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

Abstract

The embodiment of the invention discloses a preparation method of 1-butene-3, 4-diol, which comprises the following step of: reacting erythritol with trimethyl orthoformate under the action of a rhenium catalyst, organic acid and a polymerization inhibitor to obtain the 1-butene-3, 4-diol. According to the embodiment of the invention, the effects of simple steps, cheap and easily available raw materials, good catalyst selectivity, recycling, environment friendliness, low cost and easiness in industrial production are realized.

Description

Technical Field

[0001] This invention 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] 1-Buten-3,4-diol is an organic synthetic intermediate mainly used in the synthesis of lithium-ion battery electrolyte additives such as vinyl ethylene carbonate and vinyl ethylene sulfite, as well as in the synthesis of pharmaceutical intermediates. Therefore, its synthesis has high industrial demand.

[0003] The traditional method for synthesizing 1-buten-3,4-diol is to produce it by rearrangement of 2-buten-1,4-diol. Currently, the main methods for synthesizing 1-buten-3,4-diol are: (1) using 2-buten-1,4-diol to react with a catalytic amount of rhenium heptoxide to obtain 1-buten-3,4-diol; (2) using quaternary ammonium salt combined with potassium iodide to catalyze the rearrangement of 2-buten-1,4-diol to synthesize 1-buten-3,4-diol; (3) reacting 2-buten-1,4-diol with a mixed solid catalysis of solid acid molecular sieve and metal salt modified carbon material to generate 1-buten-3,4-diol.

[0004] Method (1) requires the prior synthesis of 2-buten-1,4-diol, and method (2) also requires the prior synthesis of 2-buten-1,4-diol, and both methods use a large amount of catalyst, resulting in high costs. Method (3) has low raw material conversion rate and product selectivity, and the metal salt modification of carbon materials requires a complex preparation process, making it impractical. Therefore, there is an urgent need to develop a synthesis method for 1-buten-3,4-diol suitable for large-scale industrial production, which can simplify reaction steps and improve raw material conversion rate. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention proposes a method for preparing 1-butene-3,4-diol, so as to simplify the reaction steps and improve the conversion rate of raw materials.

[0006] Specifically, the present invention provides a method for preparing 1-butene-3,4-diol, comprising: reacting erythritol with trimethyl orthoformate under the action of rhenium catalyst, organic acid and polymerization inhibitor to obtain 1-butene-3,4-diol.

[0007] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the organic acid includes one or more of formic acid, acetic acid, propionic acid, butyric acid, and benzoic acid.

[0008] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the molar ratio of erythritol to the organic acid is 1:(0.025-0.058).

[0009] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the polymerization inhibitor includes one or more of hydroquinone, phenothiazine, and cuprous chloride.

[0010] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the weight ratio of erythritol to the polymerization inhibitor is 1:(0.005-0.01).

[0011] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the rhenium catalyst comprises rhenium heptaoxide; The weight ratio of erythritol to the rhenium catalyst is 1:(0.001-0.002).

[0012] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the molar ratio of erythritol to trimethyl orthoformate is 1:(1-1.3).

[0013] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the reaction is carried out in a solvent, which includes one or more of sulfolane, dimethyl sulfoxide, 3-methylsulfolane, and 2,4-dimethylsulfolane.

[0014] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the weight ratio of erythritol to the solvent is 1:(2-3).

[0015] In one embodiment of the above-described method for preparing 1-butene-3,4-diol, the reaction temperature is 190°C-220°C, the reaction pressure is 1.5 MPa-2.5 MPa, and the reaction time is 2 h-4 h.

[0016] The above-described one or more embodiments of the present invention have at least one or more of the following beneficial effects: a new method for preparing 1-butene-3,4-diol is provided, which has simple steps, inexpensive and readily available raw materials, good catalyst selectivity, and can be recycled, is environmentally friendly, has low cost, and is easy to industrialize.

[0017] Additional aspects and advantages of the invention 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 the invention. Detailed Implementation

[0018] The following describes some embodiments of the present invention with reference to the scheme. Those skilled in the art should understand that these embodiments are merely illustrative of the technical principles of the present invention and are not intended to limit the scope of protection of the present invention.

