Synthesis method of alcohol compound

Abstract

The invention belongs to the technical field of organic synthesis, and relates to a synthesis method of an alcohol compound, which comprises the following steps: in the presence of a ruthenium-based hydrogenation catalyst, carrying out hydrogenation reaction on a carbonyl-containing compound to obtain the alcohol compound, the ruthenium-based hydrogenation catalyst comprises an active metal, an auxiliary 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 ligand is a triazole ligand; the carrier is MOFs (Metal Organic Frameworks) of MIL series. The ruthenium-based hydrogenation catalyst can be used for efficiently catalyzing p-methoxypropiophenone hydrogenation to prepare 1-(4-methoxyphenyl) propanol under proper reaction conditions, so that the problems of low conversion rate, more side reactions, high catalyst cost and the like in the prior art are solved, and the ruthenium-based hydrogenation catalyst has the advantages of high yield, high selectivity and the like.

Description

Technical Field

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

[0002] Anethole, also known as anisole, anethole, p-propenylanisole, etc., is an aromatic compound widely present in nature. It appears as a colorless or light yellow liquid or crystal. Anethole is favored by people because of its unique anise smell and is widely used in the food, daily chemical, pharmaceutical and other industries. Anethole has two isomers, cis-anethole and trans-anethole. Trans-anethole is recognized as "generally regarded as safe" by the US Food and Drug Administration (FDA) and the Flavor and Extract Manufacturers Association of the United States (FEMA) as a flavoring agent. China's GB2760-1996 also stipulates that it is an edible flavor allowed to be used. Cis-anethole has a pungent and irritating smell. When applied in the fields of food, cosmetics, etc., the content of cis-anethole cannot be greater than 1%, and generally less than 0.2% is required. Trans-anethole is one of the main components of many essential oils. It is widely used in the pharmaceutical, food, spice, and cosmetics industries; trans-anethole can also be used as a drug or health product for preventing and treating intraperitoneal adhesions, abdominal distension, gastrointestinal motility disorders, and malabsorption after abdominal surgery. The chemical structural formula of anethole is as follows:

[0003] In the chemical synthesis routes of anethole, each practical route has its own advantages and disadvantages: Using p-propenylphenol as the raw material, under alkaline conditions, methylated with dimethyl sulfate, but the starting material of this route is not easily obtained; Reacting p-methoxybenzaldehyde with ethyl Grignard reagent, and heating the product to dehydrate to obtain anethole. The main disadvantages of this route are that it requires a Grignard reaction, the reaction conditions are relatively harsh, and the heat release during the reaction is relatively intense, making it difficult to control, with relatively high danger, and the raw materials are relatively expensive, and the reaction conversion rate is not high.

[0004] The route using anisole as the raw material is the most promising. First, through Friedel-Craft acylation to generate p-methoxypropiophenone, hydrogenation reduction to generate 1-(4-methoxyphenyl)propanol, and high-temperature dehydration to obtain the target compound. The reaction equation is:

[0005] The raw materials of this route are easily accessible, and the yields of the first and third steps are relatively high. The second reduction step is the key step. When preparing 1-(4-methoxyphenyl)propanol by reducing the carbonyl group in p-methoxypropiophenone to a hydroxyl group, due to the carbonyl group being in the benzyl position and having a strong electron-donating group at the para position, a large number of side reactions are caused. Although the ruthenium-supported ligand catalyst in the prior art can catalyze the reduction of p-methoxypropiophenone to produce 1-(4-methoxyphenyl)propanol, the conversion rate is only 71%, and the catalyst used is very expensive. In addition, ammonium formate is used as a hydrogen source to reduce this similar substrate, but the disadvantage is that a large amount of ammonium formate is required for the reaction, and a large amount of waste ammonia gas is generated, causing environmental pollution.

[0006] Therefore, if a suitable, inexpensive and highly efficient hydrogenation catalyst for p-methoxypropiophenone can be developed, it has important economic value and is beneficial to the industrial large-scale production of anethole. Summary of the Invention

[0007] The present invention provides a method for synthesizing an alcohol compound. Under suitable reaction conditions, this synthesis method can efficiently catalyze the hydrogenation reaction of a carbonyl-containing compound by using a specific ruthenium-based hydrogenation catalyst. In particular, it can achieve the hydrogenation of p-methoxypropiophenone to prepare 1-(4-methoxyphenyl)propanol, so as to overcome the problems existing in the prior art such as low conversion rate, many side reactions, and high catalyst cost. It has advantages such as high yield and high selectivity. Using it as an intermediate, an anethole product with a high trans content can be further obtained.

