介孔氧化硅微囊反应器中不对称氢转移合成手性α-苯乙醇的研究
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摘要
无机介孔氧化硅材料具有规整的孔道结构、连续可调的孔径、良好的稳定性等优点,可作为催化反应的微囊反应器。今以无机介孔二氧化硅微球为微囊反应器,利用"ship-in-a-bottle"策略,将均相催化剂封装在介孔SiO2微球中,采用SEM、BET、TEM、FT-IR等手段进行表征,并应用在苯乙酮的不对称氢转移反应中。在60℃下反应6h,苯乙酮转化率和苯乙醇的对映体选择性最高分别达到52.4%和95.5%,且重复使用5次后,催化剂仍保持较高活性。以甲酸钠为氢源,考察了反应温度、反应时间、反应物的加入量对底物转化率和产物对映体选择性的影响。研究结果表明,将均相铑催化剂封装在二氧化硅微囊反应器中,在获得高转化率和对映体选择性的同时,可以提高催化剂的重复利用率,降低生产成本,符合绿色化学的要求。
Inorganic mesoporous silica can be used as a microcapsule reactor for its regular spherical structure, slits pore structure and good stability. Rhodium catalysts were synthesized in mesoporous silica through a "ship-in-a-bottle" strategy and used for asymmetric transfer hydrogenation of acetophenone. The structure of the microcapsule reactor was characterized through BET, XRD, FT-IR and TEM. Effects of reaction temperature, reaction time, reactant amount on catalyst performance were investigated with sodium formate as the hydrogen source. Under optimum conditions of 60℃, 6 h and 0.2 m L acetophenone, the catalyst shows its highest performance of acetophenone conversion(52.4%) and enantio selectivity(95.5%) of R-α-phenethyl alcohol in asymmetric transfer hydrogenation of acetophenone. The conversion and ee value maintained after recycling for five times. The results show that the catalyst supported with mesoporous silica through "ship-in-a-bottle" strategy has good catalytic performance and can be recycled, which complies with the requirements of green chemistry.
Inorganic mesoporous silica can be used as a microcapsule reactor for its regular spherical structure, slits pore structure and good stability. Rhodium catalysts were synthesized in mesoporous silica through a "ship-in-a-bottle" strategy and used for asymmetric transfer hydrogenation of acetophenone. The structure of the microcapsule reactor was characterized through BET, XRD, FT-IR and TEM. Effects of reaction temperature, reaction time, reactant amount on catalyst performance were investigated with sodium formate as the hydrogen source. Under optimum conditions of 60℃, 6 h and 0.2 m L acetophenone, the catalyst shows its highest performance of acetophenone conversion(52.4%) and enantio selectivity(95.5%) of R-α-phenethyl alcohol in asymmetric transfer hydrogenation of acetophenone. The conversion and ee value maintained after recycling for five times. The results show that the catalyst supported with mesoporous silica through "ship-in-a-bottle" strategy has good catalytic performance and can be recycled, which complies with the requirements of green chemistry.
引文
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[17]LIU Ke-tang(刘克堂),XU Yuan-yuan(徐圆圆),DUAN Meng-yuan(段梦圆),et al.Graphene oxide based chiral dianfine rhodium catalyst for asymmetric transfer hydrogenation of aromatic ketones(氧化石墨负载的手性二胺铑催化剂催化芳香酮的不对称氢转移反应)[J].Shanghai(上海):Journal of Shanghai Normal University(上海师范大学学报),2013,42(1):106-110.
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[20]YANG Heng-quan,ZHANG Lei,LI Can,et al.Asymmetric ring-opening of epoxides on chiral Co(Salen)catalyst synthesized in SBA-16 through the“ship in a bottle”strategy[J].Journal of Catalysis,2007,248(2):204-212.
[21]LI Yan(李艳).Preparation and characterization of asymmetric hydrogenation catalyst support by MCM-48(MCM-48固载不对称加氢催化剂的制备及表征)[D].Tianjin(天津):Nankai Universit(南开大学),2007.
[22]ZHANG Yu-li(张玉利).Research on preparation of mesoporous silica supported Pd,Rh original metal catalyst and catalysis reaction(介孔氧化硅负载Pd-Rh有机金属催化剂的制备及其催化反应研究)[D].Shanghai(上海):Shanghai Normal University(上海师范大学),2011.
[23]ZHANG Yue(张跃),ZHENG Peng-cheng(郑鹏程),YAN Sheng-hu(严生虎),et al.Synthesis process of glutaraldehyde by catalytic oxidation of cyclopentene in microreactor(微反应器中环戊烯催化氧化制备戊二醛)[J].Fine Chemicals(精细化工),2012,29(1):91-93.
[2]BAI S Y,YANG H Q,WANG P,et al.Enhancement of catalytic performance in asymmetric transfer hydrogenation by microenvironment engineering of the nanocage[J].Chemical Communications,2010,46(43):8145-8147.
[3]HU Ming-ming(胡明明).Investigation about preparation of chiralα-phenylethanol by acetophenone using catalytic asymmetric reduction(苯乙酮不对称催化还原制手性α-苯乙醇研究)[D].Beijing(北京):Beijing University of Chemical Technology(北京理工大学),2012.
[4]YUAN Jian(袁剑),ZHANG Bo(张波),TANG Ming-hui(汤明慧),et al.Hydrogen-Transfer Reaction of Acetophenone over ZrO2/MCM-41(ZrO2/MCM-41催化的苯乙酮氢转移反应)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2013,27(5):818-824.
