Preparation method and application of acrylic fiber-supported FLP catalyst
By solidly supporting the FLP catalyst on acrylic fibers, the problem of poor stability of homogeneous FLP catalysts is solved, and efficient alkyne activation and catalytic cycle is achieved, which is suitable for industrial catalytic reactions.
Patent Information
- Application Number
- CN202311362548.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-19
- Publication Date
- 2025-08-12
- Estimated Expiration
- 2043-10-19
AI Technical Summary
The existing homogeneous FLP catalysts have poor stability and difficulty in recycling, which limits their application in large-scale alkyne activation reactions, and the traditional catalysts are costly and have poor environmental friendliness.
Acrylic fibers were used as support and piperazine was loaded onto acrylic fibers by a one-step process, followed by reaction with 3-bromopropylene and HB(C6F5)2 to form a FLP catalyst for catalyzing the cyclization isomerization reaction of 1,5-enyne derivatives.
The preparation process is simple, with high catalytic activity and good circulation performance. It is suitable for industrial fixed beds and has potential industrial application value.
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Figure CN117643915B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of green catalysis and relates to a preparation method and application of an acrylic fiber-supported FLP catalyst. Background Art
[0002] As an important chemical raw material, alkynes have important applications in organic synthesis. Although great progress has been made in the research of transition metal-catalyzed alkyne activation and transformation, the disadvantages of high catalyst price and poor environmental friendliness have seriously restricted its further application. In the past decade, hindered Lewis acid-base pair (FLP) chemistry has developed rapidly, providing a new method and idea for the activation of small molecules, and is one of the cutting-edge research topics in the field of chemistry. At the same time, most FLP catalysts use B / Al compounds as Lewis acids and N / P compounds as Lewis bases, which have inherent advantages such as low toxicity and low cost. However, the poor stability and difficulty of recycling of homogeneous FLP seriously restrict its application in large-scale catalytic reactions. Therefore, based on the homogeneous FLP activation alkyne system, the design and development of a precisely controllable and efficient heterogeneous FLP alkyne activation system is of great research value.
[0003] Acrylic fiber (PANF) is a common synthetic fiber with high physical and chemical stability. It is not only cheap and easy to obtain, but also has many modifiable sites (-CN) on the fiber and a large specific surface area, making it an excellent polymer carrier. The present invention has developed an acrylic fiber-immobilized FLP catalyst and applied it to catalyze the cycloisomerization reaction of 1,5-enyne derivatives, thereby preparing indene derivatives with biological and pharmacological activities. During the reaction, the catalyst can activate alkynes, and at the same time, the hindered Lewis base (FLB) can cause the hindered Lewis acid (FLA) bound to the reaction intermediate to fall off, thereby completing the catalytic cycle. Moreover, the catalyst has excellent softness and stability, and therefore has broad application prospects. Summary of the Invention
[0004] The primary purpose of the present invention is to overcome the shortcomings and deficiencies of existing technologies by providing a method for preparing an acrylic fiber-supported FLP catalyst with a simple preparation process, high catalytic activity, and excellent recyclability. The present invention utilizes the acrylic fiber-supported FLP catalyst for the cycloisomerization reaction of 1,5-enyne derivatives. This method offers advantages such as a simple catalyst preparation method, high catalytic activity, and excellent recyclability, and possesses considerable industrial application value.
[0005] The present invention adopts the following technical solutions:
[0006] A method for preparing an acrylic fiber-supported FLP catalyst comprises the following steps:
[0007] (1) Adding acrylic fiber to an aqueous solution of N-aminoethylpiperazine, heating under reflux under magnetic stirring, removing the fiber, cleaning it, and drying it to obtain piperazine-functionalized acrylic fiber PANF-P;
[0008] (2) adding piperazine-functionalized acrylic fiber PANF-P to a reaction solution and stirring uniformly, adding 3-bromopropylene and stirring to react, removing the fiber, cleaning it, and drying it to obtain allyl-functionalized acrylic fiber PANF-PO; the reaction solution is prepared by adding triphenylphosphine and diisopropyl azodicarboxylate to tetrahydrofuran and stirring uniformly;
[0009] (3) Finally, the allyl functionalized acrylic fiber PANF-PO was added to the toluene solution of HB(C6F5)2 and stirred for reaction. The fiber was taken out, cleaned and dried to obtain the acrylic fiber-supported FLP catalyst PANF-FLP.
