Preparation method of 1-butene-3, 4-diol

Abstract

The embodiment of the invention discloses a preparation method of 1-butylene-3, 4-diol. 2-butene-1, 4-diol as shown in a formula I reacts under the action of a rhenium catalyst to obtain 1-butene-3, 4-diol as shown in a formula II. The method has the advantages of good catalytic effect and high repeated utilization rate, and can be used for large-scale and high-efficiency production of 1-butene-3, 4-diol.

Description

Technical Field

[0001] This application relates to the field of materials synthesis technology, and in particular to a method for preparing 1-butene-3,4-diol, which can synthesize lithium-ion electrolyte additives and pharmaceutical intermediates. Background Technology

[0002] Buten-3,4-diol is not only an important raw material for synthesizing vinyl ethylene carbonate and vinyl ethylene sulfite, additives for lithium-ion electrolytes, but also a crucial pharmaceutical intermediate. Its purity is particularly critical when used in the synthesis of lithium-ion battery electrolyte additives. The isomerization of 2-buten-1,4-diol to obtain 1-buten-3,4-diol is a commonly used method.

[0003] Currently, the methods for isomerizing 1-buten-3,4-diol from 2-buten-1,4-diol include: (1) using copper or cuprous salts as catalysts for isomerization under acidic conditions. This route has a low conversion rate, many impurities, and high industrialization costs; (2) using mercury salts as catalysts for isomerization. However, mercury salts are highly toxic and cause significant environmental damage, making this method unsuitable for industrialization; (3) using mixed solids as catalysts. This route requires a large amount of catalyst and necessitates the use of microwaves and ultrasound for heating. The method has extremely high requirements for equipment, making it difficult to scale up production; (4) Using rhenium heptaoxide as a catalyst, 2-butene-1,4-diol isomerization is directly catalyzed to obtain 1-butene-3,4-diol. The reaction has good selectivity and high conversion rate. The disadvantage is that the catalyst is expensive and the amount used is large; (5) Using rhenium heptaoxide as a catalyst, the amount of rhenium heptaoxide is reduced to five per thousand by introducing a phase transfer catalyst. However, the catalyst has a low reuse rate, so the cost still cannot meet the requirements of industrialization. Summary of the Invention

[0004] This application aims to address at least one of the technical problems existing in the prior art. To this end, this application proposes a method for preparing 1-buten-3,4-diol to solve the problem that the poor catalytic effect and low reusability of current catalysts prevent the large-scale, high-efficiency production of 1-buten-3,4-diol.

[0005] Specifically, this application discloses a method for preparing 1-butene-3,4-diol, comprising:

[0006] The 2-buten-1,4-diol of Formula I reacts with a rhenium catalyst to obtain the 1-buten-3,4-diol of Formula II:

[0007]

[0008] The general formula of the rhenium catalyst is:

[0009] Wherein: R is selected from any one of hydrogen atom, C1-C5 alkyl, aryl, and C2-C5 acyl.

[0010] In some embodiments of this application, the alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0011] The aryl group is selected from phenyl or substituted phenyl;

[0012] The acyl group is selected from any one of acetyl, propionyl, and butyryl.

[0013] In some embodiments of this application, the molar ratio of the 2-butene-1,4-diol to the rhenium catalyst is 1:(0.01%-0.1%).

[0014] In some embodiments of this application, the reaction temperature of the 2-butene-1,4-diol represented by Formula I under the action of a rhenium catalyst is 25-120°C.

[0015] In some embodiments of this application, the reaction is carried out in a solvent selected from at least one of ether solvents, ester solvents, chlorinated hydrocarbon solvents, and ketone solvents.

[0016] In some embodiments of this application, the ether solvent is selected from at least one of tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether;

[0017] The ester solvent is selected from at least one of dimethyl carbonate, diethyl carbonate, ethyl acetate, and isopropyl acetate.

[0018] The chlorinated hydrocarbon solvent is selected from at least one of dichloromethane, dichloroethane, chloroform, and tetrachloroethane;

[0019] The ketone solvent is methyl butyl ketone.

[0020] In some embodiments of this application, the preparation process of the rhenium catalyst includes the following steps:

[0021] A catalyst intermediate was prepared by reacting carbonyl rhenium with 1,2,4-trisubstituted cyclopentadiene.

