Method for synthesizing 2-methoxy-3-butene-1-ol by one-pot method

Abstract

The invention relates to a method for synthesizing 2-methoxy-3-butene-1-ol through a one-pot method, and the method comprises the following steps: mixing 1, 3-butadiene, a titanium silicalite molecular sieve, methanol, peroxide and a phase transfer catalyst, and carrying out a reaction to prepare the 2-methoxy-3-butene-1-ol. The invention provides a novel synthesis route, 2-methoxy-3-butene-1-ol is synthesized by using a titanium silicalite molecular sieve one-pot method, and the method is green, environment-friendly, short in route and more suitable for industrial production.

Description

Technical Field

[0001] The present application belongs to the field of material synthesis technology. Specifically, the present application relates to a one-pot method for synthesizing 2-methoxy-3-butene-1-ol. Background Art

[0002] 2-Methoxy-3-butene-1-ol is an important synthetic intermediate, used, for example, in the preparation of low-molecular-weight polyurethane oligomers and as a monomer for acrylic resins. Existing reported synthesis methods primarily involve reacting 1,3-butadiene with calcium hypochlorite to produce 2-chloro-3-butene-1-ol, which is then reacted with sodium hydroxide for ring closure to yield 3,4-epoxy-1-butene. Finally, a ring-opening reaction with methanol in the presence of a Lewis acid yields 2-methoxy-3-butene-1-ol. This reaction route is lengthy and yields are low. The first chlorohydrination step, using calcium hypochlorite as a chlorination agent, generates large amounts of wastewater and solid waste, produces numerous byproducts, and produces low yields, making it unsuitable for industrial production.

[0003]

[0004] There are also reports on the epoxidation of 1,3-butadiene and m-chloroperbenzoic acid. However, m-chloroperbenzoic acid itself has a large molecular weight and high unit consumption, making it difficult to control costs. Summary of the Invention

[0005] This application addresses many problems existing in existing synthesis technologies and provides a method for synthesizing 2-methoxy-3-butene-1-ol in a one-pot process using titanium silicalite molecular sieve. The method of the invention is green and environmentally friendly, has a short route and high yield, and is more suitable for industrial use.

[0006] To achieve the purpose of this invention, this application adopts the following technical solutions:

[0007] The present application provides a one-pot method for synthesizing 2-methoxy-3-butene-1-ol, the method comprising the following steps:

[0008] 1,3-butadiene, titanium silicalite molecular sieve, methanol, peroxide and a phase transfer catalyst are mixed and reacted to prepare 2-methoxy-3-butene-1-ol.

[0009] In some embodiments of the present invention, the titanium silicon molecules are selected from one or more of TS-1 and TS-2.

[0010] In some embodiments of the present invention, the peroxide is hydrogen peroxide.

[0011] In some embodiments of the present invention, the concentration of the peroxide is 30-50%.

[0012] In some embodiments of the present invention, the phase transfer catalyst is selected from one or more of tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrapropylammonium chloride.

[0013] In some embodiments of the present invention, the mass ratio of the 1,3-butadiene to the titanium silicate molecular sieve is (5-10):1.

[0014] In some embodiments of the present invention, the mass volume ratio of the 1,3-butadiene to methanol is 1 g: (3-5) mL.

[0015] In some embodiments of the present invention, the molar ratio of 1,3-butadiene to hydrogen peroxide is (1.5-2):1.

[0016] In some embodiments of the present invention, the mass ratio of the 1,3-butadiene to the phase transfer catalyst is (500-1000):1.

[0017] In some embodiments of the present invention, the mixture is stirred at room temperature for 2 to 5 hours before reacting.

[0018] In some embodiments of the present invention, the reaction temperature is 60-80°C.

[0019] In some embodiments of the present invention, the reaction time is 6 to 16 hours.

[0020] In some embodiments of the present invention, post-treatment is further included, and the post-treatment includes cooling to room temperature, filtering, concentrating the filtrate to obtain a crude product, and distilling the crude product under reduced pressure.

[0021] Compared with the prior art, this application has the following beneficial effects:

[0022] The present invention provides a new synthesis route, which utilizes the characteristics of titanium silicalite and adopts a phase transfer catalyst to overcome the difficulty of polymerization side reaction of titanium silicalite. Simultaneously with epoxidation with hydrogen peroxide, a ring-opening reaction occurs with methanol to synthesize 2-methoxy-3-butene-1-ol in a one-pot method.