[0019] As described in the background section, the method disclosed by Rainer Becker et al. of BASF Germany in patent US5336815, which utilizes 2-buten-1,4-diol in a catalytic amount of rhenium heptoxide at 130°C for 2 hours to obtain 1-buten-3,4-diol in 76% yield, requires the prior synthesis of 2-buten-1,4-diol. Similarly, the method in Chinese patent CN114149401A, which uses a quaternary ammonium salt combined with potassium iodide to catalyze the rearrangement of 2-buten-1,4-diol to synthesize 1-buten-3,4-diol, also requires the prior synthesis of 2-buten-1,4-diol, and involves a larger amount of catalyst, resulting in higher costs. Furthermore, the method for preparing 2-buten-1,4-diol under optimized conditions of 100℃ reaction for 6 hours under the mixed solid catalysis of solid acid molecular sieve and metal salt modified carbon material achieves a conversion rate of 74-79% and a selectivity of 65-67% for 1-buten-3,4-diol. The raw material conversion rate and product selectivity need further improvement. In addition, the metal salt modified carbon material requires a complex preparation process, limiting its practicality. Therefore, a new method for preparing 1-buten-3,4-diol is urgently needed, which is simple, low-cost, environmentally friendly, and suitable for industrial production.

[0020] To address the aforementioned issues, this application creatively proposes a method for preparing 1-butene-3,4-diol. The method involves reacting erythritol with trimethyl orthoformate under the action of a rhenium catalyst, organic acid, and polymerization inhibitor to obtain 1-butene-3,4-diol. This eliminates the need for prior preparation of the 2-butene-1,4-diol intermediate, is simple in procedure, low in cost, environmentally friendly, and suitable for industrial production.

[0021] The present invention will be specifically described below through specific embodiments.

[0022] Specifically, this application provides a method for preparing 1-butene-3,4-diol, comprising: reacting erythritol with trimethyl orthoformate under the action of a rhenium catalyst, an organic acid and a polymerization inhibitor to obtain 1-butene-3,4-diol.

[0023] Erythritol has the molecular formula C4H 10 O4 is a type of C4 polyol compound that can be used as a sweetener. It is relatively safe and environmentally friendly.

[0024] The one-pot reaction of erythritol to obtain 1-buten-3,4-diol is a simple procedure. Due to the use of polymerization inhibitors in the reaction, 1-buten-3,4-diol can be obtained in a higher yield, making it more practical.

[0025] The term "organic acid" refers to some organic compounds that are acidic. The most common organic acids are carboxylic acids (R-COOH), sulfonic acids (R-SO3H), sulfinic acids (R-SOOH), and thiocarboxylic acids (R-SH), etc. R can independently be any one of hydrogen atoms, alkyl groups, or aryl groups.

[0026] 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. As examples, 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.

[0027] 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.

[0028] 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.

[0029] In some embodiments, the organic acid includes one or more of formic acid, acetic acid, propionic acid, butyric acid, and benzoic acid.

[0030] In some embodiments, the molar ratio of erythritol to the organic acid is 1:(0.025-0.058). Optionally, the molar ratio of erythritol to the organic acid may be 1:0025, 1:0030, 1:0033, 1:0035, 1:0040, 1:0046, 1:0049, 1:0050, 1:0054, 1:0058, or any ratio within the above range.

[0031] Polymerization inhibitors are substances that can convert primary free radicals or chain free radicals into stable molecules or form stable free radicals with very low reactivity. They can terminate polymerization reactions to prevent olefin monomers from polymerizing during storage and transportation. By adding polymerization inhibitors, the reaction can achieve higher yields of 1-buten-3,4-diol, making it more practical.

[0032] In some embodiments, the polymerization inhibitor includes one or more of hydroquinone, phenothiazine, and cuprous chloride.

[0033] In some embodiments, the weight ratio of erythritol to the polymerization inhibitor is 1:(0.005-0.01). Optionally, the weight ratio of erythritol to the polymerization inhibitor may be 1:0.5%, 1:0.55%, 1:0.6%, 1:0.65%, 1:0.7%, 1:0.75%, 1:0.8%, 1:0.85%, 1:0.9%, 1:9.5%, 1:1%, or any ratio within the above range.

[0034] In some embodiments, the rhenium catalyst comprises rhenium heptoxide. The rhenium heptoxide catalyst can isomerize the byproduct 2-butene-1,4-diol and can be recycled.

[0035] The weight ratio of erythritol to the rhenium catalyst is 1:(0.001-0.002). Optionally, the weight ratio of erythritol to the rhenium catalyst can be 1:0.001, 1:0.0013, 1:0.0015, 1:0.0017, 1:0.0019, 1:0.002, or any ratio within the above range.

