JP2020045295A - Method for producing alicyclic oxygen-containing compound - Google Patents

Abstract

To provide a method for producing an alicyclic oxygen-containing compound that can synthesize an alicyclic oxygen-containing compound in a one-stage reaction, having high yield.SOLUTION: A method for producing an alicyclic oxygen-containing compound includes bringing a carbon number of 5 or larger aliphatic oxygen-containing compound having two or more hydroxy groups or two or more carbonyl groups, or having a hydroxy group(s) and a carbonyl group(s) in a total of two or more, into contact with a basic catalyst for dehydration cyclization to produce an alicyclic oxygen-containing compound.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an alicyclic oxygen-containing compound.

  The usefulness of alicyclic oxygen-containing compounds such as cyclopentanemethanol, cyclohexanemethanol, and cycloheptanemethanol has recently attracted attention. For example, cyclopentanemethanol is used as an active ingredient of a drug material or a volatile fungicide, cyclohexanemethanol is used as a material of a fullerene derivative or an active ingredient of a volatile fungicide, and cycloheptanemethanol is It is used as a raw material for α2B adrenergic receptor modulators and as a glucokinase activator for isoindoline-1-one.

  As a method for producing such an alicyclic oxygen-containing compound, there is a method in which cyclopentane aldehyde is synthesized from tetrahydropyran-2-methanol using activated alumina as a catalyst, and cyclopentane methanol is obtained using a hydrogenation catalyst such as Raney Ni. It has been proposed (Patent Document 1). In addition, a by-product of a reaction for obtaining n-pentanol by hydroformylating 1,3-butadiene using a water-soluble rhodium compound and a water-soluble organic phosphine as a catalyst and hydrogenating it in the presence of a Pt-activated carbon catalyst. It is known that cyclopentanemethanol can be obtained as a (condensation product of 1,6-hexanedialdehyde) (Patent Document 2). However, in each of these methods, since the reaction is multi-stage, the control of the reaction and the reaction apparatus become complicated. In addition, the method of Patent Document 2 has a problem that the yield is low and the catalyst is a noble metal, so that the catalyst is expensive and the alicyclic oxygen-containing compound is only generated as a by-product. The methods shown in References 1 and 2 also only describe that cyclopentanemethanol is obtained as a by-product, and the yield is low. A reaction is required (Non-Patent Documents 1 to 3).

U.S. Pat. No. 2,480,990 Japanese Patent No. 2609429

“The Vapor Phase Catalytic Dehydrogenation of 1,6-Hexanediol”, The Journal of Organic Chemistry, 30, 2 (1965) 335-339 “Vapor phase catalytic dehydration of terminal diols”, Catalysis Today, 164 (2011) 419-424 “First rhodium-catalyzed hydroformylation of cyclopentadiene”, Journal of Molecular Catalysis A: Chemical, Volume 406, September 2015, Pages 114-117

  An object of the present invention is to solve the above problems and to provide a method for producing an alicyclic oxygen-containing compound with a high yield that can synthesize an alicyclic oxygen-containing compound by a one-step reaction.

  In order to solve the above-mentioned problems, the present inventors have started to study a method capable of producing an alicyclic oxygen-containing compound at a high yield instead of a multi-step reaction. In the course of the study, using an aliphatic oxygen compound having 5 or more carbon atoms having two or more hydroxyl groups or carbonyl groups, or having two or more hydroxyl groups and carbonyl groups as a raw material, and converting the raw material to an apatite compound or By contacting with a basic catalyst such as hydrotalcite, the aliphatic oxygen-containing compound can be subjected to a dehydration cyclization reaction, and it has been found that an alicyclic oxygen-containing compound can be synthesized with high yield in a single-step reaction. .

That is, the present invention is specified by the following items.
(1) An aliphatic oxygen-containing compound having 5 or more carbon atoms having two or more hydroxyl groups or carbonyl groups or two or more hydroxyl groups and carbonyl groups in contact with a basic catalyst to cause a dehydration cyclization reaction. A method for producing an alicyclic oxygen-containing compound, which produces an alicyclic oxygen-containing compound.
(2) The production method according to the above (1), wherein the basic catalyst is at least one selected from an apatite compound and hydrotalcite.
(3) The production method according to the above (1) or (2), wherein when the compound has a hydroxyl group, one or more hydrogen atoms are bonded to the carbon to which the hydroxyl group is bonded.
(4) The above (1) to (3), wherein one or more hydrogen atoms are bonded to at least one carbon atom among carbon atoms in the β-position to the oxygen of the hydroxyl group or the oxygen of the carbonyl group. )).
(5) the carbon at the β-position to the oxygen of any one hydroxyl group or the oxygen of the carbonyl group and at least one of the carbon to which the other hydroxyl group is bonded or the carbon of the carbonyl group; The method according to any one of the above (1) to (4), wherein three or more carbons are present between the two.
(6) The method according to any one of the above (1) to (5), wherein the apatite compound is hydroxyapatite.

