Cyclic diol compound, method for producing the same, and catalyst for saccharide decomposition

Abstract

To provide a method for producing a cyclic diol compound derived from saccharides as a starting material, a cyclic diol compound, and a catalyst for saccharide decomposition.SOLUTION: A method for producing a cyclic diol compound represented by the following general formula (1), comprises a step of reacting glucose or mannose in the presence of zeolite and a metal oxide in an aliphatic alcohol solvent having 1 to 10 carbon atoms, wherein the metal oxide comprises at least one selected from the group consisting of oxides of Group 2 metal elements, oxides of Group 5 metal elements, oxides of Group 6 metal elements, and complex metal oxides, and the complex metal oxide is Mo3Nb2O14 or W3Nb2O14. [In the formula, R represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cyclic diol compound, a method for producing the same, and a catalyst for decomposing saccharides. [Background technology]

[0002] The utilization of non-edible biomass, whose main components are cellulose, hemicellulose, and lignin, has been attracting attention as a renewable carbon resource that can replace fossil fuels. For example, it is expected that compounds derived from glucose, a hexose sugar obtained by hydrolyzing cellulose, can be used as raw materials for chemical products.

[0003] Glucose is known to react in the presence of an acid-base catalyst to produce various carbohydrates. Among these, research has focused on erythrose and glycolaldehyde, which are produced via the retroaldol reaction of glucose. In particular, the formyl group contained in these compounds is highly reactive, making them prone to side reactions, and various reaction conditions have been investigated.

[0004] For example, Non-Patent Document 1 proposes a method of reacting glucose with tetrahydroboron in the presence of molybdenum oxide as a protecting agent to obtain erythrose as a boron complex. Non-Patent Document 2 proposes a method of reacting glucose in the presence of molybdic acid and then further reacting with acetylacetone to obtain a furan compound. Non-Patent Document 3 proposes a method of reacting glucose in the presence of a metal salt of phosphotungstic acid and an alcohol to obtain an acetal compound derived from glycolaldehyde. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Yueer Yan, Lei Feng, GangLi,Shaoying Lin, Zhen Sun, Yahong Zhang, and Yi Tang. “Borate-StabilizedTransformationof C6 Aldose to C4 Aldose” ACS Catal.,7, 7(2021):4473-4478 [Non-patent document 2] Rui Zhang, Aleksi Eronen,XiangzeDu, Enlu Ma, Ming Guo, Karina Moslova, and Timo Repo. “Acatalyticapproach via retro-aldol condensation of glucose to furanic compounds”GreenChemistry, 23 (2021):5481-5486 [Non-patent document 3] TihangLiu, Jiangang Wang, Hongyou Cui, and Jinghua Wang, “Conversion of biomass-derived sugars to 1,1,2-trialkoxyethane via a [2 + 4]retro-aldol reaction over alkaline and alkaline earth metal salts of phosphotungstic acid” Green Chemistry, 25, 11(2023):4565-4576 Summary of the Invention [Problem to be solved by the invention]

[0006] Incidentally, it is desirable to obtain a variety of compounds as raw materials for chemical products according to their applications.

[0007] In view of the above circumstances, an object of the present invention is to provide a method for producing a cyclic diol compound using glucose or the like as a raw material, the cyclic diol compound, and a catalyst for decomposing saccharides. [Means for solving the problem]

[0008] As a result of intensive research into solving the above problems, the present inventors have completed the following inventions [1] to [9]. [1] A method for producing a cellulose ester comprising the steps of: reacting glucose or mannose in an aliphatic alcohol solvent having 1 to 10 carbon atoms in the presence of a zeolite and a metal oxide; the metal oxide comprises at least one selected from the group consisting of an oxide of a Group 2 metal element, an oxide of a Group 5 metal element, an oxide of a Group 6 metal element, and a composite metal oxide; The composite metal oxide is Mo3Nb2O 14 or W3Nb2O 14 That is, A method for producing a cyclic diol compound represented by the following general formula (1): [ka] [In the formula, R represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.] [2] The method for producing a cyclic diol compound according to [1], wherein the aliphatic alcohol is ethanol or propanol. [3] The method for producing a cyclic diol compound according to [1] or [2], wherein the metal oxide is niobium(V) oxide. [4] The method for producing a cyclic diol compound according to any one of [1] to [3], wherein the zeolite is an MFI type zeolite. [5] The method for producing a cyclic diol compound according to any one of [1] to [4], wherein the zeolite contains SiO2 and Al2O3, and the ratio of the amount of SiO2 to the amount of Al2O3 is 10 to 350. [6] A method comprising the steps of reacting glucose or mannose in an aliphatic alcohol solvent having 1 to 10 carbon atoms in the presence of a composite metal oxide, The composite metal oxide is Mo3Nb2O 14 or W3Nb2O 14 and A method for producing a cyclic diol compound represented by the following general formula (1): [ka] [In the formula, R represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.] [7] The method for producing a cyclic diol compound according to [6], wherein the aliphatic alcohol is ethanol or propanol. [8] Mo3Nb2O 14 or W3Nb2O 14 A catalyst for decomposing sugars, comprising: [9] A cyclic diol compound represented by the following general formula (1): [ka] [In the formula, R represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms.] [Effects of the Invention]

