hydrocarbons such as hexane, benzene and cyclohexane. , Halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene, nitrile compounds such as acetonitrile, propionitrile, isobutyronitrile, malononitrile and adiponitrile, nitro compounds such as nitromethane and nitroethane, N, Examples thereof include amide compounds such as N-dimethylformamide and N, N-dimethylacetamide, but are not limited thereto.
Further, a mixture of these may be used as a solvent, or water may coexist.

The reaction can be carried out by any method such as a batch system or a continuous system, but it is recommended to use a reactor capable of controlling the reaction temperature and the reaction time.

[0031]

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

Example 1 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), 50% formaldehyde aqueous solution 3.
Add 0 g (0.05 mol) and 12.3 g (0.025 mol) of scandium triflate, and add 20 k of nitrogen.
It was pressurized to g / cm ² and reacted at 60 ° C. for 2 hours. When the reaction solution obtained after cooling the reactor and releasing the pressure of isobutene was analyzed, all the formaldehyde disappeared and 3
2.85 g of -methyl-3-buten-1-ol, MD
0.13 g of O and 0.82 g of 3-methyl-1,3-butanediol were produced. The conversion of formaldehyde was 100%, and the selectivity of γ, δ-unsaturated alcohol based on formaldehyde was 66.3%.

Example 2 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), 50% formaldehyde aqueous solution 3.
0 g (0.05 mol) and scandium triflate (2.46 g, 0.005 mol) were added, and nitrogen was added at 20 k.
It was pressurized to g / cm ² and reacted at 60 ° C. for 2 hours. When the reaction solution obtained after cooling the reactor and releasing the pressure of isobutene was analyzed, all the formaldehyde disappeared and 3
2.21 g of methyl-3-buten-1-ol, MD
0.21 g of O and 0.60 g of 3-methyl-1,3-butanediol were produced. The conversion of formaldehyde was 100%, and the selectivity of γ, δ-unsaturated alcohol based on formaldehyde was 51.4%.

Example 3 50 g of water was added to the reaction solution obtained in Example 2 to obtain 100 m.
The organic components were removed from the aqueous phase by extracting 3 times with 1 l of diethyl ether. When water was distilled off from the obtained aqueous phase, 3.27 g of hydrous scandium triflate was obtained. Instead of the scandium triflate used in Example 2, 3.27 g of this recovered hydrous product was used, and the reaction was carried out in the same manner as in Example 2 except for the above. When the obtained reaction liquid was analyzed, formaldehyde disappeared completely, and 3-
2.15 g of methyl-3-buten-1-ol, MDO
Of 0.18 g and 0.58 g of 3-methyl-1,3-butanediol were produced. The conversion of formaldehyde was 100%, and the selectivity of γ, δ-unsaturated alcohol based on formaldehyde was 50.1%.

Example 4 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), 50% formaldehyde aqueous solution 3.
0 g (0.05 mol) and yttrium triflate (2.68 g, 0.005 mol) were added, and nitrogen was added at 20 k.
It was pressurized to g / cm ² and reacted at 100 ° C. for 2 hours. When the reaction solution obtained after cooling the reactor and releasing the pressure of isobutene was analyzed, all the formaldehyde disappeared,
1.51 g of 3-methyl-3-buten-1-ol, M
1.23 g of DO and 0.62 g of 3-methyl-1,3-butanediol were produced. The conversion of formaldehyde was 100%, and the selectivity of γ, δ-unsaturated alcohol based on formaldehyde was 35.0%.

Example 5 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), 50% formaldehyde aqueous solution 3.
0 g (0.05 mol) and ytterbium triflate (3.10 g, 0.005 mol) were added, and the amount of nitrogen was 20.
It was pressurized to kg / cm ² and reacted at 100 ° C. for 2 hours.
When the reaction solution obtained after cooling the reactor and releasing the pressure of isobutene was analyzed, all the formaldehyde disappeared, and 3-methyl-3-buten-1-ol was 1.31.
g, 1.26 g of MDO and 0.54 g of 3-methyl-1,3-butanediol were produced. The conversion rate of formaldehyde is 100%, γ, δ-of formaldehyde standard
The selectivity of unsaturated alcohol was 30.5%.