[0022] The catalyst intermediate was refluxed in a mixture of concentrated sulfuric acid and a 35% hydrogen peroxide solution to obtain a rhenium metal catalyst.

[0023] In some embodiments of this application, the reaction temperature of the carbonyl rhenium with 1,2,4-trisubstituted cyclopentadiene is 150-210°C.

[0024] In some embodiments of this application, the volume ratio of the 35% hydrogen peroxide solution to the concentrated sulfuric acid is (40-60):1.

[0025] In some embodiments of this application, the catalyst intermediate and the mixture are refluxed at a temperature of 60-100°C.

[0026] The above-described one or more embodiments of this application have at least one or more of the following beneficial effects:

[0027] The method for preparing 1-buten-3,4-diol provided in this application uses 2-buten-1,4-diol as shown in Formula I as a raw material and prepares 1-buten-3,4-diol under the catalysis of a selected rhenium catalyst. This method is simple, mild, highly efficient, low-cost, and easy to industrialize.

[0028] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Detailed Implementation

[0029] To make the above-mentioned objectives, features, and advantages of this application more apparent and understandable, the specific embodiments of this application are described in detail below. Many specific details are set forth in the following description to provide a thorough understanding of this application. However, this application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of this application. Therefore, this application is not limited to the specific embodiments disclosed below.

[0030] As described in the background section, current US patent US4661646 uses copper or cuprous salts as catalysts to isomerize 2-buten-1,4-diol under acidic conditions. This route has a low conversion rate, many impurities, and high industrialization costs. British patent GB794685A uses mercury salts as catalysts for the isomerization of 2-buten-1,4-diol; however, due to the high toxicity of mercury salts, it is not environmentally friendly and unsuitable for industrialization. Chinese patent CN111389455 uses mixed solids as catalysts for the isomerization of 2-buten-1,4-diol, requiring a large amount of catalyst and necessitating microwave or ultrasonic heating, placing high demands on equipment. US patent US5336815A uses rhenium heptoxide as a catalyst to directly catalyze the isomerization of 2-buten-1,4-diol to 1-buten-3,4-diol, exhibiting good selectivity and high conversion rates. However, the catalysts are expensive and require a large quantity. Based on this, Chinese patent CN114149401A reduced the amount of rhenium heptoxide to 0.5% by introducing a phase transfer catalyst. However, the catalyst has a low reusability rate, so the cost still cannot meet the requirements for industrialization.

[0031] Therefore, there is an urgent need for a method to prepare 1-buten-3,4-diol that has high catalytic efficiency and allows for catalyst recycling, enabling large-scale, high-efficiency, and low-cost preparation of 1-buten-3,4-diol.

[0032] The method for preparing 1-buten-3,4-diol provided in this application uses 2-buten-1,4-diol as shown in Formula I as a raw material and prepares 1-buten-3,4-diol under the catalysis of a selected rhenium catalyst. This method is simple, mild, low in cost, and easy to industrialize.

[0033] The following describes some preferred embodiments of this application. It should be noted that the following description is for illustrative purposes only and is not intended to limit the scope of protection of this application. The steps involved in this application may be performed precisely in sequence, or various steps may be processed in reverse order or simultaneously. Furthermore, other operations may be added to these processes, or one or more steps may be removed from these processes.

[0034] Specifically, this application provides a method for preparing 1-buten-3,4-diol, comprising:

[0035] The 2-buten-1,4-diol of Formula I reacts with a rhenium catalyst to obtain the 1-buten-3,4-diol of Formula II:

[0036]

[0037] In Equation I Indicates configuration uncertainty. A double bond indicates that it can be either cis or trans, while a single bond indicates that it can be either R or S configuration.

[0038] The general formula of the rhenium catalyst is:

[0039] In the rhenium catalyst, R can be independently selected from any one of hydrogen atom, C1-C5 alkyl, aryl, and C2-C5 acyl groups.