[0009] According to the present invention, a method for producing a cyclic diol compound with high yield, a cyclic diol compound, and a catalyst for decomposing saccharides can be provided. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a graph showing the results of quantitative analysis by HPLC of the products obtained when each metal oxide was added. [Figure 2] FIG. 2 shows the results of 1H-NMR obtained for the C4 compound in Experimental Example 2-1. [Figure 3] FIG. 3 shows the results of 13C-NMR obtained for the C4 compound in Experimental Example 2-1. [Figure 4] FIG. 4 shows the results of HSQC obtained for the C4 compound in Experimental Example 2-1. DETAILED DESCRIPTION OF THE INVENTION

[0011] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0012] A method for producing a cyclic diol compound represented by the following general formula (1) according to one embodiment of the present invention comprises a step of reacting glucose or mannose in an aliphatic alcohol solvent having 1 to 10 carbon atoms in the presence of a zeolite and a metal oxide, wherein the metal oxide comprises at least one selected from the group consisting of oxides of Group 2 metal elements, oxides of Group 5 metal elements, oxides of Group 6 metal elements, and composite metal oxides. [ka] [In the formula, R represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.]

[0013] According to this production method, the cyclic diol compound represented by general formula (1) can be obtained in a relatively high yield. Although the reason why the production method of this embodiment exhibits such an effect is not necessarily clear, it is presumed that the cyclic diol compound represented by general formula (1) can be efficiently obtained by carrying out the reaction in an aliphatic alcohol solvent in the presence of zeolite and metal oxide, through the retro-aldol reaction of glucose or mannose promoted mainly by the metal oxide, and the acetalization of the resulting erythrose accompanied by cyclization promoted mainly by the zeolite.

[0014] The aliphatic hydrocarbon group having 1 to 10 carbon atoms in R in general formula (1) corresponds to the residue obtained by removing the hydroxyl group from an aliphatic alcohol having 1 to 10 carbon atoms. In the experimental examples described below, only examples using glucose as a raw material are shown, but it has been confirmed that under the reaction conditions in the experimental examples, glucose is epimerized and converted to mannose, and mannose is consumed together with glucose, thereby producing a cyclic diol compound represented by general formula (1).

[0015] Glucose has the molecular formula CH 12 Glucose is a hexose of O6. The glucose may be glucose obtained by hydrolyzing cellulose or the like, or may be commercially available glucose.

[0016] Mannose has the molecular formula CH 12 Mannose is a hexose having a molecular weight of O6. For example, mannose may be obtained by hydrolyzing a glycoprotein, may be obtained by converting another monosaccharide, or may be commercially available mannose.

[0017] Zeolite is a crystalline aluminum silicate with a structure in which SiO4 tetrahedrons and AlO4 tetrahedrons are connected three-dimensionally, sharing the apex oxygen, and its composition formula is 2 / xM x+ It is expressed as Al2O3mSiO2nH2O, where M represents a cation, x represents the valence of the cation represented by M, and m represents the silica / alumina ratio (the ratio of the amount of SiO2 to the amount of Al2O3).

[0018] The valence (x) of the cation (M) contained in the zeolite is at least 1. Examples of the cation (M) include hydrogen ions, potassium ions, sodium ions, lithium ions, and ammonium ions.

[0019] The silica / alumina ratio (ratio of the amount of SiO2 to the amount of Al2O3) may be 10-350, preferably 20-300, and more preferably 50-200.

[0020] Zeolite framework structures include MFI, MOR, LTA, FER, MWW, LTL, FAU, and BEA types, with MFI or MOR being preferred and MFI being more preferred. The above three-letter alphabets represent framework codes compiled into a database by the International Zeolite Association.

[0021] The metal oxides are oxides of Group 2 metal elements, oxides of Group 5 metal elements, and oxides of Group 6 metal elements.

[0022] Examples of oxides of Group 2 metal elements include magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO). Calcium oxide (CaO) or strontium oxide (SrO) is preferred, and strontium oxide (SrO) is more preferred.