  According to the production method of the present invention, various alicyclic oxygen-containing compounds can be produced with a high yield in a one-step reaction by appropriately selecting the raw materials. Therefore, the reaction device can have a simple structure, and the control of the reaction becomes easy.

  In the production method of the present invention, an aliphatic oxygenated compound having 5 or more carbon atoms having two or more hydroxyl groups or carbonyl groups or two or more hydroxyl groups and carbonyl groups in contact with a basic catalyst is subjected to dehydration cyclization. The reaction is characterized by producing an alicyclic oxygen-containing compound. The aliphatic oxygen-containing compound used as a raw material in the present invention is an aliphatic oxygen-containing compound having a hydroxyl group and / or a carbonyl group and having 5 or more carbon atoms, wherein two or more hydroxyl groups and two or more carbonyl groups are used. Or an aliphatic oxygen-containing compound having two or more hydroxyl groups and the carbonyl group in total. Of the hydroxyl group and the carbonyl group, it may have only two or more hydroxyl groups, may have only two or more carbonyl groups, or may have two or more hydroxyl groups and carbonyl groups in total. .

When the aliphatic oxygen-containing compound in the present invention has only two or more hydroxyl groups, for example, it can be represented by the following formula (1).

When the aliphatic oxygen-containing compound in the present invention has only two or more carbonyl groups, it can be represented by, for example, the following formula (2).

When the aliphatic oxygen-containing compound in the present invention has two or more hydroxyl groups and carbonyl groups in total, for example, it can be represented by the following formula (3).

は、［ ］内の構造をｎ個有することを表し、ｍは、ｎ個の各構造におけるＣ、Ｒ^ａ及びＲ^ｂに付与する番号であり、ｎ個の各構造におけるＣ、Ｒ^ａ及びＲ^ｂに対して、ｍは５から（４＋ｎ）までの各整数が番号として付与される。例えば、ｎが１のとき、

を表し、ｎが２のとき、

を表す。式（１）〜（３）において、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｒ^ｍａ及びＲ^ｍｂ並びにＲ^１及びＲ^４は、独立に、水素、酸素、水酸基、ヒドロキシアルキル基、脂肪族基、脂環式基若しくは芳香族基であるか、又は一緒になって脂環式基若しくは芳香族基を形成してもよい。ヒドロキシアルキル基としては、特に制限されないが、例えば、炭素数１〜１０のヒドロキシアルキル基を挙げることができ、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基等を挙げることができる。脂肪族基としては、特に制限されないが、例えば、炭素数１〜２０の脂肪族基を挙げることができ、アルキル基、アルケニル基、アルキニル基等を挙げることができる。アルキル基としては、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル等の鎖状のアルキル基（各異性体を含む）、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル等の環状のアルキル基などを挙げることができる。アルケニル基としては、例えば、ビニル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等を挙げることができる。アルキニル基としては、例えば、エチニル基、プロピニル基、ブチニル基、ペンチニル基、ヘキシニル基等を挙げることができる。中でも、炭素数１〜６の鎖状のアルキル基、アルケニル基及びアルキニル基が好ましい。脂環式基としては、特に制限されないが、例えば、炭素数３〜１０の脂環式基を挙げることができ、具体的には、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等を挙げることができる。芳香族基としては、特に制限されないが、例えば、ベンゼン環、ナフタレン環を含む基等が挙げられる。 In the formulas (1) to (3), n is an integer of 0 or more. When n is 0, m is not added. When n is 1 or more, m is an integer of 5 or more and (4 + n) or less. Represent. In equations (1) to (3)

Represents that there are n structures in [], m is a number given to C, ^Ra and ^Rb in each of the n structures, and C, ^Ra and R in each of the n structures ^{For b} , m is assigned an integer from 5 to (4 + n) as a number. For example, when n is 1,

