High-activity catalyst for synthesis of five-membered cyclic carbonate

Abstract

The invention relates to the technical field of organic synthesis, and discloses a high-activity catalyst for synthesizing five-membered cyclic carbonate. The invention relates to a high-activity catalyst for synthesis of five-membered cyclic carbonate, the structural formula of the high-activity catalyst is # imgabs0, and when the high-activity catalyst for synthesis of five-membered cyclic carbonate is applied to synthesis of five-membered cyclic carbonate, the high-activity catalyst has high catalytic activity and stability.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and more particularly, to a highly active catalyst for the synthesis of five-membered cyclic carbonates. Background Art

[0002] Five-membered cyclic carbonates are important organic compounds with excellent properties and broad application prospects, and have become one of the research hotspots in the chemical field; five-membered cyclic carbonates have many excellent chemical properties, such as high stability, thermal stability, and chemical inertness, etc., and at the same time also have excellent electron transfer properties, and are an ideal material with wide applications in the chemical industry.

[0003] Under natural conditions, carbon dioxide and epoxides are difficult to undergo cycloaddition reactions, or the efficiency of the reaction between the two to form cyclic carbonates is low; therefore, selecting a suitable catalyst can effectively improve the efficiency of the reaction between carbon dioxide and epoxides to form cyclic carbonates; in the prior art, cyclic carbonates are mostly prepared using binary catalysts composed of Lewis acid metals and Lewis bases. Among them, the Lewis acid metals include: alkali metal halides, alkaline earth metal halides, transition metal salts, transition metal complexes, or Schiff base metal complexes, and the Lewis bases include organic bases, quaternary ammonium salts, imidazolium salts, solid bases, crown ethers, molecular sieves, etc.; these catalyst systems more or less have problems such as low catalytic activity, poor stability, harsh reaction conditions, the use of highly toxic organic solvents, and high catalyst costs; therefore, developing a highly active catalyst with high catalytic activity and stability has become a technical problem that needs to be solved urgently by those skilled in the art. Summary of the Invention

[0004] The purpose of the present invention is to provide a highly active catalyst for the synthesis of five-membered cyclic carbonates, which has high catalytic activity and stability when used in the synthesis of five-membered cyclic carbonates.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] One of the technical solutions of the present invention:

[0007] A highly active catalyst for the synthesis of five-membered cyclic carbonates, whose structural formula is:

[0008]

[0009] Wherein, R 1 , R 2 , R 3 , R 4 are independently selected from: -OH, -NO 2 , -CF 3 ,

[0010]

[0011] Among them, R 5 、R 6 、R 7 are independently selected from: C1-C4 alkyl groups.

[0012] Preferably, R 1 、R 2 、R 3 、R 4 are independently selected from: -OH, -NO 2 、-CF 3 、

[0013]

[0014] More preferably, R 1 、R 2 、R 3 、R 4 are independently selected from: -OH, -NO 2 、

[0015]

[0016] Preferably, R 5 、R 6 、R 7 are independently selected from: i-Pr, i-Bu, s-Bu or t-Bu.

[0017] More preferably, R 5 、R 6 、R 7 are independently selected from: i-Bu or t-Bu.

[0018] A highly active catalyst for the synthesis of five-membered cyclic carbonates according to the present invention has a typical structure including:

[0019]

[0020]

[0021]

[0022] The second technical solution of the present invention:

[0023] A method for synthesizing a five-membered cyclic carbonate, comprising the following steps:

[0024] Using carbon dioxide and epoxide as raw materials, and using the highly active catalyst for the synthesis of five-membered cyclic carbonate described above as the catalyst, a cycloaddition reaction occurs at 100-150 °C to obtain the five-membered cyclic carbonate.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] When the highly active catalyst for the synthesis of five-membered cyclic carbonate provided by the present invention is applied to the synthesis of five-membered cyclic carbonate, it has high catalytic activity, and the product conversion rate can reach 98% at 30 min.

[0027] When the highly active catalyst for the synthesis of five-membered cyclic carbonate provided by the present invention is applied to the synthesis of five-membered cyclic carbonate, it has high stability. After being recycled three times, the product conversion rate can still reach 98%.