Example 6 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), 50% formaldehyde aqueous solution 3.
0 g (0.05 mol) and scandium tris nonafluorobutane sulfonate (4.71 g, 0.005 mol) were added, the pressure was increased to 20 kg / cm ² with nitrogen, and the temperature was 60 ° C.
And reacted for 2 hours. When the reaction solution obtained after cooling the reactor and releasing the pressure of isobutene was analyzed, 0.56 g of formaldehyde remained, 1.41 g of 3-methyl-3-buten-1-ol, and 0 of MDO. .18 g,
0.35 g of 3-methyl-1,3-butanediol was produced. The conversion of formaldehyde was 62.6%, and the selectivity for γ, δ-unsaturated alcohol based on formaldehyde was 52.3%.

Example 7 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), 50% formaldehyde aqueous solution 3.
0 g (0.05 mol) and 7.71 g of scandium trisheptadecafluorooctane sulfonate (0.
005 mol) was added, the pressure was increased to 20 kg / cm ² with nitrogen, and the mixture was reacted at 60 ° C. for 2 hours. When the reaction liquid obtained after cooling the reactor and releasing the pressure of isobutene was analyzed,
0.54 g of formaldehyde remained, 1.37 g of 3-methyl-3-buten-1-ol and MDO of 0.
16 g, 0.3 of 3-methyl-1,3-butanediol
5 g had been produced. The conversion of formaldehyde is 64.
The selectivity of γ, δ-unsaturated alcohol based on 2% of formaldehyde was 49.8%.

Comparative Example 1 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), and 3.0 g (0.05 mol) of a 50% aqueous formaldehyde solution were added, and pressurized to 20 kg / cm ² with nitrogen without adding a triflate compound to 60
The reaction was performed at 8 ° C for 8 hours. When the reaction liquid obtained after cooling the reactor and releasing the pressure of isobutene was analyzed, 1.45 g of formaldehyde and 0.03 g of MDO were produced. 3-Methyl-3-buten-1-ol was not produced at all. The conversion of formaldehyde was 3.4%, and the selectivity of γ, δ-unsaturated alcohol based on formaldehyde was 0%.

Example 8 48.0 g (0.50 mol) of methylenecyclohexane, 18.5 g (0.25 mol) of t-butanol and 3.0 g (0.05 mol) of 50% aqueous formaldehyde solution were placed in a 200 ml electromagnetic stirring autoclave. Then, 2.46 g (0.005 mol) of scandium triflate was added, and the pressure was increased to 20 kg / cm ² with nitrogen, and the reaction was performed at 60 ° C. for 2 hours. When the reactor was cooled and the resulting reaction solution was analyzed, 0.10 g of formaldehyde remained,
2.58 g of (1-cyclohexenyl) ethanol was produced. The conversion of formaldehyde was 94.2%, and the selectivity of γ, δ-unsaturated alcohol based on formaldehyde was 43.5%.

Example 9 3-Methyl-3 in a 100 ml electromagnetic stirring autoclave
-Buten-1-ol 43.0 g (0.50 mol), t
-Butanol 18.5 g (0.25 mol), 50% aqueous formaldehyde solution 3.0 g (0.05 mol), and
Add 2.46 g (0.005 mol) of scandium triflate, pressurize with nitrogen to 20 kg / cm ² and 60 ° C.
And reacted for 4 hours. Cool reactor, 3-methyl-3
When the reaction solution obtained after depressurizing the butene-1-ol was analyzed, all the formaldehyde disappeared, and 3-
Methyl-3-pentene-1,5-diol and 3-methylene-1,5-pentanediol were each 1.34
g, 1.11 g was produced. The conversion of formaldehyde is 100%.
-The total selectivity of unsaturated alcohols was 42.3%.