And when n is 2,

Represents In the formulas (1) to (3), R ^2a , R ^2b , R ^3a , R ^3b , R ^ma and R ^mb and R ¹ and R ⁴ are each independently hydrogen, oxygen, hydroxyl, hydroxyalkyl, aliphatic Or an alicyclic or aromatic group, or together may form an alicyclic or aromatic group. Although it does not specifically limit as a hydroxyalkyl group, For example, a C1-C10 hydroxyalkyl group can be mentioned, A hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group etc. are mentioned. be able to. Although it does not specifically limit as an aliphatic group, For example, a C1-C20 aliphatic group can be mentioned, and an alkyl group, an alkenyl group, an alkynyl group, etc. can be mentioned. Examples of the alkyl group include linear alkyl groups (including each isomer) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Examples include a cyclic alkyl group such as cycloheptyl. Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. Examples of the alkynyl group include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, and a hexynyl group. Especially, a C1-C6 chain alkyl group, an alkenyl group, and an alkynyl group are preferable. The alicyclic group is not particularly limited, and examples thereof include an alicyclic group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. be able to. Although it does not specifically limit as an aromatic group, For example, the group containing a benzene ring and a naphthalene ring etc. are mentioned.

  The aliphatic oxygen-containing compound in the present invention preferably has one or more hydrogens bonded to a carbon bonded to a hydroxyl group as shown in the formulas (1) and (3). Further, in the aliphatic oxygen-containing compound of the present invention, it is preferable that one or more hydrogen atoms are bonded to at least one of the carbon atoms that are in the β-position to the oxygen of the hydroxyl group or the oxygen of the carbonyl group. . In addition, between the carbon at the β-position to the oxygen of any one hydroxyl group or the oxygen of the carbonyl group and at least one of the carbon to which the other hydroxyl group is bonded or the carbon of the carbonyl group Preferably has three or more carbon atoms.

この場合、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｒ^ｍａ及びＲ^ｍｂ並びにＲ^１及びＲ^４は、独立して、水素、酸素、水酸基、ヒドロキシアルキル基、脂肪族基、脂環式基若しくは芳香族基であるか、あるいは一緒になって脂環式基若しくは芳香族基を形成してもよく、Ｒ^１及び／又はＲ^４が式（４）に示すアルキル基である場合は、Ｒ^ｐａ及びＲ^ｐｂは、独立して、水素、酸素、水酸基、ヒドロキシアルキル基、脂肪族基、脂環式基若しくは芳香族基であるか、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｒ^ｍａ及び／又はＲ^ｍｂと一緒になって脂環式基若しくは芳香族基を形成してもよい。本段落に記載のヒドロキシアルキル基、脂肪族基、脂環式基及び芳香族基は、段落［００１４］に記載したものと同じである。 For example, in the formulas (1) to (3), two (n = 0) or three (n = 2) carbons separating the carbon bonded to the hydroxyl group and / or the carbon of the carbonyl group (C ¹ and C ^{4 in the} formula). In the case of 1), at least one of R ¹ and R ⁴ is an alkyl group having at least one hydrogen atom represented by the formula (4) bonded thereto. In this case, C ^p (R ⁴ is an alkyl group represented by the formula (4)), which is a carbon at the β-position to the oxygen of the hydroxyl group bonded to C ⁴ or the oxygen of the carbonyl group, and another hydroxyl group are bonded. 3 or more carbon exists between the C ¹ is a carbon of the carbon or a carbonyl group. Similarly, when R ¹ is an alkyl group represented by the formula (4), three or more carbon atoms exist between C ^p and C ⁴ .

In this case, R ^2a , R ^2b , R ^3a , R ^3b , R ^ma and R ^mb and R ¹ and R ⁴ independently represent hydrogen, oxygen, a hydroxyl group, a hydroxyalkyl group, an aliphatic group, an alicyclic group. Or an aromatic group, or may form an alicyclic group or an aromatic group together, and when R ¹ and / or R ⁴ is an alkyl group represented by the formula (4), ^pa and R ^pb independently represent hydrogen, oxygen, a hydroxyl group, a hydroxyalkyl group, an aliphatic group, an alicyclic group or an aromatic group, or R ^2a , R ^2b , R ^3a , R ^3b , R ^ma And / or together with R ^mb may form an alicyclic or aromatic group. The hydroxyalkyl group, aliphatic group, alicyclic group and aromatic group described in this paragraph are the same as those described in paragraph [0014].