[0023] Examples of oxides of Group 5 metal elements include niobium(V) oxide (Nb2O5), niobium(IV) oxide (NbO2), niobium(II) oxide (NbO), vanadium(V) oxide (VO5), and tantalum(V) oxide (Ta2O5), of which niobium(V) oxide (Nb2O5) or vanadium(V) oxide (VO5) is preferred, and niobium(V) oxide is more preferred.

[0024] Examples of oxides of Group 6 metal elements include tungsten(VI) oxide (WO), molybdenum(VI) oxide (MoO), and chromium(III) oxide (CrO), with tungsten(VI) oxide (WO) or molybdenum(VI) oxide (MoO) being preferred, and tungsten(VI) oxide (WO) being particularly preferred.

[0025] A composite metal oxide is an oxide containing multiple metal elements, for example, two types of metal elements. A specific example is Mo3Nb2O 14 , W3Nb2O 14 etc.

[0026] The number of carbon atoms in the aliphatic alcohol is preferably 1 to 6, more preferably 2 to 3. Specific examples of the aliphatic alcohol include linear aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 1-nonanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, and 5-decanol; and branched aliphatic alcohols such as 2-propanol and isobutanol, and preferably ethanol or propanol (1-propanol or 2-propanol).

[0027] Among the aliphatic alcohols, ethanol in particular may be a synthetic alcohol or bioethanol obtained by fermenting biomass or the like.

[0028] In the production method of this embodiment, the "aliphatic alcohol solvent" may be a pure aliphatic alcohol, or may contain impurity components to the extent that the reaction is not significantly inhibited. Examples of impurity components include monosaccharides other than glucose and mannose, disaccharides, polysaccharides, and water. Among these, from the viewpoint of efficiently obtaining the target compound, the water content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the total mass of the alcohol solvent, and it is particularly preferable that the alcohol solvent contains no water.

[0029] The reaction temperature in the above reaction may be 160°C or higher, 170°C or higher, 180°C or higher, or 190°C or higher. The reaction temperature in the above reaction may be 250°C or lower, 240°C or lower, 230°C or lower, or 220°C or lower.

[0030] The reaction time for the above reaction may be 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more, and may be 300 minutes or less, 250 minutes or less, 200 minutes or less, 150 minutes or less, 100 minutes or less, or 60 minutes or less.

[0031] The pressure of the reaction system during the above reaction can be, for example, 0.5 MPa to 10 MPa. The reaction may be carried out in an air atmosphere, or in an argon or nitrogen atmosphere to avoid side reactions. When the reaction is carried out in an argon or nitrogen atmosphere, the argon or nitrogen partial pressure may be 0.5 MPa to 10 MPa.

[0032] In general formula (1), R is an aliphatic hydrocarbon group having 1 to 10 carbon atoms. The aliphatic hydrocarbon group may be either linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Methyl, ethyl, propyl, and isopropyl groups are preferred, and ethyl, propyl, and isopropyl groups are more preferred.

[0033] The stereoisomer of the cyclic diol compound is not particularly limited, and examples thereof include cyclic diol compounds having the stereoisomers described below. [ka]

[0034] The cyclic diol compound represented by general formula (1) of this embodiment has a unique structure with two hydroxyl groups in a five-membered ring containing an oxygen atom, and is therefore promising as a raw material for chemical products.

[0035] Another embodiment of the present invention relates to a method for producing a cyclic diol compound represented by the general formula (1), which comprises a step of reacting glucose or mannose in an aliphatic alcohol solvent having 1 to 10 carbon atoms in the presence of a composite metal oxide, wherein the composite metal oxide is Mo3Nb2O14 or W3Nb2O 14 is.

[0036] According to this production method, the cyclic diol compound represented by general formula (1) can be obtained in a relatively high yield. The reason why the production method of this embodiment exhibits such an effect is not entirely clear, but it is presumed that by carrying out the reaction in a fatty acid alcohol solvent in the presence of a specific composite metal oxide, both the retro-aldol reaction and the acetalization reaction are promoted, thereby efficiently obtaining the cyclic diol compound represented by general formula (I). Because the specific composite metal oxide functions as both a Lewis acid and a Brented acid, it is presumed that the cyclic diol compound represented by general formula (I) can be obtained without using the above-mentioned zeolite.

[0037] The reaction conditions, including glucose, mannose, aliphatic alcohol, reaction temperature, reaction time, and pressure of the reaction system, and the cyclic diol compound, including preferred examples, are as described above.

[0038] A catalyst for decomposing saccharides according to still another embodiment of the present invention is Mo3Nb2O 14 or W3Nb2O 14 Contains Mo3Nb2O 14 or W3Nb2O 14 The saccharide decomposition catalyst of this embodiment can be used as a catalyst for producing a cyclic diol represented by the general formula (1) above.

