Hydroformylation of 1-Dodecene Catalyzed by Water Soluble Rhodium-Phos-phine Complexes in Micellar System with Cationic Gemini Surfactant

Abstract

Abstract: The promotion of 1,2-bis(dimethylcetyl ammonium bromide) ethane[G(Et)] cationic gemini surfactant for the hydroformylation of 1-dodecene in the oil/water biphasic catalytic system is reported. The critical micelle concentration(cmc) and solubilization of laurylbenzene in G(Et) solution were determined. The cmc of G(Et) was 3.8×10^-5 mol/L, which was much lower than that 9.6×10^-4 mol/L of CTAB. The influences of the concentration of G(Et) and the stirring rate on 1-dodecene hydroformylation were studied. The results show that in the biphasic system containing the catalyst RhCl(CO)(TPPTS)₂ and TPPTS[TPPTS=tris(sodium-m-sulfonatophenyl) phosphine], the hydroformylation of 1-dodecene in the presence of gemini surfactant G(Et) occured with a higher turn over frequency(TOF=1 066 h^-1 ) and higher selectivity for normal aldehyde[n(normal)/n(iso)=5.7] than that using conventional monomeric surfactant CTAB[TOF=901 h^-1 , n(normal)/n(iso)=3.7]. The phenomena could be attributed to that G(Et) has a lower cmc and could form more compact and spherocylindrical micelle in the solution. The lower cmc and good surface tension reduction ability of G(Et) would be favorable for decreasing phase transfer energy barrier of 1-dodecene from the core of micelle to the interface of two phases where 1-dodecene coordinated with rhodium catalysts, and thereby the reaction rates was accelerated greatly. The more compact structure of the spherocylindrical micelle of G(Et) would be favorable for the formation of linear aldehyde.

Key words: Biphasic catalysis, Hydroformylation, Gemini surfactant, 1-Dodecene, Rhodium catalyst

CLC Number:

O643.32

TrendMD:

LI Min, XU Bin, CHEN Hua, HE Yu-E, HUANG Xue-Yuan, LI Li-Bo, LI Yao-Zhong, LI Xian-Jun . Hydroformylation of 1-Dodecene Catalyzed by Water Soluble Rhodium-Phos-phine Complexes in Micellar System with Cationic Gemini Surfactant[J]. Chem. J. Chinese Universities, 2004, 25(4): 717.

References

[1] Boy Corn ils.J.Mo .lCata.lA:Chem.[J],1999,143:1—10 [2] Kun tz E.G..Chem tech.[J],1987,15:570—575 [3] WU Xiao-Wei(吴小伟),WANG Yan-Hua(王艳华),CHENG Fang(程　　)et al..Chem.J.Chinese Universities(高等学校化学学报)[J],2002,23(10):1 939—1 943 [4] Van Vyve F.,Renken A..Cata.lToday[J],1999,48:237—243 [5] Riisager A.,Han son B.E..J.Mo .lCata.lA:Chem.[J],2002,189:195—202 [6] Chen H.,Li Y.Z.,Chen J.R.et al..J.Mo .lCata.lA:Chem.[J],1999,149:1—6 [7] Li Y.Z.,Chen H.,Chen J.R.et al..Ch in.J.Chem.[J],2001,19:58—62 [8] Wang L.B.,Chen H.,He Y.E.et al..App l.Catal.A:General[J],2003,242:85—88 [9] LiM.,Li Y.Z.,Chen H.et al..J.Mo .lCatal.A:Chem.[J],2003,194:13—17 [10] Zana R.,Ben rraou M.,Rueff R..Langm uir[J],1991,7:1 072—1 075 [11] Zana R.,Talmon Y..Nature[J],1993,362:228—230 [12] Hirata H.,Hatto ri N.,Ish ida M.et al..J.Phys.Chem.[J],1995,99:17 778—17 784 [13] ZHENG Ou(郑　欧),ZHAO Jian-Xi(赵剑曦),YOU Yi(游　毅).Chem.J.Ch inese Universities(高等学校化学学报)[J],2002,23(7):1 352—1 355 [14] Dreja M.,Tieke B..Langm uir[J],1998,14:800—807 [15] Cerichelli G.,Luchetti L.,Mancin i G.et al..Langm uir[J],1999,15:2 631—2 634 [16] CHEN Hua(陈　华),LIU Hai-Chao(刘海超),LI Yao-Zhong(黎耀忠)et al..J.Mo l.Catal.(分子催化)[J],1994,8(2):124—129 [17] ZHAO Jian-Xi(赵剑曦).Progress in Chem.(化学进展)[J],1999,11:348—357 [18] Chio T.S.,Sh im izu Y.,Sh irai H.et al..Dyes and Pigm en ts[J],2000,45:145—152 [19] DeSom a,Asw al V.K.,Goyal P.S.et al..J.Phys.Chem.[J],1996,100:11 664—11 671 [20] Dan ino D.,Talmon Y.,Zana R..Langm uir[J],1995,11:1 448—1 456 [21] Berheim-Gro sw asser A.,Zana R.,Talmon Y..J.Phys.Chem.B[J],2000,104:4 005—4 009 [22] Lekhal A.,Chaudhari R.V.,Wilhelm A.M.et al..Catal.Today[J],1999,48:265—272 [23] Rosen M.J.,Liu L..J.Am.Oi.lChem.Soc.[J],1996,73:885—890