Further, for example, in formulas (1) to (3), when the number of carbons separating the carbon to which the hydroxyl group is bonded and / or the carbon of the carbonyl group (C ¹ and C ^{4 in the} formula) is 4 or more (n ≧ 2), At least one of R ^2a , R ^2b , R ^3a , and R ^3b is a hydrogen atom, or at least one of R ¹ and R ⁴ is an alkyl having at least one hydrogen atom represented by formula (4) bonded thereto. Group. In this case, the carbon at the β-position to the oxygen of the hydroxyl group bonded to C ¹ and C ⁴ or the oxygen of the carbonyl group, that is, C ² and C ³ , and R ¹ and / or R ² are represented by the formula (4). In the case of an alkyl group, one or more hydrogen atoms are bonded to at least one carbon atom of C ^p . For example, hydrogen is substituted by C ³ or C ^p (when R ⁴ is an alkyl group represented by the formula (4)), which is a carbon at the β-position to the oxygen of the hydroxyl group or the oxygen of the carbonyl group bonded to C ⁴ If in combination, there are 3 or more carbons between C ¹ is a carbon carbon or a carbonyl group other hydroxyl groups are bonded. In addition, hydrogen is substituted by C ² or C ^p (when R ¹ is an alkyl group represented by the formula (4)) which is a carbon at the β-position to the oxygen of the hydroxyl group or the oxygen of the carbonyl group bonded to C ^1. If in combination, similarly there are three or more carbon between the C ⁴ is a carbon carbon or a carbonyl group other hydroxyl groups are bound

In the present invention, when the number of hydroxyl groups and / or carbonyl groups is three or more, it is only necessary that the above-mentioned relationship be established between a pair of carbon atoms. That is, the carbon at the β-position to the oxygen of any one hydroxyl group or the oxygen of the carbonyl group, and at least one carbon of the carbon to which a plurality of other hydroxyl groups are bonded or the carbon of the carbonyl group It suffices that three or more carbons exist between the two. For example, the formula (1) to (3), 3 between the case or neighboring carbon and C ⁴ of the C ^1, there are three or more carbon between the carbon and C ¹ next to C ⁴ When two or more carbons are present, a hydroxyl group may be bonded to the carbon present between C ¹ and C ⁴ , or the carbon of R ¹ and / or R ⁴ , and present between C ¹ and C ⁴ Or the carbons of R ¹ and / or R ⁴ may form a carbonyl group.

  The aliphatic oxygen-containing compound in the present invention is particularly limited as long as it is an aliphatic oxygen-containing compound having 5 or more carbon atoms having two or more hydroxyl groups or carbonyl groups, or having two or more hydroxyl groups and carbonyl groups in total. Not something. As the aliphatic oxygen-containing compound in the present invention, examples of the compound having two or more hydroxyl groups include diols such as 1,6-hexanediol and triols such as 1,2,8-octanetriol. Examples of the compound having two or more carbonyl groups include, for example, diketones such as acetonylacetone, dialdehydes such as adipaldehyde, and oxoaldehydes such as 5-oxohexanal. Examples of the compound having two or more carbonyl groups include hydroxyketones such as 5-hydroxy-2-pentanone and hydroxyaldehydes such as 5-hydroxyhexanal. Examples of the aliphatic oxygen-containing compound in the present invention include 1,4-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,5-hexanediol, 2,6-hexanetriol, 1,2,8-octanetriol, 4- (2-hydroxyethyl) cyclohexanol, 5-hydroxy-2-pentanone, acetonylacetone, adipaldehyde, 5-oxohexanal, 5- Hydroxyhexanal and the like can be mentioned. In the case of diols and triols, the hydroxyl group is preferably primary or secondary.

