JP2002322103A - Preparation method for unsaturated cyclic alcohols - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the corresponding unsaturated cyclic alcohols at a high conversion rate and with a high selectivity from unsaturated cyclic aldehydes possessing unsaturated bonds within a cyclic group. SOLUTION: In the presence of a catalyst containing at least one species of metals selected from the group III, IV, IX, XIII and XIV of the periodic table and a secondary alcohol the corresponding unsaturated cyclic alcohol compound is prepared by reducing selectively the formyl group of the unsaturated cyclic aldehydes without reducing the unsaturated carbon - carbon bonds. As the unsaturated cyclic aldehydes, C5-16 mono- or tri-cyclo-alkenecarbaldehyde and the like can be employed. The reduction reaction may be carried out at 40-120 deg.C and under the hydrogen gas pressure of roughly 0.01-5 MPa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an unsaturated cyclic alcohol useful as a raw material in the field of fine chemicals such as medicines and agricultural chemicals.

[0002]

2. Description of the Related Art As a method for producing an unsaturated alcohol having a carbon-carbon double bond in a molecule, a formyl group of an unsaturated aldehyde is selected using a secondary alcohol as a hydrogen donor and an aluminum alkoxide as a catalyst. There is known a method of so-called reduction (so-called mail wine / pond reduction). However, this method requires the use of a large amount of expensive aluminum alkoxide catalyst for aldehyde, and furthermore, extraction for separation of product and catalyst,
A complicated operation such as distillation is required, and the catalyst cannot be reused.

[0003] JP-A-8-133998 discloses that a mixed acid anhydride obtained by reacting sorbic acid with a chloroformate is reduced stoichiometrically using a metal borohydride catalyst, and the corresponding acid anhydride is reduced. It is disclosed that an aldehyde compound or an alcohol compound is obtained. However, in this method, an expensive reduction catalyst is required stoichiometrically even in the reaction with chloroformate. Furthermore, complicated operations such as extraction and distillation are required for separating the by-product salts and products after the reaction.

Proceedings of the 84th Catalyst Symposium on September, 1999 (September, 1999, "Catalyst", Vol. 41, No. 6, 389-
391) discloses that crotyl aldehyde can be obtained by reducing crotonaldehyde using a secondary alcohol in the presence of a catalyst supporting a metal catalyst such as zirconium oxide (ZrO ₂ ). ing. Further, a method of catalytically reducing an unsaturated aldehyde with hydrogen gas in the presence of a hydrogenation catalyst such as a copper chromite catalyst is also known.

[0005] However, these methods involve adding carbon-
When applied to the reduction of an unsaturated cyclic aldehyde having a carbon unsaturated bond, not only the formyl group but also the carbon-carbon unsaturated bond is easily reduced due to the steric distortion peculiar to the cyclic group,
It is difficult to selectively obtain the corresponding unsaturated cyclic alcohol. Also, it has been difficult to carry out these methods industrially.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for selectively reducing a formyl group even when an unsaturated cyclic aldehyde having an unsaturated bond in the cyclic group is used. It is an object of the present invention to provide a method for producing a corresponding unsaturated cyclic alcohol at a high rate.

It is another object of the present invention to provide a method for producing an unsaturated cyclic alcohol simply and efficiently while suppressing the reduction of carbon-carbon unsaturated bonds in the cyclic group.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, by using a catalyst composed of a specific metal in combination with a hydrogen donor, The present inventors have found that the formyl group of an unsaturated cyclic aldehyde having an unsaturated bond can be selectively reduced to efficiently produce a corresponding unsaturated cyclic alcohol, and the present invention has been completed.

That is, in the present invention, group 3 of the periodic table,
A formyl group of an unsaturated cyclic aldehyde is selectively reduced in the presence of a catalyst and a hydrogen donor containing at least one selected from Group 9, 9 and 13 metals; To manufacture. The unsaturated cyclic aldehyde may be C _5-16 mono to tricycloalkene carbaldehyde, and may be represented by the following formulas (1) to (3).
And the like.

[0010]

Embedded image

(Wherein R ¹ and R ² are the same or different,
R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom; m represents an integer of 0 to 3;
The catalyst may be composed of a simple substance of a metal belonging to Group 4 of the periodic table or a metal oxide. Particularly, the catalyst may be a solid catalyst containing zirconium oxide or a catalyst in which zirconium oxide is supported on a carrier. You may. Further, the hydrogen donor may be a secondary alcohol.