[0040] The term "alkyl" can be substituted or unsubstituted. In this document, the term "alkyl" used alone or in combination can be straight-chain, branched, or cyclic, and the number of carbon atoms can be, for example, C1–C5, C1–C4, C1–C3, C1–C2, etc. For example, alkyl includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. "Substituted" means that at least one hydrogen atom of the substituent or compound is substituted. Substituents can be, for example, deuterium, hydroxyl, amino, mercapto, halogen, cyano, nitro, carbonyl, ester, oxo, imide, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy, and any combination thereof. "Unsubstituted" means that the hydrogen atom remains hydrogen and is not substituted by another substituent.

[0041] The term "aryl" refers to a group comprising at least one aromatic hydrocarbon moiety, wherein all elements of the aromatic hydrocarbon moiety have conjugated p-orbitals, such as phenyl, naphthyl, etc.; two or more aromatic hydrocarbon moiety portions may be linked by σ bonds and may be, for example, biphenyl, terphenyl, tetraphenyl, etc.; and two or more aromatic hydrocarbon moiety portions may be directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl. Aryl groups may include monocyclic, polycyclic, or fused-ring polycyclic (i.e., rings sharing adjacent carbon atom pairs) functional groups.

[0042] The term "acyl" refers to the atomic group remaining after removing one or more hydroxyl groups from a carboxylic acid, and its structural formula can be represented by -C(=O)-R. In some embodiments, the acyl group may include acetyl, propionyl, butyryl, valerate, etc.

[0043] It should be noted that the examples above are for illustrative purposes only and are not intended to limit the scope of protection of this application. Any modifications / adjustments / updates made based on the teachings of this application are within the scope of protection of this application.

[0044] In some embodiments of this application, the molar ratio of 2-buten-1,4-diol to the rhenium catalyst is 1:(0.01%-0.1%). Optionally, the molar ratio of 2-buten-1,4-diol to the rhenium catalyst can be 1:0.01%, 1:0.03%, 1:0.05%, 1:0.07%, 1:0.09%, 1:0.1%, etc., or any ratio within the above range, such as 1:0.02%, 1:0.28%, 1:0.58%, 1:0.77%, etc.

[0045] In some embodiments of this application, the reaction temperature of 2-buten-1,4-diol represented by Formula I under the action of a rhenium catalyst is 25-120°C. Optionally, the reaction temperature of 2-buten-1,4-diol in a solvent under the action of a rhenium catalyst can be 25°C, 50°C, 76°C, 105°C, 120°C, or any temperature value within the above temperature range.

[0046] In some embodiments of this application, the reaction is carried out in a solvent selected from at least one of ether solvents, ester solvents, chlorinated hydrocarbon solvents, and ketone solvents.

[0047] In some embodiments of this application, the ether solvent is selected from at least one of tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether;

[0048] The ester solvent is selected from at least one of dimethyl carbonate, diethyl carbonate, ethyl acetate, and isopropyl acetate.

[0049] The chlorinated hydrocarbon solvent is selected from at least one of dichloromethane, dichloroethane, chloroform, and tetrachloroethane;

[0050] The ketone solvent is methyl butyl ketone.

[0051] In some embodiments of this application, before reacting the 2-buten-1,4-diol of Formula I in a solvent under the action of a rhenium catalyst to obtain the 1-buten-3,4-diol of Formula II, the method further includes:

[0052] A catalyst intermediate was prepared by reacting carbonyl rhenium with 1,2,4-trisubstituted cyclopentadiene; the molecular formula of carbonyl rhenium is Re2(CO). 10 .

[0053] The catalyst intermediate was refluxed in a mixture of concentrated sulfuric acid and a 35% hydrogen peroxide solution to obtain a rhenium metal catalyst.

[0054] In some embodiments of this application, the reaction temperature of the carbonyl rhenium with 1,2,4-trisubstituted cyclopentadiene is 150-210°C. Optionally, the reaction temperature of the carbonyl rhenium with 1,2,4-trisubstituted cyclopentadiene is 150°C, 170°C, 180°C, 190°C, 200°C, 210°C, or any temperature value within the above range.

[0055] In some embodiments of this application, the volume ratio of a 35% hydrogen peroxide solution to concentrated sulfuric acid is (40-60):1. Optionally, the volume ratio of a 35% hydrogen peroxide solution to concentrated sulfuric acid is 40:1, 43:1, 47:1, 50:1, 54:1, 57:1, 60:1, or any ratio within the above ranges.