  The alicyclic oxygen compound obtained in the present invention varies depending on the raw materials used, but the alicyclic oxygen compound in the present invention is particularly limited as long as it is an alicyclic oxygen compound obtained by the production method of the present invention. Not done. Examples of the alicyclic oxygen-containing compound in the present invention include cyclopentanol, cyclopentanemethanol, 2-cyclopentenemethanol, cyclohexanol, cyclohexanemethanol, 2-cyclohexenemethanol, cycloheptanol, cycloheptanemethanol, and 2-cycloheptanol. Tenmethanol, 3-methylcyclopentanol, 3-methyl-2-cyclopentenol, 3-hydroxycyclopentanemethanol, 3-hydroxy-2-cyclopentenmethanol, cyclohexane-1,2-ethanediol, cyclohexane-1,2 -Dimethanol, cycloheptane-1-ethanol-3-methanol, bicyclo [1,2,3] -2-octanol, cyclopentanone, 2-cyclopentenone, 3-methyl-2-cyclopenteno , 1-cyclopentene-1-carbaldehyde, 2-cyclohexenone, and 2-cyclohexen-1-ol. According to the production method of the present invention, for example, a 5- or more-membered alicyclic oxygen-containing compound, a bicyclic alicyclic oxygen-containing compound, or the like can be produced, and a 5-, 6-, or 7-membered ring can be produced. A ring alicyclic oxygen-containing compound, a bicyclic alicyclic oxygen-containing compound in which the rings are bonded to each other, and the like can be suitably produced. Further, the alicyclic oxygen-containing compound in the present invention does not include a heterocyclic compound.

  The catalyst in the production method of the present invention is not particularly limited as long as it is a basic catalyst.Examples include apatite compounds, hydrotalcite compounds, alkali metals such as sodium and potassium, and alkaline earths such as magnesium and calcium. Oxides, hydroxides, phosphates and the like of similar metals can be mentioned.

The apatite compound is a compound having the apatite structure, a concept also including a solid solution of the general formula: can be represented by _{M a (M'O b) c X} 2. The basic apatite compound is represented by M ₁₀ (M′O ₄ ) ₆ X _{2 in} which a is 10, b is 4, c is 6, and a / c is 1.67. The apatite compound is not limited to the basic apatite compound, and includes cases where a, b, and c do not take the above values. In the case of a solid solution, when a / c deviates from 1.67, when M includes an element other than divalent, and when M ′ includes an element other than pentavalent such as C or S, a, b and c are different from the above values. In the apatite compound of the present invention, a / c is preferably between 1.5 and 1.8. In the apatite compound according to the present invention, M in the general formula is not particularly limited, but for example, Ca, Sr, Pb, Mg, Cd, Fe, Co, Ni, Cu, Zn, La, One or more selected from H and the like can be mentioned. Among these, Ca is preferable. Further, M ′ is not particularly limited, and examples thereof include one or more selected from P, V, As, C, S, and the like. Among them, P or a combination of P and another element is preferable. X is not particularly limited, but examples thereof include OH, F, and Cl. Of these, OH is preferred. As the shape of the apatite compound, any one such as granules, spheres, pellets, and honeycombs can be used. The apatite compound in the present invention is not particularly limited as long as it is as described above, but hydroxyapatite is preferred. Hydroxyapatite is stoichiometrically represented by a composition of Ca ₁₀ (PO ₄ ) ₆ (OH) _2, but as described above, non-stoichiometric Ca / P molar ratio does not become 1.67. Any of these can exhibit the properties of hydroxyapatite and have an apatite structure, and include such synthetic hydroxyapatite having a Ca / P molar ratio of about 1.4 to 1.8. Particularly, in the production method of the present invention, hydroxyapatite having a Ca / P molar ratio of 1.60 to 1.80 is preferable.

The hydrotalcite compound of the general formula ^{_{[M 2+ 1-x M 3+}} x (OH) 2] can be represented by _{[A n- x / n · mH} 2 O]. M ²⁺ represents Mg ²⁺ , Fe ²⁺ , Zn ²⁺ , Ca ²⁺ , Li ²⁺ , Ni ²⁺ , Co ²⁺ , Pt ²⁺ , Pd ²⁺ , Cu ^2+, etc., and M ³⁺ represents Al ³⁺ , Fe ³⁺ , Cr ³⁺ , represents Mn ^{3+, etc., a n-is,} _CO ^{3 2-and} OH ^- represent like or may be one or more, respectively. m takes a value of 0 or more, and x generally ranges from 0.2 to 0.4, but is not limited thereto. As the hydrotalcite compound, hydrotalcite Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O is preferable. As the shape of the hydrotalcite compound, any one such as granules, spheres, pellets, and honeycombs can be used.

