陈华
主要从事水溶性膦配体及其过渡金属络合物的设计、合成;水-有机两相催化体系中烯烃氢甲酰化反应及不对称催化反应研究;天然手性源修饰的负载金属纳米催化剂的制备及不对称催化性能研究,及其在精细化学品和药物中间体的合成中的应用技术开发。
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- 姓名:陈华
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学术头衔:
博士生导师
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学科领域:
勘查地质学
- 研究兴趣:主要从事水溶性膦配体及其过渡金属络合物的设计、合成;水-有机两相催化体系中烯烃氢甲酰化反应及不对称催化反应研究;天然手性源修饰的负载金属纳米催化剂的制备及不对称催化性能研究,及其在精细化学品和药物中间体的合成中的应用技术开发。
陈华,男,1963年出生,理学博士,四川大学教授、博士生导师。1983年毕业于四川大学化学系有机化学专业,1994年获硕士学位,1999年获博士学位,1999年12月至2000年12月在香港理工大学“手性合成与创新药物开放实验室”从事博士后工作一年。主要从事水溶性膦配体及其过渡金属络合物的设计、合成;水-有机两相催化体系中烯烃氢甲酰化反应及不对称催化反应研究;天然手性源修饰的负载金属纳米催化剂的制备及不对称催化性能研究,及其在精细化学品和药物中间体的合成中的应用技术开发。 在以水溶性有机金属络合物为催化剂的水-有机两相体系研究方面,通过在体系中加入适当的表面活性剂形成的胶束与过渡金属络合物通过分子间作用力形成分子自组装体系,很好地解决了水-有机两相体系中由于有机反应底物在催化剂水溶液中溶解度低(或不溶)造成的催化活性和反应选择性下降的难题,并提出了“胶束-离子对作用机理”。首次获得了在不需搅拌的条件下即可实现高反应活性的水溶性催化体系,为人工模拟生物酶催化体系研究、解决水溶性不对称催化合成中催化活性和选择性下降的难题提供了新的途径。在水-有机两相体系催化合成方面取得了一系列创新性成果,发表论文70多篇,获授权发明专利6项。承担了国家自然科学基金、“973”基础研究和“863”高技术发展计划项目。水溶性铑-膦络合物催化烯烃氢甲酰化制备醛的系列技术开发中,“利用炼厂尾气中乙烯合成丙醛的清洁生产技术”已完成年产700吨丙醛中试技术开发,该技术的推广应用,不仅可大大减少炼油厂尾气排放造成的环境污染,而且对实现我国石油资源的综合利用意义重大,将填补我国丙醛生产的空白,并带动其下游产业――丙酸及丙酸盐系列产品的发展。
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【期刊论文】奎宁修饰的纳米铑簇合物催化丙酮酸乙酯对映选择性加氢反应研究
陈华, 熊伟, , 马红霞, 陈华, 黄艳轶, 黄裕林, 李贤均, 黎星术, 戚建英, 陈新滋
高等学校化学学报,2002,23(9)1758~1762,-0001,():
-1年11月30日
研究了奎宁作手性修饰剂修饰的负载型纳米铑簇合物催化剂(Rh PV P2C2A l2O 3)催化丙酮酸乙酯不对称氢化反应, 在该反应中手性修饰剂奎宁不仅具有手性诱导作用,而且还有明显加速反应的作用;载体C2A l2O 3在促进提高催化剂活性和对映选择性方面也有很重要的影响。在优化的反应条件[20 ℃,7.0M PaH2, c (奎宁) = 3.86×10-3mo lL,四氢呋喃作溶剂]下, 丙酮酸乙酯不对称加氢的转化频率(TO F) 为871h-1, 对映选择性达到了54.7%;反应温度降低到3 ℃时, 对映选择性达到59.2%。
纳米铑簇合物, 丙酮酸乙酯, 奎宁, 对映选择性加氢
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陈华, Min Li, Haiyan Fu, Min Yang, Hongjie Zheng, Yu-e He, Hua Chen**, Xianjun Li *
Journal of Molecular Catalysis A: Chemical 235 (2005) 130-136,-0001,():
-1年11月30日
The promotional effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. Cationic gemini surfactants with a flexible spacer (G(Eth), G(But) and G(Hex)) and rigid spacer (G(Xyl)) group were used in the reaction. The critical micelle concentration (CMC) and solubilization of laurylbenzene in gemini surfactant solutions were determined. The influence of the concentration of gemini surfactants and the stirring rate on 1-dodecene hydroformylation were investigated. The reaction results showed that in the biphasic catalytic system the hydroformylation of 1-dodecene catalyzed by RhCl(CO)(TPPTS)2-TPPTS [TPPTS = tris(sodium-m-sulfonatophenyl) phosphine] in the presence of gemini surfactants occurred with higher turn over frequency (TOF) and higher regioselectivity toward linear aldehyde (L/B) than those obtained with the conventional monomeric surfactant CTAB. The phenomena could be attributed to the fact that the gemini surfactant has lower CMC and better surface tension reduction ability; moreover it could form more compact and spherocylindrical micelle in the solution. These properties would be favorable for the decrease in the phase transfer energy barrier, thereby greatly accelerating the reaction rate. Meanwhile, the more compact structure of the spherocylindrical micelle formed from gemini surfactant could construct a favorable microenvironment for the formation of linear aldehyde. The comparison of the acceleration effect of the three type surfactants (monomeric surfactant CTAB (cetyltrimethylammonium bromide), gemini surfactant G(Eth), G(But), G(Hex)), G(Xyl) as well as double chain surfactant DCMAB (di(cetylmethyl)ammonium bromide) indicated that the surfactant structure had an important effect on the reaction rate. Their promotion order is DCMAB> G(Eth)≈G(But)≈G(Hex)≈G(Xyl) > CTAB.