[0008] To achieve the above object, the present invention provides a method for synthesizing an alcohol compound. In the presence of a ruthenium-based hydrogenation catalyst, a carbonyl-containing compound undergoes a hydrogenation reaction to obtain an alcohol compound; The reaction formula is as follows:

[0009] In the above formula, R 1 is a C1-C 12 alkyl group, a C1-C 12 alkyl group substituted by a hydroxyl group, a C2-C 12 alkenyl group, a C2-C 12 alkenyl group substituted by a hydroxyl group, a substituted or unsubstituted phenyl group, and the substituents on the phenyl group are selected from C1-C4 alkyl groups or C1-C4 alkoxy groups; R 2 is H or a C1-C4 alkyl group; The ruthenium-based hydrogenation catalyst includes an active metal, a promoter metal, a ligand, and a carrier; The active metal is ruthenium; The promoter metal is one or more of iron, nickel, zinc, and molybdenum.

[0010] 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 groups or amino groups; further preferably, it 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.

[0011] The carrier is an MIL series of MOFs, preferably one or more of MIL-53, MIL-96, MIL-100, MIL-101, MIL-120, and MIL-125.

[0012] The present invention uses a specific ruthenium-based hydrogenation catalyst to catalyze the hydrogenation reaction. This catalyst includes active metal ruthenium, promoter metal, ligand, and carrier. Among them, the promoter metal element may increase the electron density on the surface of ruthenium metal, thereby enhancing the binding energy between the C=O double bond and the hydrogen molecule, making the adsorption probability of the C=O double bond gradually increase, and improving the selectivity of carbonyl selective hydrogenation. Triazole ligands have weak basicity, and the N atoms on their molecules have the ability to be hydrogen bond acceptors, while the NH group can act as a hydrogen bond donor and interact with the reaction substrate.

[0013] Preferably, the preparation method of the ruthenium-based hydrogenation catalyst is as follows: (1) Add active metal salt, promoter metal salt, and ligand into a solvent, heat and stir for complexation to obtain a mixed solution; (2) Add a carrier to the mixed solution in step (1), heat and stir for adsorption to obtain a suspension; (3) Filter the suspension in step (2), and dry the obtained filter cake to a constant weight to obtain the ruthenium-based hydrogenation catalyst.

[0014] In step (1), the solvent is purified water, which is suitable for dispersing the added substances.

[0015] In step (1), the temperature of the complexation is 80-140°C, and the time of the complexation is 2-6 hours; the temperature of the complexation is preferably 100-120°C, and the time of the complexation is preferably 4-6 hours.

[0016] The mass ratio of the active metal salt to the promoter metal salt is 1:0.1-1.0, preferably 1:0.4-0.8.

[0017] The molar ratio of the metal salt to the ligand is 1:2.0 to 10.0, preferably 1:4.0 to 8.0, and the metal salt is calculated based on the total amount of the active metal salt and the promoter metal salt.

[0018] In step (1), the active metal salt is selected from ruthenium-containing inorganic salts, ruthenium-containing organic complexes or their hydrates, and 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, ruthenium acetylacetonate.

[0019] The promoter metal salt is selected from inorganic salts containing iron, nickel, zinc, or molybdenum or their hydrates, and the inorganic salts include chlorides, sulfates, nitrates, or ammonium salts, and preferably one of FeCl3, NiSO4·6H2O, Zn(NO3)2·6H2O, (NH4)6Mo7O 24 One of them.

[0020] In step (2), the adsorption temperature is 30 to 60 °C, and the adsorption time is 2 to 6 hours; preferably 30 to 40 °C, and the time is 4 to 6 hours.

[0021] The mass ratio of the active metal (calculated based on the active metal therein) to the carrier is 0.01 to 0.07:1.0, preferably 0.01 to 0.03:1.0.

[0022] When the carbonyl compound contains other carbon-carbon double bonds, the synthesis method can also achieve high selectivity. Preferably, the R 1 is C4~C 12 alkenyl, hydroxy-substituted C4~C 12 alkenyl, substituted or unsubstituted phenyl, and the substituents on the phenyl are selected from one or more methoxy groups. Further, the carbonyl compound is one of p-methoxypropiophenone, citral, isopentenal, cinnamaldehyde, citronellal, veratraldehyde, p-methoxybenzaldehyde, hydroxycitronellal, citronellol, benzaldehyde, and helional.