  According to the method of the present invention, an aliphatic oxygen-containing compound having 5 or more carbon atoms having two or more hydroxyl groups or carbonyl groups, or having two or more hydroxyl groups and carbonyl groups in total, is contacted with a basic catalyst to form a dehydration ring. The alicyclic oxygen-containing compound can be produced by the reaction. As a method or apparatus for bringing the aliphatic oxygen-containing compound into contact with a basic catalyst and reacting the same, a conventionally known method or apparatus can be appropriately used. When the aliphatic oxygen-containing compound as a raw material is a compound that is solid at ordinary temperature, the reaction can be carried out in the presence of a solvent. In the case of a compound that is liquid at room temperature, the reaction can be carried out in the presence or absence of a solvent. The solvent used is not particularly limited as long as the aliphatic oxygen-containing compound serving as a raw material dissolves or disperses. Examples thereof include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol. , Iso-butanol, tert-butanol, ethyl acetate, dimethyl sulfoxide, 2-methoxyethanol, acetic anhydride, tetrahydrofuran, acetonitrile, dichloromethane and the like. The liquid aliphatic oxygen-containing compound or the aliphatic oxygen-containing compound dissolved or dispersed in a solvent may be introduced into a reactor together with an inert carrier gas such as nitrogen gas or helium gas to cause a reaction.

  The reaction temperature when the aliphatic oxygen-containing compound in the present invention is brought into contact with the catalyst for reaction is not particularly limited, but is usually preferably selected in the range of 150 to 450 ° C, and is preferably selected in the range of 250 to 400 ° C. Is more preferable. The contact time (W / F) is preferably 0.01 h to 200 h (hour), more preferably 0.05 to 50 h. Here, W is the catalyst weight (g), and F is the flow rate (g / h) of the aliphatic oxygen-containing compound. The reaction time, the amount of the catalyst used, the amount of the aliphatic oxygen-containing compound to be reacted, and the like can be appropriately selected as needed. The reaction apparatus used in the production method of the present invention may be any of a batch system, a continuous system, a fixed bed, a moving bed, a fluidized bed or a slurry bed, and can be carried out under normal pressure or under pressure. For example, when a fixed bed flow reactor is used, an inert filler such as silica wool or quartz sand may be filled in the upstream and downstream of the catalyst layer. By purifying the reaction product by a known purification means such as distillation or crystallization, a high-purity alicyclic oxygen-containing compound can be obtained.

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

[Example 1]
(Evaluation of synthesis reaction and catalytic properties)
The reaction was carried out using a raw material and a catalyst shown in Table 1 using a fixed bed gas flow type catalytic reactor as the reactor. 0.15 g of the catalyst was charged into the center of a glass reaction tube having an inner diameter of 8 mm, silica wool was placed before and after the catalyst, and heat treatment was performed at 500 ° C. for 3 hours as a pretreatment. The reaction solution (1,6-hexanediol: ethanol = 1: 9 (mol: mol)) was introduced into a nitrogen gas stream at 0.98 mL / h using a syringe pump, and reacted at 375 ° C. for 5 hours. . Reaction products were collected hourly in an ice water trap. The recovered liquid was weighed and the liquid and gas products behind the trap were analyzed by GC-FID and GC-MS. GC-14B (manufactured by Shimadzu Corporation) was used for GC-FID, and DB-WAX was used for the analysis column. As the GC-MS, HP5890 (GC) (manufactured by Hewlett-Packarded) equipped with MS detector HP5972 (MDS) (manufactured by Hewlett-Packarded) was used. For liquid products, those diluted to 10 mL with butanol were analyzed.

(Selectivity of alicyclic oxygen-containing compound)
Table 1 shows the selectivity of the alicyclic oxygen-containing compound 3 hours after the start of the reaction. Using 1,6-hexanediol as a raw material, cyclopentanemethanol and 2-cyclopentenemethanol were obtained as alicyclic oxygen-containing compounds. The selectivity of the alicyclic oxygen-containing compound is the total selectivity of the cyclopentanemethanol and 2-cyclopentenemethanol.

[Example 2]
Example 2 As Example 2, the reaction and evaluation were performed in the same manner as in Example 1 except that the amount of the catalyst was 0.3 g using the raw materials and the catalysts shown in Table 1. Table 1 shows the selectivity of the alicyclic oxygen-containing compound 5 hours after the start of the reaction. As in Example 1, when 1,6-hexanediol was used as a raw material, cyclopentanemethanol and 2-cyclopentenemethanol were obtained as alicyclic oxygen-containing compounds. The selectivity of the alicyclic oxygen-containing compound is the total selectivity of the cyclopentanemethanol and 2-cyclopentenemethanol.