According to the present invention, a temperature of 40 to 40 is used in the presence of a catalyst in which zirconium oxide is supported on a carrier and a secondary alcohol.
A method for selectively reducing the formyl group of C _5-12 mono to tricycloalkene carbaldehyde at 120 ° C. and in the presence of hydrogen gas to produce the corresponding unsaturated cyclic alcohol is also included.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the reduction reaction of the present invention, the unsaturated cyclic aldehyde used as a substrate contains an unsaturated bond (carbon-containing unit) in a cyclic group (that is, as a constituent unit of a ring).
Carbon double bond) and a formyl group directly bonded to a cyclic group. In the unsaturated cyclic aldehyde, the substitution position of the formyl group is not particularly limited, and may be present at any of the secondary carbon atom and the tertiary carbon atom constituting the ring.

As the unsaturated cyclic aldehyde, C
_5-16Mono to tricycloalkene carbaldehyde [eg
If C_5-12Mono to tricycloalkene carbaldehyde
(C_{7- Ten}Of mono- or bicycloalkene carbaldehyde
Others, tricyclo [2.2.1.0 ^2,6] Hept-2-E
-5-carbaldehyde, tricyclo [5.4.0.0
^2,9] Undec-5-en-9-carbaldehyde and the like
C_7-12Tricycloalkene carbaldehyde, etc.]
Lower alkadiene carbaldehyde [1,3-cyclohexa
Diene-5-carbaldehyde, 1,3-cyclohexadi
Ene-6-carbaldehyde, 1,5-cyclooctadie
C such as N-4-carbaldehyde_5-10Cycloalkadie
Carbaldehyde (preferably C_5-8Cycloalkadie
Carbaldehyde) and the like]. Also,
Optionally, 3,6-cyclohexenedicarbaldehyde,
C such as 4,5-cyclohexenedicarbaldehyde_5-10
Cycloalkenedicarbaldehyde (C_5-8Cycloalkene
And the like may be used.

The unsaturated cyclic aldehyde may have a substituent. Such a substituent is not particularly limited as long as it does not inhibit the reduction reaction, and examples thereof include an alkyl group (such as a C _1-6 alkyl group such as a methyl and ethyl group) and an aryl group (such as a C _{6 -10} such as a phenyl group) Aryl group),
Examples include a halogen atom (fluorine, chlorine, bromine, iodine atom) and a hydroxyl group.

Among the unsaturated cyclic aldehydes, mono- or bicycloalkene carbaldehydes represented by the following formulas (1) to (3) are preferable.

[0017]

Embedded image

(Wherein R ¹ and R ² are the same or different,
R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom; m represents an integer of 0 to 3;
Examples of the alkyl group represented by R ^{1 to} R ⁴ include the alkyl groups (particularly, C _1-4 alkyl groups) exemplified in the above-mentioned substituent section, and are represented by R ¹ and R ^2. The alkyl group is preferably a C _1-2 alkyl group, especially a methyl group. As the aryl group and the halogen atom represented by R ³ and R ⁴ , the aryl group and the halogen atom exemplified in the above-mentioned substituent section can be respectively mentioned. m is preferably 0 to 2, and n is preferably 1 to 3.

The unsaturated cyclic aldehyde represented by the formula (1) includes bicyclo [2.2.0] hex-2-ene-5-carbaldehyde and bicyclo [2.2.1] hepta-2- En-5-carbaldehyde (2-norbornene-
5-carbaldehyde), 7,7-dimethyl-2-norbornene-5-carbaldehyde, 2,7,7-trimethyl-2-norbornene-5-carbaldehyde, 2-norbornene-1-carbaldehyde, 2-norbornene -7-
Carbaldehyde, 2-bornene-5-carbaldehyde,
2-bornene-4-carbaldehyde, bicyclo [2.
2.2] Bicycloalkene carbaldehydes such as oct-2-ene-5-carbaldehyde and bicyclo [2.2.3] non-2-ene-5-carbaldehyde (such as _C7-10 bicycloalkene carbaldehyde) And so on.