[0023] Further, the carbonyl compound is p-methoxypropiophenone, and the alcohol compound is 1-(4-methoxyphenyl)propanol.

[0024] 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.

[0025] The temperature of the hydrogenation reaction is 80 to 140 °C, preferably 100 to 120 °C.

[0026] The time of the hydrogenation reaction is 1 to 5 hours.

[0027] The hydrogen pressure for the hydrogenation reaction is 1.0 - 5.0 MPa, preferably 2.0 - 4.0 MPa.

[0028] The hydrogenation reaction can be carried out with a solvent or without a solvent. If a solvent is used, one or more of methanol, ethanol, isopropanol, and water are selected.

[0029] In principle, the reactor suitable for carrying out the isomerization reaction of the present invention is all common containers that allow reaction under the said conditions, especially pressure and temperature, and are suitable for the isomerization reaction, such as autoclaves, fixed beds, tubular reactors, loop reactors, etc., and there is no special limitation on this.

[0030] The method of the present invention can be operated batchwise, semi - continuously or continuously, and is especially suitable for industrial - scale production.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The synthesis method provided by the present invention has high reaction activity and selectivity. The catalyst adopted has a stable structure, and the active components are not easily lost. The catalyst can be recycled, and there is no need to frequently replace the catalyst. The operation is simple, which is beneficial to continuous industrial production and significantly improves the equipment utilization rate.

[0032] (2) Using the ruthenium - based catalyst provided by the present invention, p - methoxypropiophenone can be catalytically hydrogenated to 1 - (4 - methoxyphenyl)propanol under mild reaction conditions, and an anethole product with a high trans content can be obtained using it as an intermediate.

[0033] (3) The ruthenium - based hydrogenation catalyst provided by the present invention has a wide range of applicable substrates and can also be applied to the selective hydrogenation reaction of other carbonyl compounds containing double bonds, with a wide range of applicable substrates. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is an electron micrograph of Catalyst 1 magnified 5000 times.

[0035] Figure 2 It is a gas chromatogram of the product obtained in Application Example 1.

[0036] Figure 3 It is a mass spectrum of the product obtained in Application Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] Unless otherwise specified, the technical terms used in the following examples have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the experimental methods are all conventional methods unless otherwise specified.

[0038] Catalyst Preparation Example 1 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. Then, 1,2,4-triazole (1.877 g, 27.18 mmol) was added. The temperature was raised to 100 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and MIL-101(Fe) (10 g) was added. After stirring at a constant temperature for 4 hours, the mixture was cooled to room temperature, filtered, and the obtained filter cake was dried to a constant weight to obtain Catalyst No. 1. The electron microscope photograph is shown in Figure 1 , and the electron microscope model: JEOL JSM-6701F.

[0039] Preparation Examples 2 - 8 of the Catalyst Preparation Examples 2 - 8 of the present catalyst respectively provide a preparation method of a hydrogenation catalyst. The difference compared with Example 1 is only that the RuCl3·3H2O metal salt in Example 1 is successively replaced with hexacarbonyl ruthenium chloride (1.0129 g, 1.978 mmol), tris(triphenylphosphine)ruthenium(II) dichloride (1.8968 g, 1.978 mmol), p-cymene ruthenium dichloride dimer (1.2115 g, 1.978 mmol), (1,5-cyclooctadiene)ruthenium(II) dichloride (0.5542 g, 1.978 mmol), hexammine ruthenium(II) chloride (0.5404 g, 1.978 mmol), hexammine ruthenium(III) chloride (0.6125 g, 1.978 mmol), and ruthenium acetylacetonate (0.7881 g, 1.978 mmol), while keeping the types and amounts of the ligand, carrier, and promoter metal unchanged.

[0040] Preparation Examples 9 - 12 of the Catalyst Preparation Examples 9 - 12 of the present invention respectively provide a preparation method of a hydrogenation catalyst. The difference compared with Example 1 is that the mass ratio of ruthenium metal element (active metal atom) to the carrier is successively 0.01:1, 0.03:1, 0.05:1, and 0.07:1. At the same time, the addition amounts of the promoter metal salt FeCl3 and the ligand 1,2,4-triazole are adjusted, as shown in Table 1 specifically.