[0010] Furthermore, in step (1), the volume ratio of N-aminoethylpiperazine to distilled water is 2:1-1:2, the mass volume ratio of acrylic fiber to N-aminoethylpiperazine aqueous solution is 1:15-1:50 g / mL, and the reflux reaction time is 2-12 h.
[0011] Furthermore, in step (2), the molar ratio of triphenylphosphine to diisopropyl azodicarboxylate is 1:1-1:3, the concentration of triphenylphosphine in the reaction solution is 50-120 mmol / L, and the mass volume ratio of piperazine functionalized acrylic fiber PANF-P to the reaction solution is 1:25-1:50 g / mL.
[0012] Furthermore, in step (2), the amount of 3-bromopropene added is 1.5-3 times that of triphenylphosphine, the reaction temperature is 20-60° C., and the reaction time is 12-72 h.
[0013] Furthermore, in step (3), the concentration of the HB(C6F5)2 toluene solution is 30-100 mmol / L, the reaction temperature is 20-80°C, and the reaction time is 8-24 h.
[0014] Furthermore, in step (3), the mass volume ratio of the allyl functionalized acrylic fiber PANF-PO to the toluene solution of HB(C6F5)2 is 1:25-1:50 g / mL.
[0015] Furthermore, the acrylic fiber-supported FLP catalyst prepared by the present invention is used in catalyzing the cycloisomerization reaction of 1,5-enyne derivatives.
[0016] After adopting the above technical solution, the present invention achieves the following beneficial effects:
[0017] (1) This invention is the first to prepare a solid FLP catalyst using acrylic fiber as a carrier. This catalyst has a simple preparation process, high catalytic activity, low cost, and good recyclability. It effectively solves the problems of existing FLP catalysts, such as complex preparation processes, suboptimal catalytic activity, and easy loss of catalytic sites.
[0018] (2) The acrylic fiber-supported FLP catalyst prepared by the present invention was applied to the cycloisomerization reaction of 1,5-enyne derivatives. The catalyst exhibited excellent catalytic activity, high reaction yield, and good recyclability. Furthermore, the acrylic fiber catalyst is highly flexible and can be woven into various shapes, facilitating the packing of industrial fixed beds, demonstrating its potential for industrial application. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 Schematic diagram of the synthesis route of the acrylic fiber-supported FLP catalyst of the present invention.
[0020] Figure 2 The present invention illustrates the cycloisomerization reaction of 1,5-enyne derivatives. DETAILED DESCRIPTION
[0021] The present invention will be further described below with reference to specific examples. It should be understood that the following examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention, and that those skilled in the art may make non-essential improvements and adjustments based on the contents of the above invention.
[0022] In the following embodiments, the schematic diagram of the synthesis route of acrylic fiber immobilized FLP catalyst is as follows: Figure 1 As shown, the cycloisomerization reaction of 1,5-enyne derivatives is exemplified by Figure 2 shown.
[0023] Example 1
[0024] This embodiment provides a method for preparing an acrylic fiber-immobilized FLP catalyst, comprising the following steps:
[0025] (1) In a 100 mL round-bottom flask, 1 g of dry acrylic fiber, 10 mL of N-aminoethylpiperazine, and 5 mL of distilled water were added and heated under reflux under magnetic stirring for 2 h. The fiber was then removed, cleaned, and dried to obtain piperazine-functionalized acrylic fiber PANF-P.
[0026] (2) 1 g of PANF-P fiber, 1.25 mmol of triphenylphosphine, 1.25 mmol of diisopropyl azodicarboxylate, and 25 mL of tetrahydrofuran were mixed evenly, and then 1.25 mmol of 3-bromopropylene was added. The mixture was stirred at 20 °C for 12 h. After that, the fiber was taken out, cleaned, and dried to obtain allyl-functionalized acrylic fiber PANF-PO.
[0027] (3) 1 g of allyl-functionalized acrylic fiber PANF-PO was added to 25 mL of 30 mmol / L HB(C6F5)2 toluene solution and stirred at 20°C for 8 h. Finally, the fiber was taken out, cleaned and dried to obtain the acrylic fiber-supported FLP catalyst PANF-FLP.