[0039] The sugar is preferably a sugar that undergoes a retroaldose reaction and has a hexose structure. Among sugars having a hexose structure, hexaaldoses are preferred for deriving the diol compound of the present invention, but hexaketoses also behave similarly by isomerizing to hexaaldoses.

[0040] The sugar may be a monosaccharide, disaccharide, or polysaccharide as long as it has a hexose structure, and is preferably a monosaccharide. Examples of monosaccharides include hexaldoses such as glucose, mannose, and galactose, and hexaketoses such as fructose and tagatose, and mixtures thereof are also acceptable. Of these, glucose or mannose is particularly preferred.

[0041] Examples of disaccharides include sucrose, isomaltose, trehalose, cellobiose, lactose, maltose, etc. Examples of polysaccharides include starch, as well as dextrins such as dextrin, maltodextrin, and indigestible dextrin. [Example]

[0042] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0043] Experimental Example 1: Examination of metal oxides to be added (Reaction conditions) A solution was prepared by adding 22.5 mg of glucose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 12.5 mg of metal oxide, and 5 mL of ethanol to a Teflon® container. The Teflon® container was placed in an autoclave, and argon gas was introduced into the autoclave to a partial pressure of 3 MPa. The reaction was carried out at 190°C for 15 minutes to obtain a reaction solution. After the reaction, solid components were removed from the reaction solution by centrifugation, and the amount of product produced in the liquid phase of the reaction solution was measured by HPLC analysis. This experimental example was conducted to confirm whether metal oxides can promote the retroaldol reaction. HPLC analysis confirmed the yields of erythrose, threose, and their derivatives, as well as glycolaldehyde and its derivatives.

[0044] (HPLC analysis) The products contained in the liquid phase of the reaction solution were analyzed by high-performance liquid chromatography (HPLC). The yield of the products contained in the liquid phase of the reaction solution was calculated using HPLC analysis with the absolute calibration curve method. The product yield was expressed as a percentage, which is the ratio of the number of carbon atoms of each product contained in the reaction solution after the reaction to the number of carbon atoms of glucose contained in the solution before the reaction. The HPLC conditions are as follows. Peaks in the HPLC analysis were identified by measuring standard samples. Erythrose and threose were used as standard samples for C4 compounds, and glycolaldehyde was used as standard sample for C2 compounds. Note that an acidic aqueous solution was used as the eluent in the HPLC analysis. Therefore, acetal compounds and cyclic alkoxide compounds undergo hydrolysis in the acidic eluent, and C4 compounds are detected as erythrose or threose, and C2 compounds are detected as glycolaldehyde. Equipment: LC-2030C Plus (Shimadzu Corporation) Detector: Differential refractive index detector (LC-2030C Plus, built-in) Column: Aminex HPX-87H column (BioRad Laboratories) Column temperature: 35℃ Mobile phase: 5mM dilute sulfuric acid (0.5 mL min -1 )

[0045] The results of HPLC analysis of the products obtained when each metal oxide was added are shown in Figure 1. In Figure 1, C4 compounds refer to erythrose and threose, which have four carbon atoms; C2 compounds refer to a mixture of glycolaldehyde, which has two carbon atoms, and its derivative, 1,1,2-triethoxyethane; MAN refers to mannose; FRU refers to fructose; and others refer to glyceraldehyde, dihydroxyacetone, ethyl glycoside, and pyruvaldehyde. Missing refers to the difference between the conversion rate of the raw material glucose and the total yield of C4 compounds, C2 compounds, MAN, FRU, and others, and is a collective term for compounds produced by the conversion of glucose whose structures could not be identified. As shown in Figure 1, when metal oxides such as Group 2 metal oxides (calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO)), Group 5 metal oxides (vanadium (V) oxide (VO), niobium (V) oxide (NbO), tantalum (V) oxide (TaO)), or Group 6 metal oxides (molybdenum (VI) oxide (MoO), tungsten (VI) oxide (WO)) were added, the total yield of C4 and C2 compounds tended to increase.

[0046] Experimental Example 2: Examination of acid catalyst addition conditions (Experimental Example 2-1) A solution was prepared by adding 22.5 mg of glucose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 12.5 mg of niobium (V) oxide as a metal oxide, 12.5 mg of mordenite zeolite (H-MOR) as an acid catalyst, and 5 mL of ethanol to a Teflon container. The Teflon container was placed in an autoclave, and argon gas was introduced into the autoclave so that the partial pressure of argon gas was 3 MPa. The reaction was carried out at 190 °C for 15 minutes to obtain a reaction solution. After the reaction, solid components were removed from the reaction solution by centrifugation, and the glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and CB were calculated by HPLC analysis.