The unsaturated cyclic aldehydes represented by the above formula (2) include bicyclo [3.1.0] hex-2-ene-4-carbaldehyde and 5-isopropylbicyclo [3.1.0] hexa- 2-ene-4-carbaldehyde, bicyclo [3.1.0] hex-2-ene-6-carbaldehyde, bicyclo [3.1.1] hept-2-ene-4-carbaldehyde (2-norpinene -4-carbaldehyde), 2-norpinene-5-carbaldehyde, 2
-Norpinene-6-carbaldehyde, 2-norpinene-
7-carbaldehyde, 2,6,6-trimethyl-2-norpinene-4-carbaldehyde, bicyclo [3.2.
1] Oct-2-en-4-carbaldehyde, bicyclo [3.2.1] oct-2-ene-6-carbaldehyde, bicyclo [3.3.1] non-2-en-4-carbaldehyde Bicycloalkenecarbaldehyde (C
_7-10 bicycloalkenecarbaldehyde) and the like.

The unsaturated cyclic aldehyde represented by the above formula (3) includes 4-cyclopentenecarbaldehyde, 2,2
3, or 4-cyclohexene carbaldehyde, 1-methyl-4-cyclohexene carbaldehyde, 1,2-dimethyl-4-cyclohexene carbaldehyde, 4-methyl-4-cyclohexene carbaldehyde, 5-methyl-4
Cycloalkene carbaldehydes such as cyclohexene carbaldehyde, mensen carbaldehyde, 1,2,3,3-tetramethyl-4-cyclohexene carbaldehyde, 5-cyclooctene carbaldehyde, 6-cyclodecene carbaldehyde (C _{7- 10} cycloalkene carbaldehyde) and the like.

In the present invention, reducing the unsaturated bond (carbon-carbon unsaturated bond) in the unsaturated cyclic aldehyde having an unsaturated bond in a cyclic group in the presence of a hydrogen donor and a catalyst. Instead, the formyl group is selectively reduced to produce the corresponding unsaturated cyclic alcohol.

Examples of the hydrogen donor include secondary alcohols, hydrogen gas, and hydrides (eg, hydride reducing agents such as lithium aluminum hydride and lithium borohydride). The hydrogen donors may be used alone or in combination of two or more. Preferred hydrogen donors are secondary alcohols. The secondary alcohol may be used in combination with hydrogen gas, or may be used in the absence of hydrogen gas.

The secondary alcohol is not particularly limited as long as it does not inhibit the reaction, and includes, for example, 2-propanol,
2-butanol, 2-hexanol, 3- C _3-8 alkyl alcohols having a secondary hydroxyl group, such as hexanol (preferably C _3-6 alkyl alcohol); cyclopentanol, C _5-8 cycloalkanols such as cyclohexanol And the like. Of the secondary alcohols, 2-propanol, 2-butanol, and the like, which are easily available, and whose post-reaction is easy due to the blind value, are preferable.

The proportion of the secondary alcohol is, for example, 1 to 100 mol (for example, 2 to 100 mol), preferably 5 to 75 mol, more preferably about 10 to 50 mol, per 1 mol of the unsaturated cyclic aldehyde. And usually 10 to
It is about 40 mol. Since the reaction between the hydrogen donor and the substrate (unsaturated cyclic aldehyde) is an equilibrium reaction, it is advantageous from the viewpoint of yield that the hydrogen donor is present in excess with respect to the unsaturated cyclic aldehyde, If the proportion of the aldehyde is too small, the productivity may be reduced industrially.

When a secondary alcohol is used as the hydrogen donor, the reaction is carried out while removing the ketone compound derived from the secondary alcohol generated in the reaction system, whereby the equilibrium is shifted to the product side and the productivity is reduced. Can be improved. In such a reactive distillation system, a reactor provided with a still can be used.

When hydrogen gas is used as the hydrogen donor, it may be used by mixing with an inert gas (eg, nitrogen, helium, argon, etc.).

The hydrogen gas pressure is 0.01 to 5MPa.
a, preferably about 0.05 to 4 MPa, more preferably about 0.1 to 3 MPa, and usually 0.1 to 2 MPa.
It is about.