[0028] In the highly active catalyst for the synthesis of five-membered cyclic carbonate provided by the present invention, the positively charged nitrogen atom (N + ) can serve as a Lewis acid site to effectively activate the epoxide and promote the ring-opening reaction. At the same time, the B atom can also serve as a Lewis acid site to further enhance the activation effect on the epoxide; by adjusting different substituents (-OH, -NO 2 , -CF 3 , etc.), the electronic properties and spatial structure of the catalyst can be further optimized, and the performance of the catalyst can be further improved. For example, -OH can provide hydrogen bond interaction, enhance the interaction between the catalyst and the substrate, and may also promote the reaction as a proton source. -NO 2 is a strong electron-withdrawing group, which can adjust the electron density of N + and the B atom, and enhance its Lewis acidity. -CF 3 is also a strong electron-withdrawing group, which can further enhance its Lewis acidity and improve the stability of the catalyst; the benzene ring structure can provide π-π interaction, enhance the interaction between the catalyst and the substrate, and improve the catalytic activity and selectivity. Detailed Embodiments

[0029] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and implementation embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific implementation embodiments and are not used to limit the present invention.

[0030] In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0031] Unless otherwise noted, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0032] Without departing from the scope or spirit of the present invention, various modifications and variations can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.

[0033] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0034] In the present invention, the technical term "Me" refers to "methyl", with the chemical formula "CH 3 -"; the technical term "Et" refers to "ethyl", with the chemical formula "CH 3 CH 2 -"; the technical term "n-Pr" refers to "n-propyl", with the chemical formula "CH 3 CH 2 CH 2 -"; the technical term "i-Pr" refers to "isopropyl", with the chemical formula "(CH 3 ) 2 CH-"; the technical term "n-Bu" refers to "n-butyl", with the chemical formula "CH 3 CH 2 CH 2 CH 2 -"; the technical term "i-Bu" refers to "isobutyl", with the chemical formula "(CH 3 ) 2 CHCH 2 -"; the technical term "s-Bu" refers to "sec-butyl", with the chemical formula "CH 3 CH(CH 3 )CH2 -”; The technical term "t-Bu" refers to "tert-butyl" with the chemical formula "(CH 3 ) 3 C-".

[0035] In the following examples, a highly active catalyst for the synthesis of five-membered cyclic carbonates has the following structural formula:

[0036]

[0037] Wherein, R 1 , R 2 , R 3 , R 4 are independently selected from: -OH, -NO 2 , -CF 3 ,

[0038] Wherein, R 5 , R 6 , R 7 are independently selected from: C1-C4 alkyl groups.

[0039] In the present invention, a method for synthesizing five-membered cyclic carbonates uses carbon dioxide and epoxides as raw materials. In the following examples, ethylene oxide is taken as an example to detect the catalytic activity and catalytic stability of the highly active catalyst.

[0040] In the following examples, the synthesis equation of a highly active catalyst for the synthesis of five-membered cyclic carbonates is as follows:

[0041]

[0042] In the above synthesis equation, R in the formula needs to be reasonably selected according to the target product;

[0043] In the synthesis equation, DPPA is diphenylphosphoryl azide, DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene, PMe 3 is trimethylphosphine, RBr is bromoalkane, and DMF is N,N-dimethylformamide.

[0044] Example 1

[0045] Synthesis of a five-membered cyclic carbonate

[0046] Add 1 mol of ethylene oxide and 0.05 mol of the highly active catalyst to the reaction kettle, and fill it with CO 2 until the pressure in the reaction kettle is 5 MPa, adjust the temperature in the reaction kettle to 110 °C, and carry out the cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0047] After calculation, the yield of the five-membered cyclic carbonate in Example 1 was 96%.

[0048] The highly active catalyst used in Example 1 was recovered, and the five-membered cyclic carbonate was repeatedly prepared according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remained at 96%.

[0049] Example 2

[0050] Synthesis of a five-membered cyclic carbonate

[0051] 1 mol of ethylene oxide and 0.05 mol of highly active catalyst were added to the reaction kettle, and CO 2 was charged until the pressure in the reaction kettle reached 5 MPa, the temperature in the reaction kettle was adjusted to 100 °C, and the cycloaddition reaction was carried out for 30 min to obtain the five-membered cyclic carbonate.

[0052] After calculation, the yield of the five-membered cyclic carbonate in Example 2 was 94%.

[0053] The highly active catalyst used in Example 2 was recovered, and the five-membered cyclic carbonate was repeatedly prepared according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remained at 94%.

[0054] Example 3

[0055] Synthesis of a five-membered cyclic carbonate

[0056] 1 mol of ethylene oxide and 0.05 mol of highly active catalyst were added to the reaction kettle, and CO 2 was charged until the pressure in the reaction kettle reached 5 MPa, the temperature in the reaction kettle was adjusted to 130 °C, and the cycloaddition reaction was carried out for 30 min to obtain the five-membered cyclic carbonate.