[0041] Table 1

[0042] Preparation Examples 13 - 15 of the Catalyst Examples 13 to 15 respectively provide a method for preparing a hydrogenation catalyst, which is different from Example 1 in that the mass ratios of ruthenium metal salt RuCl3·3H2O to promoter metal salt FeCl3 are 1:0.1, 1:0.4, and 1:1.0 respectively. At the same time, the addition amounts of promoter metal salt FeCl3 and ligand 1,2,4-triazole are adjusted, as shown in Table 2.

[0043] Table 2

[0044] Examples 16 to 18 for catalyst preparation Examples 16 to 18 respectively provide a method for preparing a hydrogenation catalyst, which is different from Example 1 in that the promoter metal salt FeCl3 in Example 1 is respectively replaced by NiSO4·6H2O, Zn(NO3)2·6H2O, (NH4)6Mo7O 24 ·4H2O, and the types and amounts of ruthenium metal salt and carrier are kept unchanged. At the same time, the type of promoter metal salt and the addition amount of ligand 1,2,4-triazole are adjusted, as shown in Table 3.

[0045] Table 3

[0046] Examples 19 to 23 for catalyst preparation Examples 19 to 23 respectively provide a method for preparing a hydrogenation catalyst, which is different from Example 1 only in that the ligand 1,2,4-triazole in Example 1 is replaced by 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), 3,5-diamino-1,2,4-triazole (2.693 g; 27.18 mmol), and the types and amounts of ruthenium metal salt, promoter metal, and carrier are kept unchanged.

[0047] Examples 24 to 27 for catalyst preparation Examples 24 to 27 respectively provide a method for preparing a hydrogenation catalyst, which is different from Example 1 only in that the molar ratios of metal salt to ligand 1,2,4-triazole in Example 1 are 1:2, 1:4, 1:8, and 1:10 respectively. By adjusting the addition amount of ligand 1,2,4-triazole, the types and amounts of ruthenium metal salt, promoter metal salt, and carrier are kept unchanged, as shown in Table 4.

[0048] Table 4

[0049] a The metal salt is calculated based on the total amount of ruthenium metal salt and promoter metal salt.

[0050] Examples 28 - 32 of catalyst preparation Examples 28 - 32 respectively provide a preparation method of a hydrogenation catalyst. The difference compared with Example 1 is only that the support MIL-101(Fe) in Example 1 is replaced by MIL-53(Al), MIL-96(Al), MIL-100(Fe), MIL-120(Al), MIL-125(Ti), and the types and dosages of ruthenium metal salt, promoter metal, and ligand remain unchanged.

[0051] Examples 33 - 41 of catalyst preparation Examples 33 - 41 respectively provide a preparation method of a hydrogenation catalyst. The difference compared with Example 1 is only that the temperature and time for the complexation of metal salt and ligand are adjusted, and the temperature and time for the support to adsorb and stir are adjusted, as shown in Table 5.

[0052] Table 5

[0053] Comparative Example 1 After adding RuCl3·3H2O (0.5173 g, 1.978 mmol) to 30 mL of purified water and stirring until completely dissolved, 1,2,4-triazole (0.820 g, 11.87 mmol) was added. The temperature was raised to 100 °C, and after heating and stirring for 4 hours, the temperature was lowered to 40 °C. Then MIL-101 (10 g) was added, and after keeping the temperature and stirring for 4 hours, it was cooled to room temperature, filtered, and the obtained filter cake was dried to constant weight to obtain the catalyst of Comparative Example 1.

[0054] Comparative Example 2 After adding RuCl3·3H2O (0.5173 g, 1.978 mmol) and FeCl3 (0.4138 g, 2.551 mmol) to 30 mL of purified water and stirring until completely dissolved, the temperature was raised to 40 °C, then MIL-101 (10 g) was added, and after keeping the temperature and stirring for 4 hours, it was cooled to room temperature, filtered, and the obtained filter cake was dried to constant weight to obtain the catalyst of Comparative Example 2.

[0055] Application Example Application Example 1 In a 500 mL stainless steel autoclave, 5.0 g of Catalyst No. 1 (catalyst concentration: 5.0 wt.%) was added, along with 100 g of p-methoxypropiophenone and 100 g of water. The mixture was heated to 40 °C, and the p-methoxypropiophenone solid was dissolved under stirring. After purging with nitrogen three times, hydrogen was introduced. The temperature was slowly raised, and the temperature was controlled at 100 °C, and the hydrogen pressure was controlled at 3.0 MPa. After the hydrogenation reaction for 3 h, hydrogen absorption ceased, and the hydrogenation reaction was stopped.