[0056] In some embodiments of this application, the temperature for the reflux reaction of the catalyst intermediate and the mixture is 60-100°C. Optionally, the reflux reaction temperature can be 60°C, 70°C, 80°C, 90°C, 100°C, or any temperature value within the above temperature range.

[0057] In some embodiments of this application, the above-mentioned mixture further contains a first solvent, which is selected from at least one of benzene and toluene.

[0058] In some embodiments of this application, after reacting carbonyl rhenium with 1,2,4-trisubstituted cyclopentadiene to obtain the catalyst intermediate, a post-treatment is also included. The post-treatment includes maintaining the reaction mixture containing the catalyst intermediate at 150-210°C for 25-35 minutes, then cooling to ambient temperature, and then performing vacuum drying.

[0059] The present application will be further described in detail below with reference to the embodiments. It should be noted that the following embodiments are only used to illustrate the present application and are not intended to limit the scope of protection claimed in the present application. They should not be construed as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present application still fall within the scope of protection of the present application.

[0060] Unless otherwise specified, the reagents, materials and instruments used in the following embodiments are commercially available products that can be purchased.

[0061] Example 1: In this example, 1-buten-3,4-diol is prepared using 2-buten-1,4-diol as a raw material, 1,2,4-(tri-tert-butyl)cyclopentadienylrhenium trioxide as a catalyst, and tetrahydrofuran as a solvent. The synthesis reaction formula is as follows:

[0062]

[0063] The preparation process includes:

[0064] Add 5g of Re2(CO) to a dry reaction flask. 1010 mL of 1,2,4-(tri-tert-butyl)cyclopentadiene was added. The resulting mixture was reacted at 150 °C for 30 minutes. The reaction mixture was then maintained at 210 °C for 30 minutes. After cooling to ambient temperature, it was dried under vacuum to obtain 6.1 g of catalyst intermediate. Then, 300 mL of toluene, 0.6 mL of concentrated sulfuric acid solution, and 30 mL of a mixture of 35% H₂O₂ were added. The resulting mixture was reacted at 100 °C for 15 hours, and post-treatment was performed to obtain 5.0 g of 1,2,4-(tri-tert-butyl)cyclopentadienyl rhenium trioxide.

[0065] 88 g of 2-buten-1,4-diol, 48.3 mg of 1,2,4-(tri-tert-butyl)cyclopentadienylrhenium trioxide, and 176 g of tetrahydrofuran were accurately weighed and added to a 500 ml four-necked flask. The mixture was heated to 60 °C and reacted for 15 hours. The product was then distilled to obtain 80.9 g of product with a GC purity of 94.0% and a yield of 91.9%.

[0066] Example 2: In this example, 1-buten-3,4-diol is prepared using 2-buten-1,4-diol as a raw material, 1,2,4-(trimethyl)cyclopentadienylrhenium trioxide as a catalyst, and dimethyl carbonate as a solvent. The synthesis reaction formula is as follows:

[0067]

[0068] The preparation process includes:

[0069] Add 5g of Re2(CO) to a dry reaction flask. 10 8 mL of 1,2,4-(trimethyl)cyclopentadiene was added. The resulting mixture was reacted at 150 °C for 30 minutes. The reaction mixture was then maintained at 180 °C for 30 minutes. After cooling to ambient temperature, it was dried under vacuum to obtain 4.5 g of catalyst intermediate. Then, 225 mL of benzene, 0.375 mL of concentrated sulfuric acid solution, and 22.5 mL of a mixture of 35% H₂O₂ were added. The resulting mixture was reacted at 60 °C for 12 hours, and post-treatment was performed to obtain 3.7 g of 1,2,4-(trimethyl)cyclopentadienylrhenium trioxide.

[0070] 88 g of 2-buten-1,4-diol, 71.4 mg of 1,2,4-(trimethyl)cyclopentadienylrhenium trioxide, and 176 g of dimethyl carbonate were accurately weighed and added to a 500 ml four-necked flask. The mixture was heated to 80 °C and reacted for 15 hours. The product was then distilled to obtain 80.1 g of product with a GC purity of 94.7% and a yield of 91.0%.

