A method for synthesizing alcohol compounds

Abstract

The present invention belongs to the technical field of organic synthesis and relates to a method for synthesizing alcohol compounds. In the presence of a ruthenium-based hydrogenation catalyst, a carbonyl-containing compound is hydrogenated to produce the alcohol compound. The ruthenium-based hydrogenation catalyst comprises: an active metal, a promoter metal, a ligand, and a support. The active metal is ruthenium; the promoter metal is one or more of iron, nickel, zinc, and molybdenum; the ligand is a triazole ligand; and the support is an MIL series MOF. The ruthenium-based hydrogenation catalyst can efficiently catalyze the hydrogenation of p-methoxypropiophenone to produce 1-(4-methoxyphenyl)propanol under suitable reaction conditions, overcoming the problems of low conversion rate, numerous side reactions, and high catalyst cost in the prior art, while achieving advantages such as high yield and high selectivity.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and relates to a method for synthesizing an alcohol compound, in particular to a method for synthesizing 1-(4-methoxyphenyl)propanol, an intermediate of anethole. Background Art

[0002] Anethole, also known as anethole, anethole, and p-propenylanisole, is a widely occurring aromatic compound in nature. It appears as a colorless or pale yellow liquid or crystals. Anethole is highly sought after for its distinctive aniseed aroma and is widely used in the food, cosmetic, and pharmaceutical industries. Anethole has two isomers: cis and trans. Trans-anethole is recognized as "generally recognized as safe" as a flavoring by the U.S. Food and Drug Administration (FDA) and the Flavor and Extract Manufacturers Association (FEMA). It is also permitted for use in my country under GB2760-1996. Cis-anethole has a pungent, pungent odor. When used in food and cosmetics, the cis-anethole content must not exceed 1%, and is generally limited to less than 0.2%. Trans-anethole is a major component of many essential oils and is widely used in the pharmaceutical, food, fragrance, and cosmetic industries. It is also used as a medication or health supplement to prevent and treat abdominal adhesions, abdominal distension, gastrointestinal motility disorders, and malabsorption after abdominal surgery. The chemical structure of anethole is as follows:

[0003]

[0004] Among the chemical synthesis routes of anethole, the routes with practical value each have their own advantages and disadvantages: 1. Using p-propenylphenol as the raw material, it is methylated with dimethyl sulfate under alkaline conditions, but the starting materials of this route are not easy to obtain; 2. Using p-anisaldehyde and ethyl Grignard reagent, the product is heated and dehydrated to obtain anethole. The main disadvantage of this route is that it requires the use of Grignard reaction, the reaction conditions are relatively harsh, and the reaction process is highly exothermic, difficult to control, and relatively dangerous. In addition, the raw materials are expensive and the reaction conversion rate is not high.

[0005] The most promising route is using anisole as a raw material. First, a Friedel-Craft acylation is performed to generate p-methoxypropiophenone, which is then hydrogenated and reduced to 1-(4-methoxyphenyl)propanol. High-temperature dehydration is then performed to obtain the target compound. The reaction equation is:

[0006]

[0007] This route has readily available raw materials, and the yields of the first and third steps are relatively high. The second reduction step is a key step, and this step involves reducing the carbonyl group in p-methoxyphenylpropiophenone to a hydroxyl group to prepare 1-(4-methoxyphenyl)propanol. Because the carbonyl group is located in the benzylic position and the para-position has a strong donor group, side reactions are significantly increased. Although catalysts containing ruthenium-supported ligands are capable of catalytically reducing p-methoxyphenylpropiophenone to generate 1-(4-methoxyphenyl)propanol in the prior art, the conversion rate is only 71%, and the catalysts used are very expensive. In addition, ammonium formate is used as a hydrogen source to reduce similar substrates, but this method requires a large amount of ammonium formate and produces a large amount of waste ammonia, which pollutes the environment.