In the reduction reaction of the present invention, the catalyst comprises a catalyst component or a catalyst component and a carrier. Examples of the catalyst component include metals belonging to Group 3 of the periodic table (such as lanthanum, scandium and yttrium), metals belonging to Group 4 (such as titanium and zirconium), metals belonging to Group 9 (such as cobalt and rhodium), and metals belonging to Group 13 (boron, aluminum and gallium). ) And Group 14 metals (such as tin and lead). These metals may be used alone or in combination of two or more. A preferred metal is a Group 4 metal of the periodic table (particularly zirconium).

The catalyst component is not particularly limited as long as it contains the metal, and may be a simple metal or a metal compound. Examples of the metal compound include a metal oxide, a metal salt (for example, an inorganic acid salt, an organic acid salt, and a metal complex), a metal halide, and a metal hydroxide. Preferred catalyst components are metal oxides.

As the metal oxide, for example, La ₂
O ₃ , Sc ₂ O ₃ , Y ₂ O ₃ , TiO ₂ , ZrO ₂ , RhO ₂ ,
Metal oxides such as SiO ₂ and SnO and ZrO ₂ —SiO
_{2, B 2 O 2 -Al 2} O 3, etc. SiO ₂ -Al composite metal oxides such as ₂ O _3. These metal oxides can be used alone or in combination of two or more.

The catalyst may be a homogeneous catalyst or a heterogeneous catalyst, and is preferably a heterogeneous catalyst (for example, a solid catalyst). The solid catalyst may be the catalyst component (metal simple substance or the metal compound), or may be a supported catalyst in which the catalyst component (metal simple substance or the metal compound) is supported on a carrier.

The carrier is not particularly limited as long as the catalytic activity of the supported catalyst component can be effectively exhibited, and examples thereof include conventional carriers such as silica, alumina, silica-alumina, zeolite, activated carbon and bentonite. Further, the carrier may be a porous carrier. Preferred carriers are silica, zeolite, activated carbon and the like, especially silica and activated carbon.

[0034] The silica may be a porous silica carrier. The porous silica carrier may be a mesoporous molecular sieve having pores (particularly, mesopores). Examples of such a molecular sieve include, for example, J. Am. Chem. Soc. 1992, 114, 10834- And a mesoporous silica carrier (MCM-41) prepared according to the formulation described in 10843.

The surface area of the support may be selected from a range that does not impair the catalytic activity, for example, 10~5000m ² / g, preferably 50~2500m ² / g, more preferably 1
It is about 00 to 1000 m ² / g.

The average pore diameter of the carrier is, for example, from 1 to 100.
nm, preferably 3 to 50 nm, more preferably 5 to 50 nm.
It is about 15 nm.

The supported catalyst supporting the metal oxide as a catalyst component may be such that the metal oxide is directly supported on the carrier by chemical vapor deposition or physical vapor deposition or the like. And may be prepared by converting to a metal oxide on a carrier. The oxidation may be performed in the presence of oxygen (in air or under an oxygen atmosphere) if necessary.

Examples of the metal compound include sulfates (eg, lanthanum sulfate, zirconium sulfate, cobalt sulfate, tin sulfate, etc.) and nitrates (eg, lanthanum nitrate, zirconium nitrate, cobalt nitrate, rhodium nitrate,
Inorganic acid salts such as tin nitrate), carbonates (eg, lanthanum carbonate, cobalt carbonate, etc.); acetates (eg, lanthanum acetate, zirconium acetate, etc.), oxalates (eg, lanthanum oxalate, cobalt oxalate, etc.) Organic acid salts such as tin oxalate; bromides (eg, lanthanum bromide, zirconium bromide, cobalt bromide), chlorides (eg, lanthanum chloride, zirconium chloride, cobalt chloride, aluminum chloride, tin chloride, etc.) Hydroxides (for example, lanthanum hydroxide, zirconium hydroxide, cobalt hydroxide, aluminum hydroxide, tin hydroxide, etc.); complexes in which a ligand is coordinated to the metal element or the metal compound, etc. And the like.

Among the above-mentioned metal compounds, compounds which are water-soluble and do not produce components which inhibit the reaction after firing are preferred. Such compounds include sulfates (eg, zirconium sulfate), nitrates (eg, zirconium nitrate), acetates (eg, zirconium acetate, and the like).