[0071] Example 3: In this example, 1-buten-3,4-diol is prepared using 2-buten-1,4-diol as a raw material, 1,2,4-(triphenyl)cyclopentadienylrhenium trioxide as a catalyst, and methyl butyl ketone as a solvent. The synthesis reaction formula is as follows:

[0072]

[0073] The preparation process includes:

[0074] Add 5g of Re2(CO) to a dry reaction flask. 10 15 mL of 1,2,4-(triphenyl)cyclopentadiene was added. The resulting mixture was reacted at 150 °C for 30 minutes. The reaction mixture was then maintained at 210 °C for 30 minutes. After cooling to ambient temperature, it was dried under vacuum to obtain 6.8 g of catalyst intermediate. Then, 340 mL of benzene, 0.85 mL of concentrated sulfuric acid solution, and 34 mL of a mixture of 35% H₂O₂ were added. The resulting mixture was refluxed at 80 °C for 20 hours, and post-treatment was performed to obtain 5.6 g of 1,2,4-(triphenyl)cyclopentadienyl rhenium trioxide.

[0075] Accurately weigh 88 g of 2-buten-1,4-diol, 543 mg of 1,2,4-(triphenyl)cyclopentadienylrhenium trioxide, and 176 g of methyl butyl ketone into a 500 mL four-necked flask. Heat to 120 °C and react for 15 hours. Then, distill to obtain 78.4 g of the product with a GC purity of 93.1% and a yield of 89.1%.

[0076] Example 4: In this example, 1-buten-3,4-diol is prepared using 2-buten-1,4-diol as a raw material, 1,2,4-(triacetyl)cyclopentadienylrhenium trioxide as a catalyst, and dichloroethane as a solvent. The synthesis reaction formula is as follows:

[0077]

[0078] The preparation process includes:

[0079] Add 5g of Re2(CO) to a dry reaction flask. 10 12 mL of 1,2,4-(triacetyl)cyclopentadiene was added. The resulting mixture was reacted at 150 °C for 30 min. The reaction mixture was then maintained at 170 °C for 30 min. After cooling to ambient temperature, it was dried under vacuum to obtain 5.6 g of intermediate. Then, 280 mL of benzene, 0.56 mL of concentrated sulfuric acid solution, and 28 mL of a mixture of 35% H₂O₂ were added. The resulting mixture was refluxed at 80 °C for 13 h, and post-processed to obtain 4.6 g of 1,2,4-(triacetyl)cyclopentadienyl rhenium trioxide.

[0080] Accurately weigh 88g of 2-buten-1,4-diol, 220.5mg of 1,2,4-(triacetyl)cyclopentadienylrhenium trioxide, and 176g of dichloroethane into a 500ml four-necked flask. Heat to 30°C and react for 15 hours. Distill to obtain 76.3g of product with GC purity of 93.9% and yield of 86.7%.

[0081] Comparative Example 1: 100 g of 2-buten-1,4-diol was dissolved in 600 mL of water, and after adding 5 mL of concentrated hydrochloric acid aqueous solution and 1 g of CuCl, the mixture was heated at 100 °C. After stirring for 15 hours, distillation yielded 37.2 g of product with a GC purity of 95.1% and a yield of 37.2%.

[0082] Compared with the products obtained in the above embodiments, this route has poorer reaction selectivity and lower yield.

[0083] Comparative Example 2: 88g of 2-buten-1,4-diol, 10g of mercuric sulfate, 10g of sulfuric acid, and 220g of water were mixed and reacted at 95°C for 4 hours. After adjusting the pH to 7-8 with 5% saturated sodium bicarbonate aqueous solution, the product was obtained by distillation, with a GC purity of 95.8% and a yield of 75.6%.

[0084] Compared with the reactions in the above examples, this route has a more toxic catalyst and a lower yield.

[0085] Comparative Example 3: 150g of 2-buten-1,4-diol, 1g of rhenium heptaoxide, and 100g of paraffin oil were mixed and reacted at 130℃ for 2 hours. The product was then distilled to obtain 125.1g of product with a GC purity of 90.8% and a yield of 83.4%.

[0086] Compared with the reactions in the above embodiments, this route requires a larger amount of catalyst and has a higher cost.