Hydroformylation, 1-Dodecene, Gemini surfactant, Biphasic catalysis, Rhodium catalyst
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陈华, Wei Xiong, a, b Qi Lin, a Hongxia Ma, a Hongjie Zheng, a Hua Chena and Xianjun Lia, *
Tetrahedron: Asymmetry 16 (2005) 1959-1962,-0001,():
-1年11月30日
The catalytic performance of ruthenium phosphine complexes using (1S, 2S)-DPENDS [(1S, 2S)-1, 2-diphenyl-1, 2-ethylene diamine sulfonate disodium] as a chiral modifier in the asymmetric hydrogenation of aromatic ketones was examined in a series of hydrophilic ionic liquids [RMIM]+[p-CH3 C6 H4 SO3] (R=ethyl, butyl, octyl, dodecyl). The synergistic effect between (1S, 2S)-DPENDS and KOH significantly accelerated the reaction and enhanced the enantioselectivity. An ee value of 84.8% was obtained in the asymmetric hydrogenation of acetophenone under the optimized conditions. The products were conveniently separated with cyclohexane extraction, and both the ruthenium catalyst and (1S, 2S)-DPENDS were kept in the ionic liquid and could be reused.
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陈华, Wei Xiong, a, b Hongxia Ma, a Yanyi Hong, a Hua Chena and Xianjun Lia, *
Tetrahedron: Asymmetry 16 (2005) 1449-1452,-0001,():
-1年11月30日
Alumina supported rhodium catalyst using cinchonidine as a stabilizer exhibited excellent performance in the asymmetric hydrogenation of ethyl pyruvate with the addition of quinine. Quinine as a chiral modifier can not only induce the enantioselectivity, but also greatly accelerate the reaction. Under the optimum conditions: 293 K, 7.0 MPa of hydrogen pressure and 4.6×103 mol/L of quinine concentration in THF, TOF of Rh/2(cinchonidine)-c-Al2O3 as catalyst and ee value of (R)-ethyl lactate can achieve 894 h 1 and 71.6% ee, respectively.
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陈华, Maolin Yuan, Hua Chen*, Ruixiang Li, Yaozhong Li, and Xianjun Li*
Catalysis Letters Vol. 94, Nos. 1-2, April 2004 (2004),-0001,():
-1年11月30日
The hydroformylation of 1-dodecene under aqueous/organic two-phase reaction conditions with rhodium catalysts derived from BISBIS (sodium salt of sulfonated 2, 2
aqueous/, organic two-phase system, 1-dodecene hydroformylation, diphosphine, surfactants.,
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陈华, Maolin Yuan, Hua Chen, Ruixiang Li, Yaozhong Li, Xianjun Li*
Applied Catalysis A: General 251 (2003) 181-185,-0001,():
-1年11月30日
This paper reports the hydroformylation of 1-butene catalyzed by RhCI(CO)(TPPTS)2 (TPPTS: P(m-C6H4SO3Na)3) and BISBIS (sodium salt of sulfonated 2, 2_-bis(diphenylphosphinomethyl)-1, 1_-biphenyl) in aqueous/organic two-phase catalytic system. The effects of reaction parameters on the catalytic activity and regioselectivity were investigated under the optimum eaction conditions: 130. C, 2.5MPa (syngas pressure), [BISBIS]/[Rh]=5, [1-butene]/[H2]/[CO]=1: 1: 1, [1-butene]/[Rh]=10 400, TOF and the regioselectivity for n-valeraldehyde were 2987 h.1 and 98%, respectively. 2003 Elsevier B. V. All rights reserved.