[0047] (Experimental Example 2-2) The reaction was carried out under the same conditions as in Experimental Example 2-1, except that mordenite zeolite (H-MOR) was not added, and HPLC analysis was carried out.

[0048] (Experimental Example 2-3) The reaction was carried out under the same conditions as in Experimental Example 2-1, except that the mordenite zeolite was replaced with a strongly acidic cation exchange resin (Amberlyst-15 (registered trademark) manufactured by MP Biomedicals), and HPLC analysis was carried out.

[0049] (Experimental Example 2-4) The reaction was carried out under the same conditions as in Experimental Example 2-1, except that ethanol was replaced with water, and HPLC analysis was carried out.

[0050] (Experimental Example 2-5) The reaction was carried out under the same conditions as in Experimental Example 2-1, except that niobium (V) oxide was not added, and HPLC analysis was carried out.

[0051] Table 1 shows the glucose conversion rate, the yield of each product, and CB in Experimental Examples 2-1 to 2-5. The glucose conversion rate refers to the rate at which the reactant glucose is changed by the reaction (i.e., the percentage of the glucose contained in the reaction solution after the reaction relative to the glucose contained in the solution before the reaction). The product yield is the percentage of the carbon atom content of each product in the reaction solution after the reaction relative to the carbon atom content of glucose in the solution before the reaction. CB refers to the percentage of the total carbon atom content of glucose, C4, C2, MAN, and others relative to the carbon atom content of glucose in the solution before the reaction. In Table 1, C4 is a C4 compound and refers to a mixture of erythrose and threose, which have four carbon atoms, and their derivatives (including erythrose derivatives, which are cyclic diol compounds represented by general formula (1)); C2 is a C2 compound and refers to a mixture of glycolaldehyde, which has two carbon atoms, and its derivatives, glycolaldehyde diethyl acetal and 1,1,2-triethoxyethane; MAN means mannose, and others mean glyceraldehyde, dihydroxyacetone, ethyl glycoside, and pyruvaldehyde.

[0052] [Table 1]

[0053] As shown in Table 1, in Experimental Example 2-1, C4 compounds and C2 compounds were obtained in high yields by reacting glucose in the presence of niobium (V) oxide and zeolite.

[0054] (NMR analysis) The reaction was carried out under the conditions described in Experimental Example 2-1. After the reaction, solid components were removed from the reaction solution by centrifugation to obtain only the liquid phase of the reaction solution. Ethanol was separated from the liquid phase of the reaction solution obtained by centrifugation using an evaporator, and a syrupy product was obtained. An extraction procedure in which 10 mL of ethyl acetate was added to the obtained syrupy product was repeated three times to extract and separate the C4 compounds. A mixed solution of ethyl acetate and dichloromethane was used as the developing solvent, and the C4 compounds obtained by extraction and separation were purified by column chromatography. The structure of the purified C4 compounds was confirmed by various NMR analyses ( 1 H-NMR, 13 The NMR analysis was performed using a JNM-ECZ600 (manufactured by JEOL Ltd.).

[0055] 1 H-NMR, 13 The results of C-NMR (DEPT NMR) and HSQC NMR are shown in Figures 2 to 4. The results in Figures 2 to 4 indicate that the compound represented by the following formula (I) was produced as the C4 compound.

[0056] [ka]

[0057] The reaction was carried out under the conditions described in Experimental Examples 2-2 and 2-3, and NMR analysis was carried out in the same manner. As a result, the production of the compound represented by formula (I) above could not be confirmed under the conditions of Experimental Examples 2-2 and 2-3.

[0058] Experimental Example 3: Examination of reaction solvent conditions (Experimental Example 3-1) A solution was prepared by adding 22.5 mg of glucose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 12.5 mg of niobium (V) oxide, 12.5 mg of MOR-type zeolite with a silica / alumina ratio of 90, and 5 mL of methanol as a solvent to a Teflon® container. The Teflon® container was placed in an autoclave, and argon gas was introduced into the autoclave so that the argon gas partial pressure was 3 MPa. The reaction was carried out at 190°C for 15 minutes to obtain a reaction solution. After the reaction, solid components were removed from the reaction solution by centrifugation, and the glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated by HPLC analysis. The glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated using the same method as in Experimental Example 2.

[0059] (Experimental Example 3-2) The reaction was carried out under the same conditions as in Experimental Example 3-1, except that ethanol was used as the solvent, and HPLC analysis was carried out.

[0060] (Experimental Example 3-3) The reaction was carried out under the same conditions as in Experimental Example 3-1, except that 1-propanol was used as the solvent, and HPLC analysis was carried out.

[0061] (Experimental Example 3-4) The reaction was carried out under the same conditions as in Experimental Example 3-1, except that 2-propanol was used as the solvent, and HPLC analysis was carried out.