[0087] Comparative Example 4: 100 g of 2-buten-1,4-diol and 0.1 g of catalyst (composed of rhenium heptaoxide, tetrabutylammonium bromide, and potassium iodide in a mass ratio of 17:2:1) and 200 g of tetrahydrofuran were added to a 500 mL three-necked flask. The mixture was stirred, heated to 70 °C, and refluxed for 5 hours. Distillation yielded 95 g of product with a purity of 92.56% and a yield of 87.93%. The residue from the reaction was then re-added with 100 g of 2-buten-1,4-diol and 200 g of tetrahydrofuran, and the reaction was repeated six times with the catalyst. The results are shown in Table 1.

[0088] Table 1

[0089] Number of times to apply Product purity yield 1 91.98％ 84.20％ 2 92.03％ 81.08％ 3 90.67％ 80.05％ 4 90.95％ 70.33％ 5 91.20％ 60.19％ 6 - 39.25％

[0090] Example 1: The catalyst was reused ten times, and the results are shown in Table 2.

[0091] Table 2

[0092]

[0093]

[0094] Compared with Example 1, the catalyst used in Comparative Example 4 had low activity, and after several cycles, the catalyst gradually became ineffective, resulting in a significant decrease in product yield.

[0095] In this application, the design relationships of greater than, less than, or not equal to parameter values ​​need to exclude reasonable errors of the measuring equipment.

[0096] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1-5” is disclosed, the described range should be interpreted as including ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range. The singular form includes plural objects of discussion unless clearly indicated by the context. “Optional” or “any” means that the matter or event described thereafter may or may not occur, and the description includes both the occurrence and non-occurrence of the event.

[0097] Furthermore, the indefinite articles “a” and “an” preceding the elements or components of this application do not impose any limitation on the quantity requirement (i.e., the number of times) of the elements or components. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers to the singular form.

[0098] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0099] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0100] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A method for preparing 1-buten-3,4-diol, characterized in that, include: The 2-buten-1,4-diol of Formula I reacts with a rhenium catalyst to obtain the 1-buten-3,4-diol of Formula II: The general formula of the rhenium catalyst is: Wherein: R is selected from any one of hydrogen atom, C1-C5 alkyl, aryl, and C2-C5 acyl.

2. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. The aryl group is selected from phenyl or substituted phenyl; The acyl group is selected from any one of acetyl, propionyl, and butyryl.

3. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The molar ratio of 2-butene-1,4-diol to the rhenium catalyst is 1:(0.01%-0.1%).

4. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The reaction temperature of the 2-butene-1,4-diol represented by Formula I under the action of rhenium catalyst is 25-120℃.

5. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The reaction is carried out in a solvent selected from at least one of ether solvents, ester solvents, chlorinated hydrocarbon solvents, and ketone solvents.

6. The method for preparing 1-butene-3,4-diol according to claim 5, characterized in that, The ether solvent is selected from at least one of tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. The ester solvent is selected from at least one of dimethyl carbonate, diethyl carbonate, ethyl acetate, and isopropyl acetate. The chlorinated hydrocarbon solvent is selected from at least one of dichloromethane, dichloroethane, chloroform, and tetrachloroethane; The ketone solvent is methyl butyl ketone.

7. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The preparation process of the rhenium catalyst includes the following steps: A catalyst intermediate was prepared by reacting carbonyl rhenium with 1,2,4-trisubstituted cyclopentadiene. The catalyst intermediate was refluxed in a mixture of concentrated sulfuric acid and a 35% hydrogen peroxide solution to obtain a rhenium metal catalyst.

8. The method for preparing 1-butene-3,4-diol according to claim 7, characterized in that, The reaction temperature of the carbonyl rhenium with 1,2,4-trisubstituted cyclopentadiene is 150-210℃.

9. The method for preparing 1-butene-3,4-diol according to claim 7, characterized in that, The volume ratio of the 35% hydrogen peroxide solution to the concentrated sulfuric acid is (40-60):

1.

10. The method for preparing 1-butene-3,4-diol according to claim 9, characterized in that, The catalyst intermediate and the mixture are refluxed at a temperature of 60-100°C.

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