The loading method is not particularly limited, and a conventional loading method such as an impregnation method or a precipitation method [precipitation of an active ingredient (eg, zirconium hydroxide) on a carrier by a precipitant (eg, aqueous ammonia). By carrying out washing, drying and baking], ion exchange method [in a solution, ion exchange between an inorganic ion exchanger (for example, silica, etc.) and a zirconium salt is performed, and then baking. Supporting method], alkoxide method [During the hydrolysis of a carrier material (eg, alkoxysilane, etc.), a gel formed by coexisting a solution of a metal salt (eg, zirconium nitrate, etc.) dissolved in ethylene glycol is dried. , Firing and, if necessary, carrying out a reduction treatment to carry out the treatment] and the like, and an impregnation method is usually used. In the impregnation method, an aqueous solution in which a metal compound (e.g., zirconium nitrate) is dissolved may be immersed or sprayed on the carrier, adsorbed on the carrier, and dried and calcined to carry the carrier.

The firing temperature can be appropriately selected depending on the type of the catalyst component and the like.
Preferably 150 to 700 ° C, more preferably 150
To about 600 ° C., usually about 150 to 400 ° C.

In the supported catalyst, the proportion of the catalyst component supported on the carrier may be such that the catalytic activity can be effectively exhibited, for example, 0.1 to 50% by weight, preferably 0.5 to 35% by weight, more preferably 1 to 35% by weight. It is about 20% by weight, usually about 5 to 20% by weight.

By supporting the catalyst component (for example, the metal simple substance or the metal compound) on a carrier (for example, silica), the binding energy of the catalyst component dispersed on the carrier is shifted to the high binding energy side. The shift and higher valence appear to improve catalyst activity and selectivity.

The prepared catalyst may be used in the reaction as it is without performing pretreatment or the like. In order to improve the activity, the catalyst is pretreated in a hydrogen gas atmosphere before being used in the reaction. Is also good. The pretreatment temperature in a hydrogen gas atmosphere is, for example, 20 to 500 ° C, preferably 40 to 500 ° C.
The temperature is 400 ° C, more preferably about 50 to 300 ° C.

It is to be noted that, when the catalyst absorbs atmospheric moisture, the catalytic activity may be reduced. Therefore, it is preferable to store the catalyst in a dry closed container and avoid contact with the atmospheric moisture as much as possible.

The shape of the solid catalyst is not particularly limited, and may be, for example, granular, honeycomb, pellet, ring, or the like. In the case of the supported catalyst, the catalyst component may be supported on a carrier molded in a predetermined shape (such as the shape of the solid catalyst). May be molded.

The ratio of the catalyst is, for example, 0.01 part by weight relative to 100 parts by weight of the unsaturated cyclic aldehyde in terms of the catalyst component.
To 20 parts by weight, preferably about 0.05 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight,
About 3 parts by weight.

When a supported catalyst in which a catalyst component (such as a simple metal or a metal compound) is supported on a carrier is used as the catalyst, the ratio of the supported catalyst is, for example, 100 parts by weight of the unsaturated cyclic aldehyde. 0.1 to 50 parts by weight,
Preferably 1 to 30 parts by weight, more preferably 5 to 15 parts
It is about parts by weight.

When the catalyst is a solid catalyst or a supported catalyst supported on a carrier, it can be easily separated from the product by filtration or the like after the reaction, and the loss of the product in the product isolation step is reduced. The product can be obtained in a suppressed and high yield. Further, the separated catalyst can be regenerated and reused as necessary, and the economic efficiency can be improved.

In the present invention, even if an unsaturated cyclic aldehyde having an unsaturated bond in the cyclic group is used, the formation of by-products is suppressed, and the desired product is efficiently obtained at a high conversion and a high yield. Unsaturated cyclic alcohols can be produced.

The reduction reaction may be performed in the presence or absence of a solvent. The solvent may be any solvent that is inert to the reaction, for example, hydrocarbons (hexane, cyclohexane, toluene, etc.), nitriles (acetonitrile, etc.), esters (ethyl acetate, etc.),
Use ethers (eg, diethyl ether, dioxane, tetrahydrofuran), lower carboxylic acids (eg, formic acid, acetic acid, etc.), tertiary alcohols (eg, t-butanol), primary alcohols (eg, 1-butanol), or a mixed solvent thereof. You may. Note that a secondary alcohol which is a hydrogen donor may be used as a solvent.