[0008] Therefore, if a suitable, low-cost, and efficient catalyst for the hydrogenation of p-methoxyphenylacetone can be developed, it will have important economic value and be beneficial to the industrial production of anethole. Summary of the Invention

[0009] The present invention provides a method for synthesizing alcohol compounds. The method utilizes a specific ruthenium-based hydrogenation catalyst under suitable reaction conditions to efficiently catalyze the hydrogenation reaction of carbonyl-containing compounds, and in particular, can realize the hydrogenation of p-methoxypropiophenone to prepare 1-(4-methoxyphenyl)propanol, thereby overcoming the problems of low conversion rate, many side reactions, and high catalyst cost in the prior art. The method has the advantages of high yield and high selectivity, and a high trans-content anethole product can be further obtained by using the anethole as an intermediate.

[0010] In order to achieve the above object, the present invention provides a method for synthesizing an alcohol compound, wherein a carbonyl-containing compound is hydrogenated in the presence of a ruthenium-based hydrogenation catalyst to obtain an alcohol compound;

[0011] The reaction formula is as follows:

[0012]

[0013] In the above formula, R 1 C1~C 12 Alkyl, hydroxy substituted C1~C 12 Alkyl, C2~C 12 C2~C substituted with alkenyl or hydroxyl 12 Alkenyl, substituted or unsubstituted phenyl, wherein the substituent on the phenyl is selected from C1~C4 alkyl or C1~C4 alkoxy;

[0014] R 2 is H or C1~C4 alkyl;

[0015] The ruthenium-based hydrogenation catalyst comprises an active metal, a promoter metal, a ligand and a carrier;

[0016] The active metal is ruthenium;

[0017] The auxiliary metal is one or more of iron, nickel, zinc and molybdenum.

[0018] The ligand is a triazole ligand, and the triazole ligand is selected from one or more of substituted or unsubstituted 1,2,4-triazole, substituted or unsubstituted 1,2,3-triazole, and 1,2,3-benzotriazole. The substituents on the 1,2,4-triazole or 1,2,3-triazole are selected from one or more of C1~C4 alkyl or amino groups; further preferably, one or more of 1,2,4-triazole, 1,2,3-benzotriazole, 1-methyl-1,2,4-triazole, 1-methyl-1,2,3-triazole, 1-ethyl-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole.

[0019] The carrier is MIL series MOFs, preferably one or more of MIL-53, MIL-96, MIL-100, MIL-101, MIL-120, and MIL-125.

[0020] The present invention utilizes a specific ruthenium-based hydrogenation catalyst to catalyze the hydrogenation reaction. The catalyst comprises active ruthenium, a promoter metal, a ligand, and a support. The promoter metal element may increase the electron density on the ruthenium metal surface, thereby enhancing the binding energy between the C=O double bond and hydrogen molecules. This gradually increases the probability of C=O double bond adsorption and improves the selectivity of carbonyl selective hydrogenation. The triazole ligand is weakly basic, and the nitrogen atom on its molecule has the ability to act as a hydrogen bond acceptor, while the NH group can act as a hydrogen bond donor, interacting with the reaction substrate.

[0021] Preferably, the preparation method of the ruthenium-based hydrogenation catalyst is as follows:

[0022] (1) Add active metal salt, auxiliary metal salt and ligand to the solvent, heat and stir to carry out complexation, and obtain a mixed solution;

[0023] (2) adding a carrier to the mixed solution of step (1), heating and stirring for adsorption to obtain a suspension;

[0024] (3) The suspension obtained in step (2) is filtered, and the filter cake obtained is dried to a constant weight to obtain the ruthenium-based hydrogenation catalyst.

[0025] In step (1), the solvent is purified water, preferably capable of dispersing the added substance.

[0026] In step (1), the complexing temperature is 80-140° C., and the complexing time is 2-6 hours; the complexing temperature is preferably 100-120° C., and the complexing time is preferably 4-6 hours.

[0027] The mass ratio of the active metal salt to the auxiliary metal salt is 1:0.1-1.0, preferably 1:0.4-0.8.

[0028] The molar ratio of the metal salt to the ligand is 1:2.0-10.0, preferably 1:4.0-8.0, and the metal salt is calculated based on the total amount of the active metal salt and the auxiliary metal salt.

