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磺胺嘧啶银/超强碱协同催化CO2/醇耦合反应选择性制碳酸二甲酯

张福灿 刘平 张侃 吉可明 张建利 赵亮 宋清文

张福灿, 刘平, 张侃, 吉可明, 张建利, 赵亮, 宋清文. 磺胺嘧啶银/超强碱协同催化CO2/醇耦合反应选择性制碳酸二甲酯[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60053-7
引用本文: 张福灿, 刘平, 张侃, 吉可明, 张建利, 赵亮, 宋清文. 磺胺嘧啶银/超强碱协同催化CO2/醇耦合反应选择性制碳酸二甲酯[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60053-7
ZHANG Fu-can, LIU Ping, ZHANG Kan, JI Ke-ming, ZHANG Jian-li, ZHAO Liang, SONG Qing-wen. Synergistic silver sulfadiazine/superbase-catalyzed selective synthesis of dimethyl carbonate via the coupling reaction of CO2 and alcohols[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60053-7
Citation: ZHANG Fu-can, LIU Ping, ZHANG Kan, JI Ke-ming, ZHANG Jian-li, ZHAO Liang, SONG Qing-wen. Synergistic silver sulfadiazine/superbase-catalyzed selective synthesis of dimethyl carbonate via the coupling reaction of CO2 and alcohols[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60053-7

磺胺嘧啶银/超强碱协同催化CO2/醇耦合反应选择性制碳酸二甲酯

doi: 10.1016/S1872-5813(22)60053-7
基金项目: 山西省自然科学基金(20210302123002, 202103021223460),潞安化工集团有限公司研发基金和省部共建煤炭高效利用与绿色化工国家重点实验室开放基金(2022-K20)资助。
详细信息
    通讯作者:

    E-mail: jikeming@sxicc.ac.cn

    songqingwen@sxicc.ac.cn

  • 中图分类号: O622.5

Synergistic silver sulfadiazine/superbase-catalyzed selective synthesis of dimethyl carbonate via the coupling reaction of CO2 and alcohols

Funds: The project was supported by the Natural Science Foundation of Shanxi (20210302123002, 202103021223460), Technical research and development project from Lu'an Chemical Industry Group Co., Ltd. and the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2022-K20).
  • 摘要: 甲醇、CO2和炔丙醇三组分耦合反应为合成绿色化学品碳酸二甲酯(DMC)提供了一种热力学有利新路径。本工作针对该方法中存在的DMC收率低、中间产物转化速率慢的问题,研究了炔烃衍生物α-单取代炔丙醇在耦合反应中对DMC收率及选择性的影响。发展了磺胺嘧啶银与超强碱协同催化串联反应策略,进一步提升了反应效率。详细考察了催化剂、共催化剂、催化剂用量、溶剂、温度、原料比、压力和时间等因素的影响规律。最优的条件下,DMC选择性达89.5%,收率55.6%。研究表明,炔丙醇的结构会显著影响反应进程,同时,磺胺嘧啶银与1,8-二氮杂二环十一碳-7-烯(DBU)的协同催化作用是高收率、高选择性获得DMC的关键因素。
  • 图  1  催化剂用量的考察

    Figure  1  Investigation of the catalyst loading

    Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), DBU (228 mg, 1.5 mmol), CO2 (5 MPa), 120 ℃, 8 h. The loading of silver sulfadiazine was calculated on the basis of 1a. The results were determined by GC using biphenyl as the internal standard.

    图  2  温度对反应的影响

    Figure  2  Temperature effect on the reaction

    Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), CO2 (5 MPa), 8 h. The results were determined by GC using biphenyl as the internal standard.

    图  3  原料配比对反应的影响

    Figure  3  Effect of raw material ratio on reaction

    Reaction condition: 1a (620 mg, 5 mmol), 2a (160 ~ 640 mg, 10 ~ 40 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), CO2 (5 MPa), 120 ℃, 8 h. The yield was determined by GC using biphenyl as the internal standard.

    图  4  压力对三组分反应的影响

    Figure  4  Pressure effect on the three-component reaction

    Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), 120 ℃, 8 h. The results were determined by GC using biphenyl as the internal standard.