[0036] In some embodiments, the molar ratio of erythritol to trimethyl orthoformate is 1:(1-1.3). Optionally, the molar ratio of erythritol to trimethyl orthoformate may be 1:1, 1:1.13, 1:1.15, 1:1.17, 1:1.2, 1:1.24, 1:1.25, 1:1.28, 1:1.3, or any ratio within the above range.

[0037] In some embodiments, the reaction is carried out in a solvent, which includes one or more of sulfolane, dimethyl sulfoxide, 3-methylsulfolane, and 2,4-dimethylsulfolane.

[0038] In some embodiments, the weight ratio of erythritol to the solvent is 1:(2-3). Optionally, the weight ratio of erythritol to the solvent may be 1:2, 1:2.2, 1:2.4, 1:2.5, 1:2.6, 1:2.8, 1:3, or any ratio within the above range.

[0039] In some embodiments, the reaction temperature is 190℃-220℃, the reaction pressure is 1.5MPa-2.5MPa, and the reaction time is 2h-4h. Optionally, the reaction temperature can be 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, or any value within the above temperature range. The reaction pressure can be 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa, 2.0MPa, 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa, 2.5MPa, or any value within the above pressure range. The reaction time can be 2h, 2.5h, 3h, 3.5h, 4h, or any value within the above time range.

[0040] The technical solution of the present invention will be further illustrated below through specific embodiments.

[0041] Example 1: 48.8 g (0.4 mol) of erythritol, 0.46 g (0.01 mol) of formic acid, 140 g of sulfolane, 0.2 g of phenothiazine, 42.4 g (0.4 mol) of trimethyl orthoformate, and 0.049 g of rhenium heptaoxide were weighed and placed in a 500 ml autoclave. The autoclave was covered, and the air in the autoclave was replaced three times with nitrogen. The temperature was slowly increased until it reached 130 °C. Stirring was then started, and the temperature was further increased to 220 °C and maintained at 2.5 MPa for 2 hours. After the maintenance was completed, the autoclave was cooled to room temperature, and a sample was taken from the liquid phase port for GC analysis. The reaction solution was post-processed by first distilling off the light component (mainly methanol) under a water ring vacuum pump, and then distilling off 31 g of crude product under an oil pump. The 1-buten-3,4-diol content was 93%, with a yield of 81.9%. The remaining autoclave liquid (mainly sulfolane and rhenium heptaoxide) could be reused.

[0042] Example 2: 48.8g (0.4mol) of erythritol, 0.92g (0.020mol) of formic acid, 145g of 3-methylcyclobutane, 0.44g of hydroquinone, 42.4g (0.4mol) of trimethyl orthoformate, and 0.092g of rhenium heptoxide were weighed and placed in a 500ml autoclave. The autoclave was covered, and the air in the autoclave was replaced with nitrogen three times. The temperature was slowly increased. When the temperature reached 130℃, stirring was started, and the temperature was continued to rise to 220℃. The autoclave was held at 2.5MPa for 2 hours. After the holding period, the autoclave was cooled to room temperature, and a sample was taken from the liquid phase port for GC analysis. The reaction solution was post-processed by first distilling off the light components (mainly methanol) under a water ring vacuum pump, and then distilling off 30.3g of crude product under an oil pump. The 1-butene-3,4-diol content was 92.9%, and the yield was 80%. The remaining reactor liquid could be reused (the main components were 3-methylcyclobutanesulfone and rhenium heptaoxide).

[0043] Example 3: 48.8 g (0.4 mol) of erythritol, 1.38 g (0.023 mol) of acetic acid, 100 g of dimethyl sulfoxide, 48.8 g (0.46 mol) of trimethyl orthoformate, 0.44 g of phenothiazine, and 0.049 g of rhenium heptoxide were weighed and placed in a 500 ml autoclave. The autoclave was covered, and the air in the autoclave was replaced with nitrogen three times. The temperature was slowly increased. When the temperature reached 130 °C, stirring was started, and the temperature was increased to 190 °C. The autoclave was held at 1.5 MPa for 3 hours. After the holding period, the autoclave was cooled to room temperature, and a sample was taken from the liquid phase port for GC analysis. The reaction solution was post-processed by first distilling off the light components (mainly methanol) under a water ring vacuum pump, and then distilling off 30.1g of crude product under an oil pump. The 1-butene-3,4-diol content was 94.7%, and the yield was 81%. The remaining reactor liquid (mainly dimethyl sulfone and rhenium heptaoxide) can be reused.