[0028] Example 2
[0029] This embodiment provides a method for preparing an acrylic fiber-immobilized FLP catalyst, comprising the following steps:
[0030] (1) In a 100 mL round-bottom flask, 1 g of dry acrylic fiber, 20 mL of N-aminoethylpiperazine, and 20 mL of distilled water were added and heated under reflux for 4 h under magnetic stirring. The fiber was then removed, cleaned, and dried to obtain piperazine-functionalized acrylic fiber PANF-P.
[0031] (2) 1 g of PANF-P fiber, 2.1 mmol of triphenylphosphine, 3.15 mmol of diisopropyl azodicarboxylate, and 30 mL of tetrahydrofuran were mixed evenly, and then 4.2 mmol of 3-bromopropylene was added. The mixture was stirred at 35 °C for 24 h. After that, the fiber was taken out, cleaned, and dried to obtain allyl-functionalized acrylic fiber PANF-PO.
[0032] (3) 1 g of allyl-functionalized acrylic fiber PANF-PO was added to 30 mL of 60 mmol / L HB(C6F5)2 toluene solution and stirred at 40 °C for 12 h. Finally, the fiber was taken out, cleaned and dried to obtain the acrylic fiber-supported FLP catalyst PANF-FLP.
[0033] Example 3
[0034] This embodiment provides a method for preparing an acrylic fiber-immobilized FLP catalyst, comprising the following steps:
[0035] (1) In a 100 mL round-bottom flask, 1 g of dry acrylic fiber, 20 mL of N-aminoethylpiperazine, and 30 mL of distilled water were added and heated under reflux under magnetic stirring for 8 h. The fiber was then removed, cleaned, and dried to obtain piperazine-functionalized acrylic fiber PANF-P.
[0036] (2) 1 g of PANF-P fiber, 4 mmol of triphenylphosphine, 8 mmol of diisopropyl azodicarboxylate and 40 mL of tetrahydrofuran were stirred evenly, and then 10 mmol of 3-bromopropylene was added. The mixture was stirred and reacted at 45 °C for 48 h. After that, the fiber was taken out, cleaned and dried to obtain allyl functionalized acrylic fiber PANF-PO.
[0037] (3) 1 g of allyl-functionalized acrylic fiber PANF-PO was added to 40 mL of 80 mmol / L HB(C6F5)2 toluene solution and stirred at 60 °C for 18 h. Finally, the fiber was taken out, cleaned and dried to obtain the acrylic fiber-supported FLP catalyst PANF-FLP.
[0038] Example 4
[0039] This embodiment provides a method for preparing an acrylic fiber-immobilized FLP catalyst, comprising the following steps:
[0040] (1) In a 100 mL round-bottom flask, 1 g of dry acrylic fiber, 10 mL of N-aminoethylpiperazine, and 20 mL of distilled water were added and heated under reflux for 12 h under magnetic stirring. The fiber was then removed, cleaned, and dried to obtain piperazine-functionalized acrylic fiber PANF-P.
[0041] (2) 1 g of PANF-P fiber, 7.5 mmol of triphenylphosphine, 22.5 mmol of diisopropyl azodicarboxylate, and 50 mL of tetrahydrofuran were stirred evenly, and then 22.5 mmol of 3-bromopropylene was added. The mixture was stirred and reacted at 60 °C for 72 h. After that, the fiber was taken out, cleaned, and dried to obtain allyl-functionalized acrylic fiber PANF-PO.
[0042] (3) 1 g of allyl-functionalized acrylic fiber PANF-PO was added to 50 mL of 100 mmol / L HB(C6F5)2 toluene solution and stirred at 80 °C for 24 h. Finally, the fiber was taken out, cleaned and dried to obtain the acrylic fiber-supported FLP catalyst PANF-FLP.
[0043] Example 5
[0044] The acrylic fiber-supported FLP catalyst prepared in the above example was used to catalyze the cycloisomerization reaction of 1,5-enyne derivatives, and the reaction was carried out as follows:
[0045] 2-(1-Isobutenyl)diphenylacetylene (1 mmol), a fiber catalyst (20 mol%), and 5 mL of toluene were added to a nitrogen-filled reaction tube. After nitrogen replacement three times, the reaction solution was stirred at 90°C for 20 hours. After the reaction solution cooled to room temperature, the catalyst was removed and washed three times with toluene. The organic phases were combined and spin-dried to obtain a crude product, which was then separated by column chromatography to obtain the final product. The experimental results are shown in Tables 1 and 2.