[0062] (Experimental Example 3-5) The reaction was carried out under the same conditions as in Experimental Example 3-1, except that water was used as the solvent, and HPLC analysis was carried out.

[0063] The results of HPLC analysis in Experimental Examples 3-1 to 3-5 are shown in Table 2. As shown in Table 2, when methanol, ethanol, 1-propanol, and 2-propanol were used as solvents, C4 compounds and C2 compounds were produced, but when water was used as solvent, C4 compounds and C2 compounds were not produced.

[0064] In Table 2, C4 means a C4 compound. Among the C4 compounds, derivatives of erythrose having four carbon atoms (including cyclic diol compounds represented by general formula (1)) and derivatives of threose have different structures depending on the solvent used in the reaction. For example, in Experimental Example 3-1, derivatives of erythrose and threose having four carbon atoms refer to derivatives of erythrose and threose having a structure derived from methanol, and in Experimental Example 3-2, derivatives of erythrose and threose having four carbon atoms refer to derivatives of erythrose and threose having a structure derived from ethanol.

[0065] In Table 2, C2 refers to the C2 compound. Among the C2 compounds, glycolaldehyde diethyl acetal, which is a derivative of glycolaldehyde, and 1,1,2-triethoxyethane are compounds produced in Experimental Example 3-2, in which ethanol was used in the reaction. Different compounds are produced depending on the solvent used in the reaction. For example, in Experimental Example 3-1, in which methanol was used in the reaction, glycolaldehyde dimethyl acetal and 1,1,2-trimethoxyethane are produced as derivatives of glycolaldehyde.

[0066] [Table 2]

[0067] Experimental Example 4: Examination of reaction temperature (Experimental Example 4-1) A solution was prepared by adding 22.5 mg of glucose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 12.5 mg of niobium (V) oxide, 12.5 mg of MOR-type zeolite with a silica / alumina ratio of 90, and 5 mL of ethanol to a Teflon (registered trademark) container. The Teflon (registered trademark) container was placed in an autoclave, and argon gas was introduced into the autoclave so that the argon partial pressure was 3 MPa. The reaction was carried out at 160 °C for 15 minutes to obtain a reaction solution. After the reaction, solid components were removed from the reaction solution by centrifugation, and the glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated by HPLC analysis. The glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated using the same method as in Experimental Example 2.

[0068] (Experimental Example 4-2) The reaction was carried out under the same conditions as in Experimental Example 4-1 except that the reaction temperature was set to 170°C, and HPLC analysis was carried out.

[0069] (Experimental Example 4-3) The reaction was carried out under the same conditions as in Experimental Example 4-1, except that the reaction temperature was set to 180° C., and HPLC analysis was carried out.

[0070] (Experimental Example 4-4) The reaction was carried out under the same conditions as in Experimental Example 4-1 except that the reaction temperature was set to 190°C, and HPLC analysis was carried out.

[0071] The results of HPLC analysis for Experimental Examples 4-1 to 4-4 are shown in Table 3. In Table 3, C4 refers to a C4 compound, which is a mixture of erythrose and threose, each having four carbon atoms, and their derivatives (including an erythrose derivative, which is a cyclic diol compound represented by general formula (1)); C2 refers to a C2 compound, which is a mixture of glycolaldehyde, which has two carbon atoms, and its derivative, glycolaldehyde diethyl acetal, and 1,1,2-triethoxyethane; MAN refers to mannose, and others refer to glyceraldehyde, dihydroxyacetone, ethyl glycoside, and pyruvaldehyde. As shown in Table 3, as the reaction temperature increased, the conversion rate increased, and the yields of C4 and C2 compounds also increased.

[0072] [Table 3]

[0073] Experimental Example 5: Examination of reaction time (Experimental Example 5-1) A solution was prepared by adding 22.5 mg of glucose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 12.5 mg of niobium (V) oxide, 12.5 mg of MOR-type zeolite with a silica / alumina ratio of 90, and 5 mL of ethanol to a Teflon (registered trademark) container. The Teflon (registered trademark) container was placed in an autoclave, and argon gas was introduced into the autoclave so that the argon gas partial pressure was 3 MPa. The reaction was carried out at 190 °C for 10 minutes to obtain a reaction solution. After the reaction, solid components were removed from the reaction solution by centrifugation, and the glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated by HPLC analysis. The glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated using the same method as in Experimental Example 2.

[0074] (Experimental Example 5-2) The reaction was carried out under the same conditions as in Experimental Example 5-1, except that the reaction time was changed to 15 minutes, and HPLC analysis was carried out.