[0044] Example 4: 48.8 g (0.4 mol) of erythritol, 1.06 g (0.023 mol) of formic acid, 125 g of 2,4-dimethylcyclobutane sulfolane, 46.6 g (0.44 mol) of trimethyl orthoformate, 0.4 g of cuprous chloride, and 0.073 g of rhenium heptoxide were weighed and placed in a 500 ml autoclave. The autoclave was covered, and the air in the autoclave was replaced three times with nitrogen. The temperature was slowly increased until it reached 130 °C. Stirring was then started, and the temperature was further increased to 220 °C and maintained at this temperature for 4 hours at a pressure of 2.5 MPa. After the maintenance was completed, the autoclave was cooled to room temperature, and a sample was taken from the liquid phase port for GC analysis. The reaction solution was post-processed by first distilling off the light component (mainly methanol) under a water ring vacuum pump, and then distilling off 31.5 g of crude product under an oil pump. The 1-buten-3,4-diol content was 93.86%, with a yield of 84%.

[0045] Example 5: 48.8 g (0.4 mol) of erythritol, 1.96 g (0.016 mol) of benzoic acid, 130 g of sulfolane, 46.6 g of trimethyl orthoformate, 0.3 g of cuprous chloride, and 0.049 g of rhenium heptoxide were weighed and placed in a 500 ml autoclave. The autoclave was covered, and the air in the autoclave was replaced three times with nitrogen. The temperature was slowly increased until it reached 130 °C. Stirring was then started, and the temperature was further increased to 20 °C. The autoclave was held at this temperature for 2 hours at a pressure of 2.0 MPa. After the holding period, the autoclave was cooled to room temperature, and a sample was taken from the liquid phase port for GC analysis. The reaction solution was post-processed by first distilling off the light component (mainly methanol) under a water ring vacuum pump, and then distilling off 31.7 g of product under an oil pump. The 1-buten-3,4-diol content was 92.8%, with a yield of approximately 83.5%.

[0046] Comparative Example 1: 48.8 g (0.4 mol) of erythritol, 0.46 g (0.01 mol) of formic acid, 140 g of sulfolane, 42.4 g (0.4 mol) of trimethyl orthoformate, and 0.049 g of rhenium heptaoxide were weighed and placed in a 500 ml autoclave. The autoclave was covered, and the air in the autoclave was replaced three times with nitrogen. The temperature was slowly increased until it reached 130 °C. Stirring was then started, and the temperature was further increased to 220 °C. The autoclave was held at this temperature for 2 hours at a pressure of 2.5 MPa. After the holding period, the autoclave was cooled to room temperature, and a sample was taken from the liquid phase port for GC analysis. The reaction solution was post-processed by first distilling off the light component (mainly methanol) under a water-ring vacuum pump, and then distilling off 26 g of crude product under an oil pump. The 1-buten-3,4-diol content was 88.1%, with a yield of 65%. The remaining autoclave liquid (mainly sulfolane and rhenium heptaoxide) could be reused.

[0047] In the description of this specification, 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 the invention. 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.

[0048] 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 invention, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0049] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing 1-butene-3,4-diol, characterized in that, include: Erythritol reacts with trimethyl orthoformate under the action of rhenium catalyst, organic acid and polymerization inhibitor to yield 1-butene-3,4-diol.

2. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The organic acid includes one or more of formic acid, acetic acid, propionic acid, butyric acid, and benzoic acid.

3. The method for preparing 1-butene-3,4-diol according to claim 1 or 2, characterized in that, The molar ratio of erythritol to the organic acid is 1:(0.025-0.058).

4. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The polymerization inhibitor includes one or more of hydroquinone, phenothiazine, and cuprous chloride.

5. The method for preparing 1-butene-3,4-diol according to claim 1 or 4, characterized in that, The weight ratio of erythritol to the polymerization inhibitor is 1:(0.005-0.01).

6. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The rhenium catalyst comprises rhenium heptaoxide; The weight ratio of erythritol to the rhenium catalyst is 1:(0.001-0.002).

7. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The molar ratio of erythritol to trimethyl orthoformate is 1:(1-1.3).

8. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The reaction is carried out in a solvent, which includes one or more of sulfolane, dimethyl sulfoxide, 3-methylsulfolane, and 2,4-dimethylsulfolane.

9. The method for preparing 1-butene-3,4-diol according to claim 8, characterized in that, The weight ratio of erythritol to the solvent is 1:(2-3).

10. The method for preparing 1-butene-3,4-diol according to claim 1, characterized in that, The reaction temperature is 190℃-220℃, the reaction pressure is 1.5Mpa-2.5Mpa, and the reaction time is 2h-4h.