研究了在阳离子表面活性剂存在下水/有机两相中水溶性铑配合物RhCI(CO)(TPPTS)2(TPPTS:P(m-C6H4SO3Na)3)催化双环戊二烯氢甲酰化反应,考察了反应温度、催化剂浓度、不同水溶性膦配体TPPTS和TPPDS(C5H5P(m-C6H4SO3Na)2),以及表面活性剂结构对催化反应的影响.结果表明,配体TPPTS比TPPDS表现出更好的助催化效果;阳离子表面活性剂C16H33N(CH3)2CnH2n+1Br(n=1,8,12,16)的加入可大大加速反应,但加速作用随着其中CnH2n+1Br(n=1,8,12,16)链长的增加而减弱;在阳离子表面活性剂(0.05～5.00mmol/L)存在下,双环戊二烯的转化率随表面活性剂浓度的增加先增加后降低.含催化剂的水相循环使用4次后,催化活性和区域选择性没有明显下降.
Dicyclopentadiene (DCPD) hydroformylation catalyzed by the water soluble rhodium complex RhCI(CO)(TPPTS)2 (TPPTS:P(m-C6H4SO3Na)3) was studied in an aqueous/organic two phase system containing a cationic surfactant. The effects of various reaction parameters such as reaction temperature, catalyst concentration, water soluble phosphine TPPTS or TPPDS (C6H5P(m-C6H4SO3Na)2), and surfactant structure were examined. The catalytic activity was better with the ligand TPPTS than with TPPDS. The reaction was accelerated by the addition of the cationic surfactant C16H33N(CH3)2CnH2n+1Br(n = 1, 8, 12, 16) but the accelerating effect was attenuated with an increase of the n value. In the presence of the surfactant, the DCPD conversion increased initially and then decreased as the rhodium concentration increased in the range of 0.05-5.00 mmol/L. The catalyst containing aqueous phase was reused four times without significant decrease in activity and regioselectivity.
参考文献
| [1] | Fujikura Y;Inamoto Y;Takaishi N;Ykeda H .[J].Synthetic Communications,1976,6:199. |
| [2] | Aigami K;Inamoto Y;Takaishi N;Fujiura Y Takatsuki A Tamura G .[J].Journal of Medicinal Chemistry,1976,19:536. |
| [3] | Garlaschell L;Marchionna M;Iapalucci M C;Longoni G .[J].Journal of Molecular Catalysis,1991,68:7. |
| [4] | Cornils B;Wiebus E .[J].Chemtech,1995,23:33. |
| [5] | Wiebus E;Cornils B .[J].Hydrocarbon Processing,1996,75:63. |
| [6] | Deshpande R M;Purwanto H;Delmas H;Chaudhari R V .[J].Industrial and Engineering Chemistry Research,1996,35:3927. |
| [7] | Chaudhari R V;Bhanage B M;Deshpande R M;Delmas H .[J].Nature,1995,373:501. |
| [8] | Ding H;Kang J;Hanson B E;Kohlpaintner C W .[J].Journal of Molecular Catalysis A:Chemical,1997,124:21. |
| [9] | Hanson B E;Ding H;Kohlpaintner C W .[J].Catalysis Today,1998,42:421. |
| [10] | Goedheijt M S;Hanson B E;Reek J N H;Kamer P C J Van Leeuwen P W N M .[J].Journal of the American Chemical Society,2000,122:1650. |
| [11] | Peng Q R;Liao X L;Yuan Y Zh .[J].Catalyst Communication,2004,5:447. |
| [12] | Sieffert N;Wipff G .[J].Journal of Physical Chemistry B,2006,110:4125. |
| [13] | Monflier E;Bricout H;Hapiot F;Tilloy S Aghmiz A Masdeu-Bultó A M .[J].Advanced Synthesis and Catalysis,2004,346:425. |
| [14] | Legrand F X;Hapiot F;Tilloy S;Guerriero A Peruzzini M Gonsalvi L Monflier E .[J].Applied Catalysis A:General,2009,362:62. |
| [15] | Jin Z L;Zheng X L;Fell B .[J].Journal of Molecular Catalysis A:Chemical,1997,116:55. |
| [16] | Wang Y H;Jiang J Y;Wu X W;Cheng F Jin Z L .[J].Catalysis Letters,2002,79:55. |
| [17] | Russell M J H .[J].Platinum Metals Review,1988,32:179. |
| [18] | Riisager A.;Hanson BE. .CTAB micelles and the hydroformylation of octene with rhodium/TPPTS catalysts - Evidence for the interaction of TPPTS with micelle surfaces[J].Journal of molecular catalysis, A. Chemical,2002(2):195-202. |
| [19] | Miyagawa CC;Kupka J;Schumpe A .Rhodium-catalyzed hydroformylation of 1-octene in micro-emulsions and micellar media[J].Journal of molecular catalysis, A. Chemical,2005(1/2):9-17. |
| [20] | Fu H Y;Li M;Chen J;Zhang R M Jiang W D Yuan M L Chen H Li X J .[J].Journal of Molecular Catalysis A:Chemical,2008,292:21. |
| [21] | Chen H;Li Y Zh;Chen J R;Cheng P M He Y E Li X J .[J].Journal of Molecular Catalysis A:Chemical,1999,149:1. |
| [22] | Li M;Fu H Y;Yang M;Zheng H J He Y E Chen H Li X J .[J].Journal of Molecular Catalysis A:Chemical,2005,235:130. |
| [23] | Fu HY;Li M;Chen H;Li XJ .Higher olefin hydroformylation in organic/aqueous biphasic system accelerated by double long-chain cationic surfactants[J].Journal of molecular catalysis, A. Chemical,2006(1/2):156-160. |
| [24] | Fu H Y;Li M;Mao H;Lin Q Yuan M L Li X J Chen H .[J].Catalyst Communication,2008,9:1539. |
| [25] | 毛卉,付海燕,陈华,李瑞祥,李贤均.水/有机两相体系1-癸烯氢氨甲基化反应中TPPTS和TPPDS的协同效应[J].催化学报,2009(12):1192-1196. |
| [26] | 赵明;袁刚 .[J].精细化工,1996,13:32. |
| [27] | 陈华;刘海超;黎耀忠;程溥明 李贤均 .[J].分子催化,1994,8:124. |
| [28] | Chen H;Li Y;Chen J;Cheng P Li X .[J].Catalysis Today,2002,74:131. |
| [29] | MacDougall J K;Simpson M C;Greem M J;Cole-Hamilton D J.[J].Journal of the Chemical Society,Dalton Transactions,1996:1161. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%