[5]WANG Fei(王飞).Research on asymmetric transfer hydrogenation of ketones in aqueous media(水介质中酮的不对称氢转移反应的研究)[D].Chengdu(成都):Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences(中国科学院成都有机化学研究所),2005.
[6]SHI Jing(史静).Research on synthesis and application of microcapsular reactor(沸石微囊反应器合成与应用研究)[D].Shanghai(上海):Fudan University(复旦大学),2012.
[7]Ren Y,Ma Z,Bruce P G.Ordered mesoporous metal oxides:synthesis and applications[J].Chemical Society Reviews,2012,41(14),4909-4927.
[8]ZHOU Chun-hui(周春晖),LI Chun-sheng(李春生),TONG Dong-shen(童东绅),et al.Structure and catalytic feature of InCl3impregnated nesoporous HMS solid catalyst for alkylation reaction of a chromatic compounds(InCl3/HMS介孔催化剂的结构及其催化烷基化作用特征)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2005,19(4):468-473.
[9]YU Xi-meng(余锡孟),SHEN Zhong-quan(沈忠权),DU Xi-yong(杜锡勇),et al.Liquid-phase oxidation of cyclohexane in a microchannel reactor(微通道反应器中环己烷液相氧化反应工艺的研究)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2017,31(6):1372-1378.
[10]Aleman J,Cabrera S.Applications of asymmetric organocatalysis in medicinal chemistry[J].Chemical Society Reviews,2013,42(2):774-793.
[11]HAO Zhi-xian(郝志显),WANG Le-le(王乐乐),CHENG Yi-yi(程艺艺),et al.Syntheses of silica microspheres by SDBS-modified urea-formaldehyde polymer hybridization(十二烷基苯磺酸钠改性的尿素和甲醛聚合杂化法合成氧化硅微球)[J].Chinese Journal of Inorganic Chemistry(无机化学学报),2012,28(7):1389-1396
[12]HAO Zhi-xian(郝志显),WANG Shu-zhen(王淑珍),WANG Le-le(王乐乐),et al.Urea formaldehyde polymerization controlled by using glyoxal(乙二醛存在时脲醛树脂的控制性聚合现象)[J].Acta Polymerica Sinica(高分子学报),2013,7(7):878-887.
[13]XU Xiao-ning(徐晓宁),CAO Fa-hai(曹发海).Preparation of mesoporous silica microsphere supported ruthenium catalysts for asymmetric transfer hydrogenation of acetophenone(二氧化硅微球负载钌催化剂的制备及其在苯乙酮不对称氢转移反应中的应用)[J].CIESC Journal(化工学报),2016,67(6):2340-2348.
[14]XU Xiao-ning(徐晓宁).Research on the synthesis of chiralα-phenylethanol by asymmetric transfer hydrogenation(不对称氢转移反应合成手性α-苯乙醇催化剂研究)[D].Shanghai(上海):East China University of Science and Technology(华东理工大学),2015.
[15]SHI Jing(史静),REN Nan(任楠),ZHANG Ya-hong(张亚红),et al.Advances in the research of microcapsular reactor(微囊反应器研究进展)[J].Progress in Chemistry(化学进展),2009,21(9):1750-1756.
[16]Raghu V M,XIAO Chao-xian,WANG Lin-lin,et al.A Ship-in-a-bottle strategy to synthesize encapsulated intermetallic-nanoparticle catalysts:exemplified for furfural hydrogenation[J].ACS Catalysis,2016,6(3):1754-1763.
[17]LIU Ke-tang(刘克堂),XU Yuan-yuan(徐圆圆),DUAN Meng-yuan(段梦圆),et al.Graphene oxide based chiral dianfine rhodium catalyst for asymmetric transfer hydrogenation of aromatic ketones(氧化石墨负载的手性二胺铑催化剂催化芳香酮的不对称氢转移反应)[J].Shanghai(上海):Journal of Shanghai Normal University(上海师范大学学报),2013,42(1):106-110.
[18]Atsushi F,Naonori H,Yuzuru S,et al.Ship-in-bottle synthesis and catalytic performances of platinum carbonyl clusters,nanowires,and nanoparticles in micro-and mesoporous materials[J].Catalysis Today,2001,66(1),23-31.
[19]LI Can,ZHANG Hui-dong.Chiral catalysis in nanopores of mesoporous materials[J].Chemical communications,2007,2007(6):547-558.
[20]YANG Heng-quan,ZHANG Lei,LI Can,et al.Asymmetric ring-opening of epoxides on chiral Co(Salen)catalyst synthesized in SBA-16 through the“ship in a bottle”strategy[J].Journal of Catalysis,2007,248(2):204-212.
[21]LI Yan(李艳).Preparation and characterization of asymmetric hydrogenation catalyst support by MCM-48(MCM-48固载不对称加氢催化剂的制备及表征)[D].Tianjin(天津):Nankai Universit(南开大学),2007.
[22]ZHANG Yu-li(张玉利).Research on preparation of mesoporous silica supported Pd,Rh original metal catalyst and catalysis reaction(介孔氧化硅负载Pd-Rh有机金属催化剂的制备及其催化反应研究)[D].Shanghai(上海):Shanghai Normal University(上海师范大学),2011.
[23]ZHANG Yue(张跃),ZHENG Peng-cheng(郑鹏程),YAN Sheng-hu(严生虎),et al.Synthesis process of glutaraldehyde by catalytic oxidation of cyclopentene in microreactor(微反应器中环戊烯催化氧化制备戊二醛)[J].Fine Chemicals(精细化工),2012,29(1):91-93.