[Comparative Example 1]
The reaction and evaluation were carried out in the same manner as in Example 1 using the raw materials and catalysts shown in Table 1. Table 1 shows the selectivity of the alicyclic oxygen-containing compound 5 hours after the start of the reaction. In the reaction of Comparative Example 1, no alicyclic oxygen-containing compound was obtained.

[Examples 3 and 4]
As Example 3, the reaction and evaluation were performed in the same manner as in Example 1 except that the reaction temperature was changed to 400 ° C. Example 4 As Example 4, the reaction and evaluation were performed in the same manner as in Example 1 except that the reaction temperature was 250 ° C. and the amount of catalyst charged was 0.8 g. In Examples 3 and 4, as in Example 1, cyclopentanemethanol and 2-cyclopentenemethanol were obtained as alicyclic oxygen-containing compounds. Table 2 shows the results 5 hours after the start of the reaction.

[Comparative Example 2]
The reaction and evaluation were carried out in the same manner as in Example 1, except that the raw material was 1,4-butanediol, the reaction temperature was 300 ° C., and the catalyst loading was 0.2 g. When 1,4-butanediol was used as a raw material, an alicyclic oxygen-containing compound was not generated, but tetrahydrofuran, which was a heterocyclic compound, was generated. Table 2 shows the results 5 hours after the start of the reaction.

[Example 5]
The reaction was carried out in the same manner as in Example 1 except that the raw material was 1,7-heptanediol, the reaction temperature was 375 ° C., the catalyst loading was 0.2 g, the dilution solvent was methanol, and the raw material dilution ratio was 1:49. And evaluation. When 1,7-heptanediol was used as a raw material, cyclohexanemethanol and 2-cyclohexenemethanol were formed as alicyclic oxygen-containing compounds. Table 3 shows the results 5 hours after the start of the reaction. The selectivity of the alicyclic oxygen-containing compound is the total selectivity of the above cyclohexanemethanol and 2-cyclohexenemethanol.

[Example 6]
The reaction and evaluation were carried out in the same manner as in Example 5, except that the raw material was 1,8-octanediol and the amount of catalyst was 0.1 g. When 1,8-octanediol was used as a raw material, cycloheptanemethanol and 2-cycloheptenemethanol were formed as alicyclic oxygen-containing compounds. Table 3 shows the results 5 hours after the start of the reaction. The selectivity of the alicyclic oxygen-containing compound is the total selectivity of the above cycloheptanemethanol and 2-cycloheptenemethanol.

[Example 7]
The reaction and evaluation were carried out in the same manner as in Example 5, except that the raw material was acetonylacetone, the catalyst loading amount was 0.05 g, and the raw material dilution ratio was 1:19. When acetonylacetone was used as a raw material, 3-methyl-2-cyclopentenone was generated as an alicyclic oxygen-containing compound. Table 3 shows the results 3 hours after the start of the reaction. The selectivity of the alicyclic oxygen-containing compound is the selectivity of the 3-methyl-2-cyclopentenone.

The production method of the present invention produces cycloaliphatic oxygen-containing compounds such as cyclopentanemethanol, cyclohexanemethanol, and cycloheptanemethanol which are useful in various fields such as pharmaceutical raw materials and fungicides in a high yield with a simple reaction mechanism. Therefore, it is useful as a method for producing an alicyclic oxygen-containing compound.

Claims (6)

  An alicyclic compound is obtained by contacting an aliphatic oxygen-containing compound having 5 or more carbon atoms having 2 or more hydroxyl groups or carbonyl groups, or having 2 or more hydroxyl groups and carbonyl groups, with a basic catalyst to effect a dehydration cyclization reaction. A method for producing an alicyclic oxygen-containing compound, which produces an oxygen-containing compound.   The method according to claim 1, wherein the basic catalyst is at least one selected from an apatite compound and hydrotalcite.   3. The method according to claim 1, wherein when the compound has a hydroxyl group, at least one hydrogen is bonded to the carbon to which the hydroxyl group is bonded. 4.   4. The method according to claim 1, wherein one or more hydrogen atoms are bonded to at least one of the carbon atoms at the β-position to the oxygen of the hydroxyl group or the oxygen of the carbonyl group. Production method.   Between the carbon at the β-position to the oxygen of any one of the hydroxyl groups or the oxygen of the carbonyl group and at least one of the carbon to which the other hydroxyl group is bonded or the carbon of the carbonyl group; The method according to any one of claims 1 to 4, wherein three or more carbon atoms are present. The method according to any one of claims 1 to 5, wherein the apatite compound is hydroxyapatite.