[0023] Compared with the existing technical routes, this route is shorter, produces only water as waste, has a high yield, low cost, and is more suitable for industrial production. DETAILED DESCRIPTION

[0024] The following detailed description specifically discloses an embodiment of the one-pot method for synthesizing 2-methoxy-3-butene-1-ol of the present application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters or repeated descriptions of substantially identical structures may be omitted. This is to avoid unnecessary length in the following description and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to facilitate a thorough understanding of the present application by those skilled in the art and is not intended to limit the subject matter recited in the claims.

[0025] " range " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a range with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0026] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0027] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0028] Unless otherwise specified, the terms "include" and "comprising" used in this application may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0029] Titanium silicate molecular sieves are widely used in epoxidation and ring-opening reactions. The present invention utilizes the properties of titanium silicate molecular sieves and employs a phase transfer catalyst to overcome the difficulties of titanium silicate polymerization side reactions. Simultaneously with hydrogen peroxide epoxidation, a ring-opening reaction occurs with methanol, resulting in a one-pot synthesis of 2-methoxy-3-butene-1-ol. This method is environmentally friendly, has a short route, and a high yield. It is more suitable for industrial use. Based on this, the present application has been completed.

[0030] One-pot synthesis of 2-methoxy-3-butene-1-ol

[0031] The present application provides a one-pot method for synthesizing 2-methoxy-3-butene-1-ol. The synthesis method comprises: mixing 1,3-butadiene, titanium silicon molecular sieve, methanol, peroxide, and a phase transfer catalyst to react to prepare 2-methoxy-3-butene-1-ol.

[0032]

[0033] In the one-pot synthesis method of 2-methoxy-3-butene-1-ol provided by the present invention, the titanium silicalite molecular sieve is selected from one or more of TS-1 and TS-2. In some embodiments, the titanium content of the titanium silicalite molecular sieve is Si / Ti: ~30, SSA (specific surface area): 300~450m 2 / g.

[0034] In the one-pot method for synthesizing 2-methoxy-3-butene-1-ol provided by the present invention, methanol serves as both a solvent and a raw material.

[0035] In the one-pot method for synthesizing 2-methoxy-3-butene-1-ol provided by the present invention, the peroxide is selected from hydrogen peroxide, and the concentration of the peroxide is ≥30%, for example, 30-50%.

[0036] In the one-pot method for synthesizing 2-methoxy-3-butene-1-ol provided by the present invention, the phase transfer catalyst is selected from one or more of tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrapropylammonium chloride. The addition of the phase transfer catalyst can overcome polymerization of the silicon titanium molecular sieve.

[0037] In the one-pot synthesis method of 2-methoxy-3-butene-1-ol provided by the present invention, the mass ratio of 1,3-butadiene to titanium silicalite is (5-10):1, which can be optionally (5-8):1 or (8-10):1.

[0038] The mass volume ratio of the 1,3-butadiene to methanol is 1 g: (3-5) mL, which can be 1 g: (3-4) mL or 1 g: (4-5) mL.

[0039] The molar ratio of 1,3-butadiene to hydrogen peroxide is (1.5-2):1, and can be (1.5-1.8):1 or (1.8-2):1.

[0040] The mass ratio of the 1,3-butadiene to the phase transfer catalyst is (500-1000):1. The mass ratio may be (500-800):1, (800-1000):1, (500-600):1, (600-700):1, (700-800):1, (800-900):1 or (900-1000):1.

[0041] In the one-pot synthesis method of 2-methoxy-3-butene-1-ol provided by the present invention, the mixture is stirred at room temperature for 2 to 5 hours before reacting. Optionally, the stirring time can be, for example, 2 to 3 hours, 3 to 5 hours, 2 to 4 hours, or 4 to 5 hours.

[0042] In the one-pot synthesis method of 2-methoxy-3-butene-1-ol provided by the present invention, the reaction temperature is 60-80° C., optionally, the reaction temperature can be, for example, 60-70° C. or 70-80° C. The reaction time is 6-16 hours, optionally, the reaction time can be 6-10 hours or 10-16 hours.

[0043] The one-pot synthesis method of 2-methoxy-3-butene-1-ol provided by the present invention further comprises post-processing, which comprises cooling to room temperature, filtering, concentrating the filtrate to obtain a crude product, and distilling the crude product under reduced pressure.

[0044] The following is a clear and complete description of the technical solution of the present application in conjunction with the embodiments of the present application. It is necessary to point out that the following embodiments are only used to further illustrate the present application and are not to be construed as limiting the scope of protection of the present application. Any non-essential improvements and adjustments made by professionals in this field based on the contents of the present application are still within the scope of protection of the present application.

[0045] In the following examples, all reagents, materials and instruments used are commercially available unless otherwise specified.