[0046] Comparative Example 1
[0047] B(C6F5)3 was used to catalyze the cycloisomerization reaction of 1,5-enyne derivatives according to the following scheme:
[0048] 2-(1-Isobutenyl)toluene (1 mmol), B(C6F5)3 (20 mol%), and 5 mL of toluene were added to a nitrogen-filled reaction tube. After nitrogen replacement three times, the reaction solution was stirred at 90°C for 20 hours. After the reaction solution cooled to room temperature, the catalyst was removed and washed three times with toluene. The organic phases were combined and spin-dried to obtain a crude product, which was then separated by column chromatography to obtain the final product. The experimental results are shown in Table 1.
[0049] Table 1 Evaluation of the catalytic activity of acrylic fiber-supported FLP in the cycloisomerization reaction of 1,5-enyne derivatives
[0050] catalyst Yield (%) Example 1 85 Example 2 93 Example 3 88 Example 4 86 Comparative Example 1 20
[0051] Table 2 Evaluation of catalyst cycle performance in Example 2
[0052] Number of cycles 2 4 6 8 10 Yield (%) 92 92 91 90 90
[0053] Table 1 shows that the catalyst of this invention efficiently catalyzes the cycloisomerization reaction of 1,5-enyne derivatives with a yield as high as 93%. Under optimal conditions, the catalyst of Example 2 was used in a cyclic performance test, with the results shown in Table 2. After 10 cycles, the catalyst still achieved a 90% yield and retained 97% of its catalytic activity, demonstrating the catalyst's excellent cyclic performance.
[0054] It should be understood that the embodiments of the present invention are intended to be illustrative and not to limit the scope of protection of the present invention in any form. Those skilled in the art may make improvements based on the above examples, and all such improvements shall fall within the scope of protection of the appended claims of the present invention.
Claims
1. Use of an acrylic fiber-supported FLP catalyst in the catalytic cycloisomerization reaction of 1,5-enyne derivatives, characterized by: The preparation method of the acrylic fiber-supported FLP catalyst comprises the following steps: (1) Add acrylic fiber N -aminoethylpiperazine in an aqueous solution, heated under reflux under magnetic stirring for reaction, and then the fiber was taken out, cleaned and dried to obtain piperazine functionalized acrylic fiber PANF-P; (2) adding piperazine functionalized acrylic fiber PANF-P fiber to the reaction solution and mixing and stirring uniformly, adding 3-bromopropylene and stirring to react, taking out the fiber, cleaning it and drying it to obtain allyl functionalized acrylic fiber PANF-PO; the reaction solution is prepared by adding triphenylphosphine and diisopropyl azodicarboxylate to tetrahydrofuran and mixing and stirring uniformly; (3) Finally, the allyl functionalized acrylic fiber PANF-PO was added to the toluene solution of HB(C6F5)2 and stirred for reaction. The fiber was then taken out, cleaned and dried to obtain the acrylic fiber-supported FLP catalyst PANF-FLP.
2. The use according to claim 1, characterized in that: In step (1), N -The volume ratio of aminoethylpiperazine to distilled water is 2:1-1:2, acrylic fiber and N The mass volume ratio of the 2-aminoethylpiperazine aqueous solution is 1:15-1:50 g / mL, and the reflux reaction time is 2-12 h.
3. The use according to claim 1, characterized in that: In step (2), the molar ratio of triphenylphosphine to diisopropyl azodicarboxylate is 1:1-1:3, the concentration of triphenylphosphine in the reaction solution is 50-120 mmol / L, and the mass volume ratio of piperazine functionalized acrylic fiber PANF-P to the reaction solution is 1:25-1:50 g / mL.
4. The use according to claim 1, characterized in that: In step (2), the amount of 3-bromopropene added is 1.5-3 times that of triphenylphosphine, the reaction temperature is 20-60°C, and the reaction time is 12-72 h.
5. The use according to claim 1, characterized in that: In step (3), the concentration of the HB(C6F5)2 toluene solution is 30-100 mmol / L, the reaction temperature is 20-80°C, and the reaction time is 8-24 h.
6. The use according to claim 1, characterized in that: In step (3), the mass volume ratio of the allyl functionalized acrylic fiber PANF-PO to the toluene solution of HB(C6F5)2 is 1:25-1:50 g / mL.
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