[0075] (Experimental Example 5-3) The reaction was carried out under the same conditions as in Experimental Example 5-1, except that the reaction time was changed to 20 minutes, and HPLC analysis was carried out.

[0076] (Experimental Example 5-4) The reaction was carried out under the same conditions as in Experimental Example 5-1, except that the reaction time was changed to 25 minutes, and HPLC analysis was carried out.

[0077] (Experimental Example 5-5) The reaction was carried out under the same conditions as in Experimental Example 5-1, except that the reaction time was changed to 30 minutes, and HPLC analysis was carried out.

[0078] The results of HPLC analysis for Experimental Examples 5-1 to 5-5 are shown in Table 4. In Table 4, C4 refers to a C4 compound, a mixture of erythrose and threose, each having four carbon atoms, and their derivatives (including an erythrose derivative, which is a cyclic diol compound represented by general formula (1)). C2 refers to a C2 compound, a mixture of glycolaldehyde, each having two carbon atoms, and its derivative, glycolaldehyde diethyl acetal, and 1,1,2-triethoxyethane. MAN refers to mannose, and the others refer to glyceraldehyde, dihydroxyacetone, ethyl glycoside, and pyruvaldehyde. As shown in Table 4, the glucose conversion rate and the yields of C4 and C2 compounds increased with a reaction time of up to 15 minutes, and showed no significant changes thereafter. The yield of MAN increased with a reaction time of up to 10 minutes, and then decreased after 15 minutes.

[0079] [Table 4]

[0080] Experimental Example 6: Investigation of zeolite crystal structure and silica / alumina ratio (Experimental Example 6-1) A solution was prepared by adding 22.5 mg of glucose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 12.5 mg of niobium (V) oxide, 12.5 mg of MOR-type zeolite with a silica / alumina ratio of 15, and 5 mL of ethanol to a Teflon® container. The Teflon® container was placed in an autoclave, and argon gas was introduced into the autoclave so that the argon partial pressure was 3 MPa. The reaction was carried out at 190°C for 15 minutes to obtain a reaction solution. After the reaction, solid components were removed from the reaction solution by centrifugation, and the glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated by HPLC analysis. The glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated using the same method as in Experimental Example 2.

[0081] (Experimental Example 6-2) A reaction was carried out under the same conditions as in Experimental Example 6-1, except that the MOR zeolite having a silica / alumina ratio of 15 was changed to an MOR zeolite having a silica / alumina ratio of 30, and HPLC analysis was performed.

[0082] (Experimental Example 6-3) A reaction was carried out under the same conditions as in Experimental Example 6-1, except that the MOR zeolite having a silica / alumina ratio of 15 was changed to an MOR zeolite having a silica / alumina ratio of 240, and HPLC analysis was performed.

[0083] (Experimental Example 6-4) The reaction was carried out under the same conditions as in Experimental Example 6-1, except that the MOR zeolite having a silica / alumina ratio of 15 was changed to an MFI zeolite having a silica / alumina ratio of 23, and HPLC analysis was performed.

[0084] (Experimental Example 6-5) The reaction was carried out under the same conditions as in Experimental Example 6-1, except that the MOR zeolite having a silica / alumina ratio of 15 was changed to an MFI zeolite having a silica / alumina ratio of 80, and HPLC analysis was carried out.

[0085] (Experimental Example 6-6) The reaction was carried out under the same conditions as in Experimental Example 6-1, except that the MOR zeolite having a silica / alumina ratio of 15 was changed to an MFI zeolite having a silica / alumina ratio of 300, and HPLC analysis was carried out.

[0086] The results of HPLC analysis in Experimental Examples 6-1 to 6-6 are shown in Table 5. In Table 5, C4 and C2 have the same meanings as in Table 1. As shown in Table 5, when MFI zeolite was added rather than MOR zeolite, the yield of C4 compounds was higher. Furthermore, when MFI zeolite having a silica / alumina ratio of 80 was added, the yield of C4 compounds was higher.

[0087] [Table 5]

[0088] Experimental Example 7: WNbO 14 Synthesis of Solution A was prepared by adding 15 mmol of niobium(V) chloride to 30 mL of methanol containing 112.5 mmol of citric acid and 60 mmol of propylene glycol. Solution B (W / EDA solution) was prepared by adding 1.9 mmol of ammonium tungstate parapentahydrate to 10 mL of water containing 225 mmol of ethylenediamine while stirring at 200 rpm in an ice bath. Solutions A and B were mixed and heated to 80°C while stirring at 200 rpm to dissolve each component. Next, the mixture was heated to 130°C while stirring at 200 rpm to evaporate the solvent and dry the mixture. The mixture was then heated from 200°C to 460°C and further heated at 550°C for 2 hours. Finally, it was calcined at 750°C for 5 hours to obtain W3Nb2O. 14 obtained.