[0029] In step (1), the active metal salt is selected from a ruthenium-containing inorganic salt, a ruthenium-containing organic complex or a hydrate thereof, and is preferably one of RuCl3·3H2O, hexacarbonyl ruthenium chloride, tris(triphenylphosphine) ruthenium dichloride, p-cymene ruthenium dichloride dimer, (1,5-cyclooctadiene) ruthenium dichloride, hexaammine ruthenium chloride, hexaammine ruthenium chloride, and ruthenium acetylacetonate.

[0030] The auxiliary metal salt is selected from inorganic salts containing iron, nickel, zinc, molybdenum or their hydrates, and the inorganic salt includes chloride, sulfate, nitrate or ammonium salt, preferably FeCl3, NiSO4·6H2O, Zn(NO3)2·6H2O, (NH4)6Mo7O 24 One of them.

[0031] In step (2), the adsorption temperature is 30-60°C, and the adsorption time is 2-6 hours; preferably 30-40°C, and the adsorption time is 4-6 hours.

[0032] The mass ratio of the active metal (calculated as the active metal therein) to the carrier is 0.01-0.07:1.0, preferably 0.01-0.03:1.0.

[0033] When the carbonyl-containing compound also contains other carbon-carbon double bonds, the synthesis method can also achieve higher selectivity. Preferably, the R 1 C4~C 12 C4~C substituted with alkenyl or hydroxyl 12 The carbonyl group-containing compound is selected from the group consisting of alkenyl, substituted or unsubstituted phenyl, and the substituents on the phenyl group are selected from one or more methoxy groups. Furthermore, the carbonyl-containing compound is one of p-methoxypropiophenone, citral, isopentenal, cinnamaldehyde, citronellal, veratraldehyde, p-anisaldehyde, hydroxycitronellal, citronellal, benzaldehyde, and lyral.

[0034] Furthermore, the carbonyl-containing compound is p-methoxypropiophenone, and the alcohol compound is 1-(4-methoxyphenyl)propanol.

[0035] The mass ratio of the ruthenium-based hydrogenation catalyst to the p-methoxypropiophenone is 1.0% to 9.0%:1, preferably 3.0% to 7.0%:1.

[0036] The temperature of the hydrogenation reaction is 80-140°C, preferably 100-120°C.

[0037] The hydrogenation reaction time is 1 to 5 hours.

[0038] The hydrogen pressure of the hydrogenation reaction is 1.0-5.0 MPa, preferably 2.0-4.0 MPa.

[0039] The hydrogenation reaction may be carried out in the presence of a solvent or in the absence of a solvent. If a solvent is used, one or more of methanol, ethanol, isopropanol, and water may be used.

[0040] The reactors suitable for carrying out the isomerization reaction of the present invention are, in principle, all common containers that allow reaction under the aforementioned conditions, especially pressure and temperature, and are suitable for isomerization reaction, such as autoclaves, fixed beds, tubular reactors, loop reactors, etc., without particular limitation.

[0041] The process of the present invention can be operated batchwise, semi-continuously or continuously and is particularly suitable for industrial-scale production.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] (1) The synthesis method provided by the present invention has high reaction activity and selectivity. The catalyst structure used is stable and the active ingredients are not easily lost. The catalyst can be recycled without frequent catalyst replacement. The operation is simple, which is conducive to continuous industrial production and significantly improves equipment utilization.

[0044] (2) The ruthenium-based catalyst provided by the present invention can be used to catalyze the hydrogenation of p-methoxyphenylpropiophenone under mild reaction conditions to obtain 1-(4-methoxyphenyl)propanol, which can be used as an intermediate to obtain a high-trans content anethole product.

[0045] (3) The ruthenium-based hydrogenation catalyst provided by the present invention is applicable to a wide range of substrates and can also be used in the selective hydrogenation reaction of other carbonyl compounds containing double bonds. It is applicable to a wide range of substrates. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is an electron microscope photograph of catalyst 1 magnified 5000 times.

[0047] Figure 2 This is the gas chromatogram of the product obtained in Application Example 1.