[0046] TS-1 was purchased from Adamas. The silicon-titanium ratio (Si / Ti) is 30 and the specific surface area (BET / SSA) is 300-450m 2 / g

[0047] Example 1

[0048] To an autoclave, add 50g of 1,3-butadiene, 200ml of methanol, 10g of TS-1, 0.1g of tetrabutylammonium chloride, and 73g of 30% hydrogen peroxide. Stir at room temperature for 2 hours. Then, heat to 70°C and react for 6 hours. Cool to room temperature, filter, and concentrate the filtrate. The crude product is then distilled under reduced pressure to yield 46g of 2-methoxy-3-butene-1-ol, a 70% yield. 1 H NMR (CDCl3, 399.972): 5.72-5.63 (m, 1H, H3); 5.35-5.29 (m, 2H, CH2 H4); 3.74-3.69 (m, 1H, H2); 3.60-3.54 (m, 2H, CH2H1); 3.34 (s, 3H, OCH3).

[0049] Example 2

[0050] To an autoclave, add 50g of 1,3-butadiene, 300ml of methanol, 5g of TS-1, 0.1g of tetrabutylammonium bromide, and 73g of 30% hydrogen peroxide. Stir at room temperature for 3 hours. Then, heat to 60°C and react for 6 hours. Cool to room temperature, filter, and concentrate the filtrate. The crude product is distilled under reduced pressure to yield 44.7g of 2-methoxy-3-butene-1-ol, a yield of 68%.

[0051] Example 3

[0052] To an autoclave, add 50g of 1,3-butadiene, 200ml of methanol, 10g of TS-1, 0.05g of tetrapropylammonium chloride, and 52g of 30% hydrogen peroxide. Stir at room temperature for 2 hours. Then heat to 80°C and react for 16 hours. Cool to room temperature, filter, and concentrate the filtrate. The crude product is then distilled under reduced pressure to yield 31.8g of 2-methoxy-3-butene-1-ol, a yield of 68%.

[0053] Comparative Example 1

[0054] To an autoclave, add 50 g of 1,3-butadiene, 200 ml of dichloromethane (DCM), 10 g of TS-1, 0.1 g of tetrabutylammonium chloride, and 73 g of 30% hydrogen peroxide. Stir at room temperature for 2 hours. Then, heat to 70°C and react for 6 hours. GC monitoring indicates no product formation.

[0055] Comparative Example 2

[0056] Add 50g of 1,3-butadiene, 200ml of methanol, 10g of TS-1, and 73g of 30% hydrogen peroxide to an autoclave. Stir at room temperature for 2 hours. Then heat to 70°C and react for 6 hours. Cool to room temperature, filter, and concentrate the filtrate. Distill the crude product under reduced pressure to obtain 23g.

[0057] The applicant declares that while the above-mentioned examples are used to illustrate the one-pot synthesis method for 2-methoxy-3-butene-1-ol, the present application is not limited to the above-mentioned examples, and does not necessarily rely on the above-mentioned examples for implementation. Those skilled in the art should understand that any improvements to the present application, equivalent replacements for the raw materials of the present product, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present application.

[0058] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner unless there is any contradiction. In order to avoid unnecessary repetition, this application will not further describe various possible combinations.

Claims

1. A one-pot method for synthesizing 2-methoxy-3-butene-1-ol, characterized in that: The method comprises: mixing 1,3-butadiene, titanium silicon molecular sieve, methanol, peroxide and a phase transfer catalyst to react and prepare 2-methoxy-3-butene-1-ol.

2. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, wherein The titanium silicon molecules are selected from one or more of TS-1 and TS-2.

3. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, wherein The peroxide is hydrogen peroxide.

4. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, wherein The concentration of the peroxide is 30-50%.

5. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, wherein The phase transfer catalyst is selected from one or more of tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrapropylammonium chloride.

6. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, wherein Also includes any one or more of the following conditions: A1) the mass ratio of 1,3-butadiene to titanium silicalite is (5-10):1; A2) the mass volume ratio of 1,3-butadiene and methanol is 1 g: (3-5) mL; A3) the molar ratio of 1,3-butadiene to hydrogen peroxide is (1.5-2):1; A4) The mass ratio of the 1,3-butadiene to the phase transfer catalyst is (500-1000):

1.

7. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, characterized in that: After mixing, stir at room temperature for 2 to 5 hours and then react.

8. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, wherein: The reaction temperature is 60-80°C.

9. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, wherein: The reaction time is 6 to 16 hours.

10. The one-pot synthesis method of 2-methoxy-3-butene-1-ol according to claim 1, characterized in that: The method further comprises post-processing, wherein the post-processing comprises cooling to room temperature, filtering, concentrating the filtrate to obtain a crude product, and performing reduced-pressure distillation of the crude product.

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