[0089] Experimental Example 8: Mo3Nb2O 14 Synthesis of Solution A was prepared by adding 15 mmol of niobium(V) chloride to 30 mL of methanol containing 112.5 mmol of citric acid and 60 mmol of propylene glycol. Solution B (Mo / EDA solution) was prepared by adding 22.5 mmol of MoO3 to 10 mL of water containing 225 mmol of ethylenediamine while stirring at 200 rpm in an ice bath. Solutions A and B were mixed and heated to 80°C while stirring at 200 rpm to dissolve each component. Next, the mixture was heated to 130°C while stirring at 200 rpm to evaporate the solvent and dry the mixture. The mixture was then heated from 200°C to 460°C and further heated at 550°C for 2 hours. Finally, it was calcined at 750°C for 5 hours to obtain Mo3Nb2O. 14 obtained.

[0090] Experimental Example 9: Examination of the reactivity of complex metal oxides in the absence of zeolite (Experimental Example 9-1) In a Teflon (registered trademark) container, 22.5 mg of glucose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and WNbO 14 A solution was prepared by adding 12.5 mg of glucose and 5 mL of ethanol. The Teflon container was placed in an autoclave, and argon gas was introduced into the autoclave so that the partial pressure of argon gas was 3 MPa. The reaction was carried out at 190°C for 15 minutes to obtain a reaction solution. After the reaction, the solid components were removed from the reaction solution by centrifugation, and the glucose conversion rate, the yield of each product contained in the liquid phase of the reaction solution, and the CB were calculated by HPLC analysis.

[0091] (Experimental Example 9-2) Metal oxide: Mo3Nb2O 14 The reaction was carried out under the same conditions as in Experimental Example 7-1, except that the above was added, and then HPLC analysis was carried out.

[0092] (Experimental Example 9-3) The reaction was carried out under the same conditions as in Experimental Example 7-1, except that VNbO4 was added as the metal oxide, and then HPLC analysis was carried out.

[0093] (Experimental Example 9-4) Metal oxide: MoNb2V4O 18 The reaction was carried out under the same conditions as in Experimental Example 7-1, except that the above was added, and then HPLC analysis was carried out.

[0094] (Experimental Example 9-5) Metal oxide: MoNb 14 O 44 The reaction was carried out under the same conditions as in Experimental Example 7-1, except that the above was added, and then HPLC analysis was carried out.

[0095] The results of HPLC analysis for Experimental Examples 9-1 to 9-5 are shown in Table 6. In Table 6, C4 and C2 have the same meanings as in Table 1. As shown in Table 6, W3Nb2O 14 and Mo3Nb2O 14 The yield of C4 compounds was high even without adding zeolite.

[0096] [Table 6]

Claims

1. The method comprises a step of reacting glucose or mannose in an aliphatic alcohol solvent having 1 to 10 carbon atoms in the presence of a zeolite and a metal oxide, the metal oxide comprises at least one selected from the group consisting of an oxide of a Group 2 metal element, an oxide of a Group 5 metal element, an oxide of a Group 6 metal element, and a composite metal oxide; The composite metal oxide is Mo ３ Nb ２ O １４ Or W ３ Nb ２ O １４ That is, A method for producing a cyclic diol compound represented by the following general formula (1): 【Chemistry 1】 [In the formula, R represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.]

2. The method for producing a cyclic diol compound according to claim 1 , wherein the aliphatic alcohol is ethanol or propanol.

3. The method for producing a cyclic diol compound according to claim 1 or 2, wherein the metal oxide is niobium (V) oxide.

4. The method for producing a cyclic diol compound according to claim 1 or 2, wherein the zeolite is an MFI type zeolite.

5. The zeolite is SiO ２ and Al ２ O ３ Contains Al ２ O ３ SiO relative to the amount of substance ２ The method for producing a cyclic diol compound according to claim 4, wherein the ratio of the amounts of substances is 10 to 350.

6. The method comprises a step of reacting glucose or mannose in an aliphatic alcohol solvent having 1 to 10 carbon atoms in the presence of a composite metal oxide, The composite metal oxide is Mo ３ Nb ２ O １４ Or W ３ Nb ２ O １４ and A method for producing a cyclic diol compound represented by the following general formula (1): 【Chemistry 2】 [In the formula, R represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.]

7. The method for producing a cyclic diol compound according to claim 6, wherein the aliphatic alcohol is ethanol or propanol.

8. Mo ３ Nb ２ O １４ Or W ３ Nb ２ O １４ A catalyst for decomposing sugars, comprising:

9. A cyclic diol compound represented by the following general formula (1): 【Transformation 3】 [In the formula, R represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms.]

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