[0057] After calculation, the yield of the five-membered cyclic carbonate in Example 3 was 97%.

[0058] The highly active catalyst used in Example 3 was recovered, and the five-membered cyclic carbonate was repeatedly prepared according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remained at 97%.

[0059] Example 4

[0060] Synthesis of a five-membered cyclic carbonate

[0061] 1 mol of ethylene oxide and 0.05 mol of highly active catalyst were added to the reaction kettle, and CO 2Until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 120 °C, and carry out the cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0062] After calculation, the yield of the five-membered cyclic carbonate in Example 4 is 95%.

[0063] Recover the highly active catalyst used in Example 4, and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 95%.

[0064] Example 5

[0065] Synthesis of a five-membered cyclic carbonate

[0066] Add 1 mol of ethylene oxide and 0.05 mol of highly active catalyst to the reaction kettle, and fill it with CO 2 Until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 100 °C, and carry out the cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0067] After calculation, the yield of the five-membered cyclic carbonate in Example 5 is 98%.

[0068] Recover the highly active catalyst used in Example 5, and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 98%.

[0069] Example 6

[0070] Synthesis of a five-membered cyclic carbonate

[0071] Add 1 mol of ethylene oxide and 0.05 mol of highly active catalyst to the reaction kettle, and fill it with CO 2 Until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 140 °C, and carry out the cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0072] After calculation, the yield of the five-membered cyclic carbonate in Example 6 is 92%.

[0073] Recover the highly active catalyst used in Example 6, and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 92%.

[0074] Example 7

[0075] Synthesis of a five-membered cyclic carbonate

[0076] Add 1 mol of ethylene oxide and 0.05 mol of highly active catalyst Add it to the reaction kettle and charge it with CO 2 Until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 140 °C, and carry out the cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0077] After calculation, the yield of the five-membered cyclic carbonate in Example 7 is 87%.

[0078] Recover the highly active catalyst used in Example 7, and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 87%.

[0079] Example 8

[0080] Synthesis of a five-membered cyclic carbonate

[0081] Add 1 mol of ethylene oxide and 0.05 mol of highly active catalyst Add it to the reaction kettle and charge it with CO 2 Until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 130 °C, and carry out the cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0082] After calculation, the yield of the five-membered cyclic carbonate in Example 8 is 83%.

[0083] Recover the highly active catalyst used in Example 8, and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 83%.

[0084] Example 9

[0085] Synthesis of a five-membered cyclic carbonate

[0086] Add 1 mol of ethylene oxide and 0.05 mol of highly active catalyst Add it to the reaction kettle and charge it with CO 2 Until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 110 °C, and carry out the cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0087] After calculation, the yield of the five-membered cyclic carbonate in Example 9 is 95%.

[0088] Recover the highly active catalyst used in Example 9, and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 95%.

[0089] Example 10

[0090] Synthesis of a five-membered cyclic carbonate

[0091] Add 1 mol of ethylene oxide and 0.05 mol of a highly active catalyst to a reaction kettle and charge it with CO 2 until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 110 °C, and carry out a cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0092] Calculated, the yield of the five-membered cyclic carbonate in Example 10 is 95%.

[0093] Recover the highly active catalyst used in Example 10 and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 95%.

[0094] Example 11

[0095] Synthesis of a five-membered cyclic carbonate

[0096] Add 1 mol of ethylene oxide and 0.05 mol of a highly active catalyst to a reaction kettle and charge it with CO 2 until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 120 °C, and carry out a cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0097] Calculated, the yield of the five-membered cyclic carbonate in Example 11 is 93%.

[0098] Recover the highly active catalyst used in Example 11 and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 93%.

[0099] Example 12

[0100] Synthesis of a five-membered cyclic carbonate

[0101] Add 1 mol of ethylene oxide and 0.05 mol of a highly active catalyst to a reaction kettle and charge it with CO 2 until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 120 °C, and carry out a cycloaddition reaction for 30 min to obtain the five-membered cyclic carbonate.

[0102] Calculated, the yield of the five-membered cyclic carbonate in Example 12 is 91%.

[0103] Recover the highly active catalyst used in Example 12 and repeat the preparation of the five-membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five-membered cyclic carbonate remains at 91%.