Hydroformylation, 1-Butene, Water-soluble rhodium complex, Two-phase catalysis
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陈华, Liangbing Wang, Hua Chen, Yu-e He, Yaozhong Li, Min Li, Xianjun Li*
Applied Catalysis A: General 242 (2003) 85-88,-0001,():
-1年11月30日
The effect of TPPTS [p(m-C6H4SO3Na)3], RhCl(CO)(TPPTS)2 and olefin on CMC (critical micelle concentration) of the aqueous solution containing cationic surfactant cetyltrimethylammonium bromide (CTAB) was studied by the maximum bubble pressure method. The apparent molar mass of micelle was determined by a light scattering method. The results showed that the addition of TPPTS and RhCl(CO)(TPPTS)2 into aqueous solutions of CTAB caused the decrease of CMC and the increase of the apparent molar mass of micelle. The data supported the suggestions about enrichment of rhodium catalyst in micelle interface layer and about the solubilization of olefin in micelle. This explanation was confirmed by the measurements of rhodium concentration in the interface layer using ICP method. The acceleration mechanism of long chain olefin hydroformylation in a biphasic catalytic system containing a cationic surfactant was provided.
Olefin hydroformylation, Biphasic catalysis, Rhodium complex, Micelle concentration
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陈华, Hua Chen, Yaozhong Li, Ruixiang Li, Puming Cheng, Xianjun Li*
Journal of Molecular Catalysis A: Chemical 198 (2003) 1-7,-0001,():
-1年11月30日
The hydroformylation of 1-dodecene catalyzed by RhCl (CO) (TPPTS) 2-BISBIS [TPPTS: P (m-C6 H4 SO3 Na) 3, BISBIS: sulfonated 1,1-bis (diphenylphosphino methyl)-2, 2-biphenyl] in aqueous/organic two-phase systemwas studied. The addition of cationic surfactant cetyltrimethylamonium bromide (CTAB) greatly accelerated the reaction rate and the high regioselictivity for linear aldehyde using diphosphine as ligand was attained under two-phase conditions. Both high activity (TOF: 740 h−1) and excellent regioselectivity (96.5% of 1-tridecanal) were obtained at 120℃, 2.0 MPa and [BISBIS]/[Rh] ratio of 3 in thepresence of CTAB.
Aqueous two-phase system, 1-Dodecene hydroformylation, Diphosphine, Surfactant
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陈华, Hongxia Ma, Hua Chen, Qin Zhang, Xianjun Li*
Journal of Molecular Catalysis A: Chemical 196 (2003) 131-135,-0001,():
-1年11月30日
The enantioselective hydrogenation of ethyl pyruvate in the presence of TS-1 supported rhodium nanoclusters and chiral modifier cinchonidine, cinchonine and quinine was investigated. The results showed that cinchonidine was the best modifier and THF was an excellent solvent for the reaction. Cinchonidine and quinine not only induced the enantioselectivity, but also accelerated the reaction. The interaction between the support and rhodium nanoclusters, as well as the adsorption of modifier on the support surface played an important role in promoting the increase of the catalytic activity and enantioselectivity. Under the optimum conditions, 268 K, 7MPa of hydrogen pressure and 4.0×10−3 mol/l of cinchonidine in THF, the mole conversion of ethyl pyruvate and enantiomeric excess of R-ethyl lactate reached up to 100 and 63.1%, respectively.
Supported rhodium nanoclusters, Enantioselective hydrogenation, Ethyl pyruvate, Cinchonidine, Quinine
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【期刊论文】Studies on 1-dodecene hydroformylation in biphasic catalytic system containing mixed micelle
陈华, Min Li, Yaozhong Li, Hua Chen, Yu-e He, Xianjun Li*
Journal of Molecular Catalysis A: Chemical 194 (2003) 13-17,-0001,():
-1年11月30日
Hydroformylation of 1-dodecene catalyzed by water-soluble rhodium-phosphine complex, RhCl (CO) (TPPTS)2 (TPPTS: P(m-C6 H4 SO3 Na)), in the presence of various mixed micelles was investigated. When either an anionic surfactant sodium dodecyl sulfate (SDS) or dodecylbenzonesulphonate (DBS), a nonionic surfactant Triton X-100 or Brij 35, or alcohol was added into cationic surfactant cetyl pyrindium bromide (CPB) solution, a mixed micelle formed. The decrease in critical micelle concentration (CMC) and the increase in solubilization of 1-dodecene in the mixed micelle were observed. Hydroformylation of 1-dodecene exhibited higher conversion and higher regioselectivity in the mixed micellar solution than in the single micelle of CPB. The synergistic mechanism of two different surfactants was discussed.
Hydroformylation, 1-Dodecene, Mixed micelle, Biphasic catalysis
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