    图  5  时间对反应的影响。(a)原料1a和2a转化率;(b)产物DMC和4a收率;(c)产物DMC和4a选择性。

    Figure  5  Law of time on the reaction. (a) Conversion of raw materials 1a and 2a; (b) Yield of DMC and 4a; (c) Selectivity of DMC and 4a.

    Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), CO2 (5 MPa), 120 ℃. The results were determined by GC using biphenyl as the internal standard.

    图  6  炔丙醇结构与DMC收率和选择性的关系

    Figure  6  Relationship between propargyl alcohol structure and the yield/selectivity of DMC

    Reaction condition: propargyl alcohol (5 mmol), methanol (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), CO2 (5 MPa), 120 ℃, 8 h. The results were determined by GC using biphenyl as the internal standard.

    图  7  磺胺嘧啶银/DBU催化炔丙醇、甲醇和CO2三组分耦合反应机理

    Figure  7  Cascade reaction mechanism of propargyl alcohol, methanol and CO2 catalyzed by silver sulfadiazine/DBU

    表  1  催化剂考察

    Table  1  Catalysts investigation

    EntryCatalyst1a Conv./%2a Conv./%DMC Yield/%4a Yield/%DMC Sel./%4a Sel./%
    1a-0000--
    2-62.950.015.625.231.250.4
    3CoCO314.110.23.75.636.354.9
    4NiBr233.732.33.38.010.224.8
    5CuBr96.548.635.436.372.974.7
    6ZnCl299.980.329.634.736.943.2
    7ZnBr298.777.533.139.042.754.6
    8ZnI298.340.617.827.143.842.5
    9Zn(OAc)299.258.630.441.651.971.1
    10AgCl98.139.230.535.177.789.6
    11AgI99.538.116.723.743.862.1
    12AgOAc99.044.034.841.579.194.2
    13Ag2SO499.364.926.235.940.555.4
    14Ag3PO496.341.927.736.966.288.1
    15AgVO353.635.820.027.756.177.5
    16CF3SO3Ag95.762.810.123.116.036.9
    17C7H5AgO297.238.925.229.764.876.3
    18Ag2CO376.861.912.246.919.775.9
    19Ag2O98.853.840.446.375.186.1
    20silver sulfadiazine99.953.141.842.678.780.4
    Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), catalyst (1 mmol), DBU (228 mg, 1.5 mmol), CO2 (5 MPa), 120 ℃, 8 h. aIn the absence of any catalyst and cocatalyst. The results were determined by GC using biphenyl as the internal standard. Conversion (Conv.), selectivity (sel.).
    下载: 导出CSV

    表  2  共催化剂考察

    Table  2  Co-catalyst investigation

    EntryCo-catalyst1a Conv./%2a Conv./%DMC
    Yield/%
    4a Yield/%DMC Sel./%4a Sel./%
    1a-87.642.32.24.45.210.4
    2DBU99.953.141.842.678.780.2
    3DBN98.572.721.934.830.147.9
    4TMG99.765.017.518.526.928.5
    5TBD98.772.62.23.53.04.8
    6TBAB100.088.23.23.43.63.9
    7TEAC99.578.74.77.26.09.1
    8TBAB/DBU99.773.622.835.531.048.2
    9PPh3/DBU100.049.22.86.45.713.0
    Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (1 mmol), cocatalyst (1.5 mmol), CO2 (5 MPa), 120 ℃, 8 h. aOnly silver sulfadiazine was used. The results were determined by GC using biphenyl as the internal standard.
    下载: 导出CSV

    表  3  溶剂对反应的影响

    Table  3  Solvent effect on the reaction

    EntrySolvent1a
    Conv./%
    2a Conv./%DMC
    Yield/%
    4a Yield/%DMC Sel./%4a Sel./%
    1Blank99.953.141.842.678.780.4
    2DMSO99.662.155.659.489.595.7
    3DMF99.553.935.739.066.372.4
    4CH3CN99.558.234.437.859.165.0
    5EtOAc99.448.724.433.350.068.4
    6PhCH398.051.337.341.772.881.3
    7tetrahydrofuran99.649.229.235.259.371.5
    Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), solvent (1 mL), CO2 (5 MPa), 120 ℃, 8 h. The results were determined by GC using biphenyl as the internal standard.
    下载: 导出CSV
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  • 收稿日期:  2022-05-19
  • 录用日期:  2022-07-13
  • 修回日期:  2022-07-07
  • 网络出版日期:  2022-07-28

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