[0048] Figure 3 This is the mass spectrum of the product obtained in Application Example 1. DETAILED DESCRIPTION

[0049] Unless otherwise specified, the technical terms used in the following examples have the same meanings as those commonly understood by those skilled in the art to which this invention belongs. The experimental reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods described, unless otherwise specified, are all conventional methods.

[0050] Catalyst Preparation Example 1

[0051] Add RuCl3·3H2O (0.5173 g, 1.978 mmol) and FeCl3 (0.4138 g, 2.551 mmol) to 30 mL of purified water and stir until completely dissolved. Then add 1,2,4-triazole (1.877 g, 27.18 mmol). Heat to 100°C, stir for 4 hours, then cool to 40°C, add MIL-101(Fe) (10 g), stir for 4 hours, then cool to room temperature, filter, and dry the filter cake to constant weight to obtain catalyst No. 1. Its electron microscope photo is shown in Figure 1 , electron microscope model: JEOL JSM-6701F.

[0052] Catalyst Preparation Examples 2 to 8

[0053] Catalyst Preparation Examples 2 to 8 provide a preparation method for a hydrogenation catalyst, respectively. The only difference from Example 1 is that the RuCl3·3H2O metal salt in Example 1 is replaced with hexacarbonylruthenium chloride (1.0129 g, 1.978 mmol), tris(triphenylphosphine)ruthenium dichloride (1.8968 g, 1.978 mmol), p-cymene dichlororuthenium dimer (1.2115 g, 1.978 mmol), (1,5-cyclooctadiene)dichlororuthenium (II) (0.5542 g, 1.978 mmol), hexaammineruthenium (II) chloride (0.5404 g, 1.978 mmol), hexaammineruthenium (III) chloride (0.6125 g, 1.978 mmol), and ruthenium acetylacetonate (0.7881 g, 1.978 mmol), respectively, and the types and amounts of the ligand, support, and auxiliary metal are kept unchanged.

[0054] Catalyst Preparation Examples 9-12

[0055] Examples 9 to 12 provide a method for preparing a hydrogenation catalyst, respectively. The difference from Example 1 is that the mass ratios of ruthenium metal element (active metal atom) to carrier are 0.01:1, 0.03:1, 0.05:1, and 0.07:1, respectively, and the amounts of the auxiliary metal salt FeCl3 and the ligand 1,2,4-triazole added are adjusted, as shown in Table 1.

[0056] Table 1

[0057]

[0058] Catalyst Preparation Examples 13-15

[0059] Examples 13 to 15 provide a method for preparing a hydrogenation catalyst, respectively. The difference from Example 1 is that the mass ratios of the ruthenium metal salt RuCl3·3H2O and the auxiliary metal salt FeCl3 are 1:0.1, 1:0.4, and 1:1.0, respectively, and the amounts of the auxiliary metal salt FeCl3 and the ligand 1,2,4-triazole added are adjusted as shown in Table 2.

[0060] Table 2

[0061]

[0062] Catalyst Preparation Examples 16-18

[0063] Examples 16 to 18 provide a method for preparing a hydrogenation catalyst, which differs from Example 1 in that the auxiliary metal salt FeCl3 in Example 1 is replaced by NiSO4·6H2O, Zn(NO3)2·6H2O, (NH4)6Mo7O, etc. 24 4H2O, and keep the types and amounts of ruthenium metal salt and carrier unchanged, while adjusting the types of auxiliary metal salt and the amount of ligand 1,2,4-triazole, as shown in Table 3.

[0064] Table 3

[0065]

[0066] Catalyst Preparation Examples 19-23

[0067] Examples 19 to 23 provide a preparation method of a hydrogenation catalyst, respectively. The only difference compared to Example 1 is that the ligand 1,2,4-triazole in Example 1 is replaced with 1,2,3-benzotriazole (3.237 g; 27.18 mmol), 1-methyl-1,2,4-triazole (2.258 g; 27.18 mmol), 1-methyl-1,2,3-triazole (2.258 g; 27.18 mmol), 1-ethyl-1,2,4-triazole (2.639 g; 27.18 mmol), and 3,5-diamino-1,2,4-triazole (2.693 g; 27.18 mmol), and the types and amounts of ruthenium metal salt, auxiliary metal, and carrier are kept unchanged.