The reaction temperature is not particularly limited as long as it does not affect the productivity and the decomposition reaction of the substrate (unsaturated cyclic aldehyde), and is, for example, 40 to 200 ° C. (for example, 60 to 200 ° C.).
200 ° C), preferably about 40 to 150 ° C, more preferably about 40 to 130 ° C, for example, 40 to 120 ° C.
The product can be efficiently produced at a relatively low temperature of about ° C (for example, 60 to 120 ° C). If the reaction temperature is too high, not only the formyl group but also the carbon-carbon unsaturated bond will be reduced, so that the selectivity may be reduced.

The reaction time is, for example, 10 minutes to 20 hours,
It is preferably about 15 minutes to 15 hours, more preferably about 20 minutes to 10 hours. When the reduction reaction is performed in a hydrogen gas atmosphere, the catalytic activity can be improved. For example, the reaction time is 10 minutes to 8 hours, preferably 2 minutes.
The time can be reduced to about 0 minute to 6 hours, more preferably about 1 to 5 hours.

The reduction reaction may be performed under pressure or at normal pressure. When the reduction reaction is performed under pressure, hydrogen gas or an inert gas (eg, nitrogen, helium, argon, or the like) may be used.

The reaction mode is not particularly limited. For example, a complete mixing tank system in which the catalyst fine powder is stirred and suspended in the reaction solution, the raw material liquid or the raw material gas is continuously passed through a packed bed of the formed granular catalyst. A flow reaction method or the like can be used.

After completion of the reaction, the obtained unsaturated cyclic alcohol can be easily separated and purified by conventional separation and purification means, for example, filtration, distillation, concentration, extraction, recrystallization, chromatography and the like. In particular, in the present invention, an unsaturated cyclic alcohol can be obtained with high conversion and selectivity, so that even with a simple operation (for example, filtration), an unsaturated cyclic alcohol can be obtained with high purity.

The unsaturated cyclic alcohol thus obtained is useful as a raw material in the field of fine chemicals such as pharmaceuticals and agricultural chemicals.

[0058]

According to the present invention, a specific metal catalyst and a hydrogen donor are used to selectively reduce the formyl group of an unsaturated cyclic aldehyde. Alcohol can be produced with high selectivity and high conversion. Further, an unsaturated cyclic alcohol can be easily and efficiently produced while suppressing reduction of carbon-carbon unsaturated bonds.

[0059]

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

Preparation Example 1 Zirconyl nitrate [ZrO (NO ₃ ) ₂ .2H ₂ O]
15.2 g of a 4% by weight aqueous solution was added to J. Am. Chem. Soc.
2, 114, 10834, impregnated in 0.5 g of a mesoporous silica carrier MCM-41 prepared according to the formulation described above, dried with stirring on a hot water bath, and then dried in an air stream.
Firing at 0 ° C for 5 hours, zirconium oxide 15% by weight
(Zr weight basis) A supported MCM-41 was prepared.

Example 1 100 mg of the zirconium oxide-supported MCM-41 catalyst prepared in Preparation Example 1 and 4-cyclohexene carbaldehyde were placed in a stainless steel autoclave having an internal volume of 100 mL.
02 g (9.28 mmol) and 2-butanol 20 m
L was charged, hydrogen was sealed so that the hydrogen pressure of the reaction system became 1 MPa, and the mixture was reacted at 100 ° C. for 4 hours with stirring. After cooling, the reaction mixture was centrifuged, and the supernatant was analyzed by gas chromatography under the following conditions. As a result, it was confirmed that 4-cyclohexenecarbaldehyde completely disappeared, and that 9.09 mmol of 4-cyclohexenemethanol was produced. Was. The yield of 4-cyclohexenemethanol based on the consumed 4-cyclohexenecarbaldehyde was 98%.
Met.

Example 2 The same operation as in Example 1 was carried out except that 2-propanol was used instead of 2-butanol. When the supernatant of the reaction mixture was analyzed in the same manner as in Example 1, 4
-Cyclohexenecarbaldehyde disappears completely,
The production of 9.00 mmol of cyclohexenemethanol was confirmed. The yield of the consumed 4-cyclohexenemethanol based on 4-cyclohexenecarbaldehyde was 97%.