[0056] The temperature was lowered to room temperature, and the catalyst was recovered by filtration. The reaction solution was detected by gas chromatography. The conversion rate was 99.10%, and the selectivity was 99.30%. The filtrate was allowed to stand and layer to obtain the oil phase. 99.36 g of 1-(4-methoxyphenyl)propanol (GC content: 99.44%) was obtained by vacuum distillation, and the yield was 98.15%. The gas chromatogram and mass spectrum of the product are shown in Figure 2 and Figure 3 .

[0057] Among them, the catalyst recovered in Application Example 1 was washed 2 - 3 times with deionized water to obtain the recovered catalyst. The recovered catalyst was used for recycling. The first use of the recovered catalyst was counted as 1 cycle of recycling, the second use was counted as 2 cycles of recycling, and so on. The conversion rate of p-methoxypropiophenone and the selectivity of 1-(4-methoxyphenyl)propanol were calculated. The results are shown in Table 6.

[0058] Gas chromatograph model: Fuli GC 9790 plus Chromatographic column model: HP-5 (30 m × 0.32 mm × 0.25 μm); detector temperature: 260 °C; injector temperature: 260 °C; column temperature: held at 100 °C for 10 min, then raised to 220 °C at a rate of 40 °C / min and held for 13 min.

[0059] Table 6

[0060] Application Examples 2 - 4 The differences between Application Examples 2 - 4 and Application Example 1 were only in that the types of solvents were changed to ethanol, isopropanol, and methanol in sequence, the solvents were recovered at atmospheric pressure, and 1-(4-methoxyphenyl)propanol was obtained by vacuum distillation. The other conditions were the same as those in Application Example 1. The results are shown in Table 7.

[0061] Application Examples 5 - 6 The differences between Application Examples 5 - 6 and Application Example 1 were only in that the amounts of solvents were changed to 200 g and 300 g in sequence, and the other conditions were the same as those in Application Example 1. The results are shown in Table 7.

[0062] Application Examples 7 - 10 The differences between Application Examples 7 to 10 and Application Example 1 are only that the dosages of Catalyst 1 are changed to 1.0%, 3.0%, 7.0%, and 9.0% in sequence, and the corresponding catalyst dosages are 1.0 g, 3.0 g, 7.0 g, and 9.0 g in sequence, and the others are the same as Application Example 1. The results are shown in Table 7.

[0063] Application Examples 11 to 21 The differences between Application Examples 11 to 21 and Application Example 1 are only that the hydrogen pressure, reaction temperature, and reaction time are changed, and the others are the same as Application Example 1. The hydrogen pressures of Application Examples 11, 12, 13, and 14 are 1.0 MPa, 2.0 MPa, 4.0 MPa, and 5.0 MPa in sequence, and the others are the same as Application Example 1. The temperatures of Application Examples 15, 16, and 17 are 80 °C, 120 °C, and 140 °C in sequence, and the others are the same as Application Example 1. The reaction times of Application Examples 18, 19, 20, and 21 are 1 hour, 2 hours, 4 hours, and 5 hours in sequence, and the others are the same as Application Example 1. The results are shown in Table 7.

[0064] Application Examples 22 to 61 Application Examples 22 to 61 respectively provide an application of a hydrogenation catalyst. The hydrogenation catalysts used are the hydrogenation catalysts provided in Catalyst Examples 2 to 41 above in sequence, and are used for preparing 1-(4-methoxyphenyl)propanol from p-methoxypropiophenone. The preparation method includes: In a 500 mL stainless steel autoclave, add the catalyst (5.0 g, catalyst concentration 5.0%), p-methoxypropiophenone (100 g, 0.609 mol), and 100 g of water, heat to 40 °C, stir to dissolve the p-methoxypropiophenone solid, displace with nitrogen three times and then introduce hydrogen, slowly raise the temperature, control the temperature at 100 °C, control the hydrogen pressure at 3.0 MPa, and stop the hydrogenation reaction after 3 h of hydrogenation reaction when hydrogen absorption stops.