Example 10 2-butene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), 50% formaldehyde aqueous solution 3.
0 g (0.05 mol) and scandium triflate (2.46 g, 0.005 mol) were added, and nitrogen was added at 20 k.
It was pressurized to g / cm ² and reacted at 60 ° C. for 2 hours. When the reaction solution obtained after cooling the reactor and releasing the pressure of isobutene was analyzed, all the formaldehyde disappeared and 2
-Methyl-3-buten-1-ol 1.59 g, 4,
0.12 g of 5-dimethyl-1,3-dioxane, 2-
0.31 g of methyl-1,3-butanediol was produced. The conversion of formaldehyde was 78.2%, and the selectivity for γ, δ-unsaturated alcohol based on formaldehyde was 47.2%.

Example 11 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), benzaldehyde 5.3 g (0.0
5 mol) and 2.46 g of scandium triflate
(0.005 mol) was added, and the pressure was increased to 20 kg / cm ² with nitrogen, and the mixture was reacted at 60 ° C. for 4 hours. Cool the reactor,
When the reaction liquid obtained after depressurizing the isobutene was analyzed, 3.85 g of benzaldehyde remained, and 1-
Phenyl-3-methyl-3-buten-1-ol is 0.
70 g had been produced. Conversion rate of benzaldehyde is 2
The selectivity for γ, δ-unsaturated alcohol based on benzaldehyde was 31.7%.

Example 12 Isobutene 2 was added to a 100 ml electromagnetic stirring type autoclave.
8.1 g (0.50 mol), t-butanol 18.5 g
(0.25 mol), trichloroacetaldehyde 7.3
8 g (0.05 mol) and 2.46 g (0.005 mol) of scandium triflate were added, and nitrogen was added at 20 k.
It was pressurized to g / cm ² and reacted at 120 ° C. for 2 hours. When the reaction solution obtained after cooling the reactor and releasing the pressure of isobutene was analyzed, 2.71 g of trichloroacetaldehyde remained and 1-trichloromethyl-3-methyl-3-buten-1-ol was 2%. .40 g was produced. The conversion rate of trichloroacetaldehyde is 63.2.
%, The selectivity of γ, δ-unsaturated alcohol based on trichloroacetaldehyde was 37.3%.

Example 13 1.93 g (0.0125 mol) of citronellal and 25 g of nitromethane were placed in a 100 ml electromagnetic stirring autoclave.
And scandium triflate 0.62 g (1.2
5 mmol) and 0.45 g (0.025 mol) of water were added, the pressure was increased to 20 kg / cm ² with nitrogen, and the reaction was carried out at 20 ° C. for 1 hour. After cooling the reactor, the reaction solution obtained was analyzed and as a result, 0.05 g of citronellal remained and 1.38 g of isopulegol was produced. The conversion of citronellal was 97.5%, and the selectivity of isopulegol based on citronellal was 73.5%.

[0046]

Industrial Applicability According to the present invention, an unsaturated alcohol is produced from an olefin and an aldehyde using a catalyst which can be reused in the presence of a catalytic amount of a metal salt under mild conditions in which water coexists. You can

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C07C 33/42

Claims (3)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each have 1 carbon atom which may be substituted with a hydrogen atom or a hydroxyl group.
To 10 alkyl, alkenyl and aryl groups. ) And an olefin represented by the general formula (II): (Wherein R ⁶ represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group or aryl group having 1 to 10 carbon atoms),
General formula (III): (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above), in the production of the unsaturated alcohol represented by the general formula (IV) ] (Wherein M represents at least one metal selected from Group IIIA metals of the periodic table, R ⁷ represents a perfluoroalkyl group,
It represents a perfluoroaryl group or a trifluoromethylaryl group. ) The process for producing an unsaturated alcohol, which comprises reacting in the presence of a metal salt represented by 2. The method according to claim 1, wherein the metal salt represented by the general formula (IV) is scandium triflate. 3. The method according to claim 2, wherein the aldehyde represented by the general formula (II) is formaldehyde.