Example 3 A 50 mL three-necked flask equipped with a reflux condenser was loaded with the zirconium oxide-supported MCM prepared in Preparation Example 1.
100 mg of -41 catalyst, 1.02 g (9.28 mmol) of 4-cyclohexenecarbaldehyde, and 20 mL of 2-butanol were charged, and the reaction system was reacted at 96 ° C for 8 hours with stirring under a nitrogen gas atmosphere. After cooling, the reaction mixture was centrifuged, and the supernatant was analyzed by gas chromatography. As a result, 98% of 4-cyclohexenecarbaldehyde had disappeared, and formation of 8.82 mmol of 4-cyclohexenemethanol was confirmed. The yield of the consumed 4-cyclohexenemethanol based on 4-cyclohexenecarbaldehyde was 97%.

Example 4 The zirconium oxide-supported MCM prepared in Preparation Example 1 was placed in a 50 mL three-necked flask equipped with a reflux condenser.
100 mg of -41 catalyst, 1.00 g (8.20 mmol) of 2-norbornene-5-carbaldehyde and 20 mL of 2-butanol were charged, and the reaction system was reacted at 96 ° C. for 8 hours with stirring under a nitrogen gas atmosphere. Was. After cooling, the reaction mixture was centrifuged, and the supernatant was analyzed by gas chromatography. As a result, 94% of 2-norbornene-5-carbaldehyde disappeared, and 7.48 mmol of 2-norbornen-5-ylmethanol was removed. Generation was confirmed. The yield of consumed 2-norbornen-5-ylmethanol based on 2-norbornene-5-carbaldehyde was 97%.

Preparation Example 2 The procedure of Preparation Example 1 was repeated, except that activated carbon (manufactured by Kansai Thermochemical Co., Ltd., mcs-30) was used instead of the mesoporous silica carrier MCM-41.
A weight% (based on Zr) supported activated carbon catalyst was prepared.

Example 5 The same operation as in Example 3 was carried out except that the activated carbon catalyst prepared in Preparation Example 2 was used as the catalyst. When the supernatant of the obtained reaction mixture was analyzed, 99% of the charged 4-cyclohexenecarbaldehyde had disappeared, and formation of 8.91 mmol of 4-cyclohexenemethanol was confirmed. The yield of consumed 4-cyclohexenemethanol based on 4-cyclohexenecarbaldehyde was 97%.
Met.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasutaka Tanaka 610-1 F-term (reference) 4H006 AA02 AC41 BA08 BA09 BA10 BA11 BA20 BA24 BA30 BA31 BE20 FC22 FC34 FC74 FE11 4H039 CA60 CB40

Claims (7)

[Claims] A formyl group of an unsaturated cyclic aldehyde in the presence of a catalyst containing at least one metal selected from Group 3, 4, 9, 13 and 14 metals and a hydrogen donor. A method for selectively reducing to produce a corresponding unsaturated cyclic alcohol. 2. The method according to claim 1, wherein the unsaturated cyclic aldehyde is C _5-16 mono to tricycloalkene carbaldehyde. 3. The unsaturated cyclic aldehyde of the formula (1)
2. The method according to claim 1, wherein the method is at least one selected from (3). Embedded image (Wherein, R ¹ and R ² are the same or different and represent a hydrogen atom or an alkyl group, and R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. Represents an integer of 0 to 3, and n represents an integer of 1 to 4.) 4. The production method according to claim 1, wherein the catalyst is composed of a simple substance or a metal oxide of Group 4 metal of the periodic table. 5. The method according to claim 1, wherein the catalyst is a solid catalyst containing zirconium oxide or a catalyst in which zirconium oxide is supported on a carrier. 6. The method according to claim 1, wherein the hydrogen donor is a secondary alcohol. 7. Formyl group of C _5-12 mono to tricycloalkene carbaldehyde selectively at a temperature of 40 to 120 ° C. and in the presence of hydrogen gas in the presence of a secondary alcohol and a catalyst in which zirconium oxide is supported on a carrier. To produce the corresponding unsaturated cyclic alcohol.