[0068] Catalyst Preparation Examples 24-27

[0069] Examples 24 to 27 provide a method for preparing a hydrogenation catalyst, respectively. The only difference from Example 1 is that the molar ratios of the metal salt to the ligand 1,2,4-triazole in Example 1 are 1:2, 1:4, 1:8, and 1:10, respectively. By adjusting the amount of ligand 1,2,4-triazole added, the types and amounts of ruthenium metal salt, auxiliary metal salt, and carrier are kept unchanged, as shown in Table 4.

[0070] Table 4

[0071]

[0072] a The metal salt is calculated based on the total amount of the ruthenium metal salt and the auxiliary metal salt.

[0073] Catalyst Preparation Examples 28-32

[0074] Examples 28 to 32 respectively provide a method for preparing a hydrogenation catalyst. The only difference compared with Example 1 is that the carrier MIL-101 (Fe) in Example 1 is replaced with MIL-53 (Al), MIL-96 (Al), MIL-100 (Fe), MIL-120 (Al), and MIL-125 (Ti), and the types and amounts of ruthenium metal salts, auxiliary metals, and ligands remain unchanged.

[0075] Catalyst Preparation Examples 33-41

[0076] Examples 33 to 41 provide a method for preparing a hydrogenation catalyst, respectively. The only difference from Example 1 is that the temperature and time for complexing the metal salt with the ligand, and the temperature and time for adsorption and stirring of the carrier are adjusted, as shown in Table 5.

[0077] Table 5

[0078]

[0079] Comparative Example 1

[0080] RuCl3·3H2O (0.5173 g, 1.978 mmol) was added to 30 mL of purified water and stirred until completely dissolved. Then, 1,2,4-triazole (0.820 g, 11.87 mmol) was added. The temperature was raised to 100°C and heated with stirring for 4 hours. The temperature was then lowered to 40°C. MIL-101 (10 g) was added. After stirring at this temperature for 4 hours, the temperature was lowered to room temperature and filtered. The filter cake was dried to constant weight to obtain the catalyst of Comparative Example 1.

[0081] Comparative Example 2

[0082] RuCl3·3H2O (0.5173 g, 1.978 mmol) and FeCl3 (0.4138 g, 2.551 mmol) were added to 30 mL of purified water and stirred until completely dissolved. The temperature was then raised to 40°C, and MIL-101 (10 g) was added. After stirring for 4 hours, the temperature was cooled to room temperature and filtered. The filter cake was dried to constant weight to obtain the catalyst of Comparative Example 2.

[0083] Application Examples

[0084] Application Example 1

[0085] In a 500 mL stainless steel autoclave, add 5.0 g (catalyst concentration is 5.0 wt.%) of catalyst No. 1, 100 g of p-methoxypropiophenone, and 100 g of water. Heat to 40°C and dissolve the p-methoxypropiophenone solid under stirring. Replace the atmosphere with nitrogen three times and then introduce hydrogen. Slowly raise the temperature to control the temperature at 100°C and the hydrogen pressure at 3.0 MPa. After 3 h of hydrogenation, the reaction stops when no hydrogen is absorbed.

[0086] The mixture was cooled to room temperature, filtered to recover the catalyst, and the reaction solution was detected by gas chromatography. The conversion was 99.10% and the selectivity was 99.30%. The filtrate was allowed to stand and stratify to obtain an oil phase, which was then distilled under reduced pressure to obtain 99.36 g of 1-(4-methoxyphenyl)propanol (GC content: 99.44%) with a yield of 98.15%. The gas chromatogram and mass spectrum of the product are shown in Figure 2. Figure 2 and Figure 3 .

[0087] Among them, the catalyst recovered in Application Example 1 was washed with deionized water 2 to 3 times to obtain a recovered catalyst, and the catalyst was reused. The first use of the recovered catalyst was regarded as one reuse, the second use of the recovered catalyst was regarded as two reuses, and so on. The conversion rate of p-methoxyphenylpropiophenone and the selectivity of 1-(4-methoxyphenyl)propanol were calculated, and the results are shown in Table 6.