[0065] Cool to room temperature, filter to recover the catalyst, use gas chromatography to detect the reaction solution, let the filtrate stand and separate into layers to obtain the oil phase, and perform vacuum distillation to obtain 1-(4-methoxyphenyl)propanol. The results are shown in Table 7.

[0066] Application Comparative Examples 1 to 2 Application Comparative Examples 1 to 2 respectively provide an application of a hydrogenation catalyst. The differences from Application Example 1 are only that the hydrogenation catalysts used are the hydrogenation catalysts provided in Comparative Examples 1 to 2 above in sequence. After the reaction, use a gas chromatograph to analyze the reaction solution, and calculate the conversion rate of p-methoxypropiophenone and the selectivity of 1-(4-methoxyphenyl)propanol. The results are shown in Table 7.

[0067] Application Examples 62 to 71 To promote the application of the catalyst of the present invention in complex hydrogenation reactions, the differences between Application Examples 62 to 71 and Application Example 1 are only that the types of reaction substrates are changed, and p-methoxypropiophenone is successively 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), neral (100 g, 0.520 mol), benzaldehyde (100 g, 0.942 mol), helional (100 g, 0.475 mol), and the others are the same as Application Example 1. The results are shown in Table 8.

[0068] Table 7

[0069]

[0070] Table 8

[0071] The applicant declares that the above description is only the specific implementation manner of the present invention, but the protection scope 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 protection scope and the disclosure scope 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 compound undergoes a hydrogenation reaction to obtain an alcohol compound; The reaction formula is as follows: ； In the above formula, R 1 is C1~C 12 alkyl, hydroxy-substituted C1~C 12 alkyl, C2~C 12 alkenyl, hydroxy-substituted C2~C 12 alkenyl, substituted or unsubstituted phenyl, and the substituents on the phenyl are selected from C1~C4 alkyl or C1~C4 alkoxy; R 2 is H or a C1-C4 alkyl group; The ruthenium-based hydrogenation catalyst includes: 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 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 groups or amino groups; The support is an MIL series of MOFs.

2. The synthesis method of the alcohol compound according to claim 1, characterized in that, 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.

3. The synthesis method of the alcohol compound according to claim 1, wherein The support is one or more of MIL-53, MIL-96, MIL-100, MIL-101, MIL-120, and MIL-125.

4. 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 an active metal salt, a promoter metal salt, and a ligand to a solvent, heat and stir for complexation to obtain a mixed solution; (2) Add a support to the mixed solution in step (1), heat and stir for adsorption to obtain a suspension; (3) Filter the suspension in step (2), and dry the obtained filter cake to a constant weight to obtain the ruthenium-based hydrogenation catalyst.

5. The synthesis method of the alcohol compound according to claim 4, characterized in that, In step (1), the solvent is purified water; In step (1), the temperature of the complexation is 80-140 °C, and the time of the complexation is 2-6 hours; The active metal salt is selected from ruthenium-containing inorganic salts, ruthenium-containing organic complexes, or their hydrates; The promoter metal salt is selected from inorganic salts containing iron, nickel, zinc, or molybdenum, or their hydrates; The mass ratio of the active metal salt to the promoter 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 promoter metal salt.

6. The synthesis method of the alcohol compound according to claim 4, wherein In step (2), the temperature of the adsorption is 30-60 °C, and the time of the adsorption is 2-6 hours; The mass ratio of the active metal salt to the support is 0.01-0.07:1.0, and the active metal salt is calculated based on the active metal therein.

7. According to the synthesis method of the alcohol compound according to any one of claims 1-6, characterized in that The carbonyl compound is one of p-methoxypropiophenone, citral, isopentenal, cinnamaldehyde, citronellal, veratraldehyde, p-methoxybenzaldehyde, hydroxycitronellal, citronellyl acetate, benzaldehyde, and lyral.

8. The method for synthesizing an alcohol compound according to any one of claims 1 to 6, characterized in that, The carbonyl compound is p-methoxypropiophenone, and the alcohol compound is 1-(4-methoxyphenyl)propanol.

9. The synthesis method of the alcohol compound according to any one of claims 1 to 6, characterized in that, The mass ratio of the ruthenium-based hydrogenation catalyst to the carbonyl compound is 1.0%-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 1.0~5.0 MPa.

10. The synthesis method of the alcohol compound according to any one of claims 1 to 6, characterized in that, The hydrogenation reaction is carried out under solvent or solvent-free conditions; The solvent is selected from one or more of methanol, ethanol, isopropanol, and water.

Images