[0104] Example 13

[0105] Synthesis of a five - membered cyclic carbonate

[0106] Add 1 mol of ethylene oxide and 0.05 mol of a highly active catalyst into a reaction kettle, and fill it with CO 2 until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 130 °C, and carry out a cycloaddition reaction for 30 min to obtain the five - membered cyclic carbonate.

[0107] Calculated, the yield of the five - membered cyclic carbonate in Example 13 is 96%.

[0108] Recover the highly active catalyst used in Example 13, and repeat the preparation of the five - membered cyclic carbonate according to the above - mentioned preparation method. After three repeated preparations, the yield of the five - membered cyclic carbonate remains at 96%.

[0109] Example 14

[0110] Synthesis of a five - membered cyclic carbonate

[0111] Add 1 mol of ethylene oxide and 0.05 mol of a highly active catalyst into a reaction kettle, and fill it with CO 2 until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 100 °C, and carry out a cycloaddition reaction for 30 min to obtain the five - membered cyclic carbonate.

[0112] Calculated, the yield of the five - membered cyclic carbonate in Example 14 is 98%.

[0113] Recover the highly active catalyst used in Example 14, and repeat the preparation of the five - membered cyclic carbonate according to the above - mentioned preparation method. After three repeated preparations, the yield of the five - membered cyclic carbonate remains at 98%.

[0114] Example 15

[0115] Synthesis of a five - membered cyclic carbonate

[0116] Add 1 mol of ethylene oxide and 0.05 mol of a highly active catalyst into a reaction kettle, and fill it with CO 2 until the pressure in the reaction kettle reaches 5 MPa, adjust the temperature in the reaction kettle to 140 °C, and carry out a cycloaddition reaction for 30 min to obtain the five - membered cyclic carbonate.

[0117] Calculated, the yield of the five - membered cyclic carbonate in Example 15 is 87%.

[0118] Recover the highly active catalyst used in Example 15, and repeat the preparation of the five - membered cyclic carbonate according to the above - mentioned preparation method. After three repeated preparations, the yield of the five - membered cyclic carbonate remains at 87%.

[0119] Example 16

[0120] Synthesis of a five - membered cyclic carbonate

[0121] Add 1 mol of ethylene oxide and 0.05 mol of a highly active catalyst into a reaction kettle, and fill it with CO 2 until the pressure in the reaction kettle is 5 MPa, adjust the temperature in the reaction kettle to 150 °C, and carry out a cycloaddition reaction for 30 min to obtain the five - membered cyclic carbonate.

[0122] Calculated, the yield of the five - membered cyclic carbonate in Example 16 is 79%.

[0123] Recover the highly active catalyst used in Example 16, and repeat the preparation of the five - membered cyclic carbonate according to the above preparation method. After three repeated preparations, the yield of the five - membered cyclic carbonate remains at 79%.

[0124] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to the above examples, those of ordinary skill in the art should understand that: modifications or equivalent replacements can still be made to the specific embodiments of the present invention. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention shall be covered by the protection scope of the claims of the present invention.

Claims

1. A highly active catalyst for the synthesis of five-membered ring carbonates, characterized in that: The structural formula of the highly active catalyst for the synthesis of five-membered ring carbonate is: Wherein, R1, R2, R3, and R4 are independently selected from: -OH, -NO2, -CF3, Wherein, R5, R6, and R7 are independently selected from: C1-C4 alkyl.

2. A highly active catalyst for the synthesis of five-membered ring carbonate according to claim 1, characterized in that: The R1, R2, R3, and R4 are independently selected from: -OH, -NO2, -CF3, 3. A highly active catalyst for the synthesis of five-membered ring carbonate according to claim 1, characterized in that: The R1, R2, R3, and R4 are independently selected from: -OH, -NO2, 4. A highly active catalyst for the synthesis of five-membered ring carbonate according to claim 1, characterized in that: The R5, R6, and R7 are independently selected from: i-Pr, i-Bu, s-Bu or t-Bu.

5. A highly active catalyst for the synthesis of five-membered ring carbonate according to claim 1, characterized in that: The R5, R6, and R7 are independently selected from: i-Bu or t-Bu.

6. A method for synthesizing a five-membered ring carbonate, characterized in that: The following steps are involved: Carbon dioxide and epoxide are used as raw materials, and the highly active catalyst for synthesizing five-membered ring carbonate as claimed in any one of claims 1 to 5 is used as a catalyst to carry out a cycloaddition reaction at 100 to 150° C. to obtain the five-membered ring carbonate.

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