[0088] Gas phase instrument model: Fuli GC 9790 plus

[0089] Chromatographic column model: HP-5 (30m×0.32mm×0.25μm); detector temperature: 260℃; injector temperature: 260℃; column temperature: 100℃ for 10 min, then increase to 220℃ at 40℃ / min and hold for 13 min.

[0090] Table 6

[0091]

[0092] Application Examples 2~4

[0093] The only difference between Application Examples 2 to 4 and Application Example 1 is that the solvents were changed to ethanol, isopropanol, and methanol, respectively, and the solvents were recovered under normal pressure and distilled under reduced pressure to obtain 1-(4-methoxyphenyl)propanol. All other differences were the same as in Application Example 1. The results are shown in Table 7.

[0094] Application Examples 5-6

[0095] The difference between Application Examples 5 and 6 and Application Example 1 is that the amount of solvent used is changed to 200 g and 300 g respectively, and the rest is the same as Application Example 1. The results are shown in Table 7.

[0096] Application Examples 7-10

[0097] The only difference between Application Examples 7 to 10 and Application Example 1 is that the amount of Catalyst 1 is changed to 1.0%, 3.0%, 7.0%, and 9.0%, respectively, and the corresponding catalyst amounts are 1.0 g, 3.0 g, 7.0 g, and 9.0 g, respectively. Other factors are the same as those in Application Example 1. The results are shown in Table 7.

[0098] Application Examples 11-21

[0099] Application Examples 11 to 21 differed from Application Example 1 only in the hydrogen pressure, reaction temperature, and reaction time; otherwise, the conditions were the same as in Application Example 1. The hydrogen pressures in Application Examples 11, 12, 13, and 14 were 1.0 MPa, 2.0 MPa, 4.0 MPa, and 5.0 MPa, respectively; otherwise, the conditions were the same as in Application Example 1. The temperatures in Application Examples 15, 16, and 17 were 80°C, 120°C, and 140°C, respectively; otherwise, the conditions were the same as in Application Example 1. The reaction times in Application Examples 18, 19, 20, and 21 were 1 hour, 2 hours, 4 hours, and 5 hours, respectively; otherwise, the conditions were the same as in Application Example 1. The results are shown in Table 7.

[0100] Application Examples 22~61

[0101] Application Examples 22 to 61 provide applications of a hydrogenation catalyst, respectively. The hydrogenation catalysts are sequentially the hydrogenation catalysts provided in Catalyst Examples 2 to 41 above, and are used to prepare 1-(4-methoxyphenyl)propanol from p-methoxypropiophenone. The preparation method comprises:

[0102] In a 500 mL stainless steel autoclave, add catalyst (5.0 g, catalyst concentration 5.0%), p-methoxypropiophenone (100 g, 0.609 mol), and 100 g of water. Heat to 40°C and dissolve the p-methoxypropiophenone solid under stirring. Replace with nitrogen three times and then introduce hydrogen. Slowly raise the temperature and control the temperature at 100°C. The hydrogen pressure is controlled at 3.0 MPa. After 3 h of hydrogenation, the reaction stops absorbing hydrogen and the hydrogenation reaction is stopped.

[0103] The temperature was lowered to room temperature, the catalyst was recovered by filtration, the reaction solution was detected by gas chromatography, the filtrate was allowed to stand and separate to obtain an oil phase, and 1-(4-methoxyphenyl)propanol was obtained by distillation under reduced pressure. The results are shown in Table 7.

[0104] Application Comparative Examples 1~2

[0105] Comparative Examples 1 and 2 of this application each provide an application of a hydrogenation catalyst. The only difference from Application Example 1 is that the hydrogenation catalysts provided in Comparative Examples 1 and 2 are used, respectively. After the reaction, the reaction liquid was analyzed using a gas chromatograph to calculate the conversion of p-methoxypropiophenone and the selectivity for 1-(4-methoxyphenyl)propanol. The results are shown in Table 7.

[0106] Application Examples 62~71

[0107] To promote the application of the catalyst of the present invention in complex hydrogenation reactions, Application Examples 62-71 differ from Application Example 1 only in the type of reaction substrates: p-methoxypropiophenone was replaced with citral (100 g, 0.657 mol), isopentenal (100 g, 1.189 mol), cinnamaldehyde (100 g, 0.757 mol), citronellal (100 g, 0.648 mol), veratraldehyde (100 g, 0.602 mol), p-methoxybenzaldehyde (100 g, 0.734 mol), hydroxycitronellal (100 g, 0.581 mol), citronellal (100 g, 0.520 mol), benzaldehyde (100 g, 0.942 mol), and lyral (100 g, 0.475 mol), with the remaining reactions being the same as in Application Example 1. The results are shown in Table 8.

[0108] Table 7

[0109]

[0110]

[0111] Table 8

[0112]

[0113] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for synthesizing an alcohol compound, characterized in that: In the presence of a ruthenium-based hydrogenation catalyst, a carbonyl-containing compound undergoes hydrogenation to obtain an alcohol compound; The ruthenium-based hydrogenation catalyst comprises: an active metal, a promoter metal, a ligand and a carrier; The active metal is ruthenium; The auxiliary metal is one or more of iron, nickel, zinc and molybdenum; The carrier is MOFs of the MIL series; The ligand is one or more of 1,2,4-triazole, 1,2,3-benzotriazole, 1-methyl-1,2,4-triazole, 1-methyl-1,2,3-triazole, 1-ethyl-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole; The carbonyl-containing compound is p-methoxypropiophenone, and the alcohol compound is 1-(4-methoxyphenyl)propanol.

2. The method for synthesizing an alcohol compound according to claim 1, wherein The carrier is one or more of MIL-53, MIL-96, MIL-100, MIL-101, MIL-120, and MIL-125.

3. The method for synthesizing an alcohol compound according to claim 1, wherein The preparation method of the ruthenium-based hydrogenation catalyst is as follows: (1) Add active metal salt, auxiliary metal salt and ligand to the solvent, heat and stir to carry out complexation, and obtain a mixed solution; (2) adding a carrier to the mixed solution of step (1), heating and stirring for adsorption to obtain a suspension; (3) The suspension obtained in step (2) is filtered, and the filter cake obtained is dried to a constant weight to obtain the ruthenium-based hydrogenation catalyst.

4. The method for synthesizing an alcohol compound according to claim 3, wherein In step (1), the solvent is purified water; In step (1), the complexation temperature is 80-140° C., and the complexation time is 2-6 hours; The active metal salt is selected from a ruthenium-containing inorganic salt, a ruthenium-containing organic complex or a hydrate thereof; The auxiliary metal salt is selected from inorganic salts containing iron, nickel, zinc, molybdenum or their hydrates; The mass ratio of the active metal salt to the auxiliary metal salt is 1:0.1~1.0; The molar ratio of the metal salt to the ligand is 1:2.0-10.0, and the metal salt is calculated based on the total amount of the active metal salt and the auxiliary metal salt.

5. The method for synthesizing an alcohol compound according to claim 3, wherein In step (2), the adsorption temperature is 30-60°C, and the adsorption time is 2-6 hours; The mass ratio of the active metal salt to the carrier is 0.01-0.07:1.0, and the active metal salt is calculated based on the active metal therein.

6. The method for synthesizing an alcohol compound according to any one of claims 1 to 5, wherein: The mass ratio of the ruthenium-based hydrogenation catalyst to the carbonyl-containing compound is 1.0% to 9.0%:1; The temperature of the hydrogenation reaction is 80-140° C., and the time of the hydrogenation reaction is 1-5 hours; The hydrogen pressure of the hydrogenation reaction is 1.0~5.0MPa.

7. The method for synthesizing an alcohol compound according to any one of claims 1 to 5, wherein: The hydrogenation reaction is carried out in the presence of a solvent or without a solvent; The solvent is selected from one or more of methanol, ethanol, isopropanol and water.

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