聚合物固载环金属化合物的合成及其催化性能研究
摘要
一、本论文共合成了四个系列共27种未见文献报道的聚合物固载的亚胺配体及其相应的亚胺环钯化合物。通过元素分析、红外光谱确定了它们的结构和组成。
化合物A_1-A_9 化合物B_1-B_8
化合物C_1-C_6 化合物D_1-D_4
二、聚合物固载的亚胺环钯化合物对Heck反应的催化性能研究
1．考察了上述制备的四个系列聚合物固载亚胺环钯化合物对卤代苯与丙烯酸酯偶联反应的催化活性，实验结果表明，所有固载环金属催化剂均可有效催化Heck反应，且转化数达到10~4-10~5，转化效率最高可达21000。以化合物A_1-A_9为催化剂，考察了在不同溶剂(DMF、CH_3CN)中催化碘代苯与丙烯酸丁酯的偶联，发现偶联反应均可在较短时间内完成。
中文摘要
2.以化合物A:一扬为催化剂，考察了聚合物固载的环铭化合物用于催化碘代
苯与苯乙烯的偶联反应。实验结果表明，所用催化剂对该类Heck反应具有同均相
类似物相近的催化活性，且反式产物与1，1一二苯基乙烯产物之比约为10/1。
仔，·一裂戮黯千导心·黔:一
l2
3.以化合物AS为代表，研究了聚合物固载的环把化合物对芳基嗅化物和氯化
物与丙烯酸丁酷的偶联反应的催化活性，发现聚合物固载的环把化合物可用于催
化多种带有活化基团的芳基澳化物和芳基氯化物，但活性均低于相应的芳基碘化
物。
R蕊〕~X‘eHZ一CHC02C4Hg
Cat.100℃
R粉
+
COZC;H。
R二H，P一NOZ，m一NOZ，P一N02，BrX=Cl，Br
4.考察了聚合物固载的亚胺环把化合物在催化碘代苯和丙烯酸丁酷的偶联反
应中的稳定性和反复使用的可能性，发现随着催化剂使用次数增多，完成反应的
时间增长，转化效率普遍降低，但在经历反复加热催化和冷却过程中催化剂仍具
有很好的稳定性和选择性。
5.用气相色谱方法跟踪了催化偶联反应的进程。根据反应结果，结合聚合物
固载亚胺环把化合物的特点，提出了聚合物固载催化剂催化Heek反应的可能机理。
BaseHX
B一少
{Pd
备
可
H·[Pd]一X
R一IPd]X
、人R、:Pd卜x少分
ProPosed meehanism for Heck reaction catalyzed
by Polymer一suPPorted eycloPalladated imine comPounds
1. In this thesis, four series, Twenty-seven polymer-supported cyclopalladated inline compounds have been prepared and characterized by IR and E.A.
compounds A1-A9 compounds B1-B8
compounds C1-C9 compounds
2. The catalytic properties of the four series polymer-supported cyclopalladated compounds in the Heck reaction have been studied as follows:
a. The results obtained indicated that all of the catalysts studied could catalyze the coupling reaction of iodobenzene with acrylates. The TON and TOP were as high as 104-105 and 21000, respectively. Compounds A1-A9 were used as catalysts to catalyze the coupling reaction of iodobenzene with butyl acrylate in different solvent, such as DMF or CH3CN, in which the coupling reactions could be completed at 100癈 in short time.
b. The catalysts A1-A9 were also used to catalyze the coupling reaction of iodobenzene with styrene. About 10/1 of trans-stilbene/l,l-diphenylethylene were obtained .The activity of the catalysts catalyzing this Heck reaction was almost the same as the homocatalyst analogues reported in the literature.
c. The coupling reactions of aryl bromides and aryl chlorides with butyl acrylate catalyzed by catalyst A8 were also studied. It was found that the catalyst was also efficient to catalyzed the Heck reaction in the case of aryl bromides and aryl chlorides. But their activities were much lower than the corresponding aryl iodides.
d. The catalyst A8 used to catalyze the coupling of indobenzene with butyl acrylate could be reused at least five times.
e. The coordination of coupling reaction was followed by GC. According to the results and the properties of the polymer-supported cyclopalladated compounds, the mechanism based ori Pd(0) /Pd( II) circle was proposed.
Proposed mechanism for Heck reaction catalyzed by polymer-supported cyclopalladated imine compounds
化合物A_1-A_9 化合物B_1-B_8
化合物C_1-C_6 化合物D_1-D_4
二、聚合物固载的亚胺环钯化合物对Heck反应的催化性能研究
1．考察了上述制备的四个系列聚合物固载亚胺环钯化合物对卤代苯与丙烯酸酯偶联反应的催化活性，实验结果表明，所有固载环金属催化剂均可有效催化Heck反应，且转化数达到10~4-10~5，转化效率最高可达21000。以化合物A_1-A_9为催化剂，考察了在不同溶剂(DMF、CH_3CN)中催化碘代苯与丙烯酸丁酯的偶联，发现偶联反应均可在较短时间内完成。
中文摘要
2.以化合物A:一扬为催化剂，考察了聚合物固载的环铭化合物用于催化碘代
苯与苯乙烯的偶联反应。实验结果表明，所用催化剂对该类Heck反应具有同均相
类似物相近的催化活性，且反式产物与1，1一二苯基乙烯产物之比约为10/1。
仔，·一裂戮黯千导心·黔:一
l2
3.以化合物AS为代表，研究了聚合物固载的环把化合物对芳基嗅化物和氯化
物与丙烯酸丁酷的偶联反应的催化活性，发现聚合物固载的环把化合物可用于催
化多种带有活化基团的芳基澳化物和芳基氯化物，但活性均低于相应的芳基碘化
物。
R蕊〕~X‘eHZ一CHC02C4Hg
Cat.100℃
R粉
+
COZC;H。
R二H，P一NOZ，m一NOZ，P一N02，BrX=Cl，Br
4.考察了聚合物固载的亚胺环把化合物在催化碘代苯和丙烯酸丁酷的偶联反
应中的稳定性和反复使用的可能性，发现随着催化剂使用次数增多，完成反应的
时间增长，转化效率普遍降低，但在经历反复加热催化和冷却过程中催化剂仍具
有很好的稳定性和选择性。
5.用气相色谱方法跟踪了催化偶联反应的进程。根据反应结果，结合聚合物
固载亚胺环把化合物的特点，提出了聚合物固载催化剂催化Heek反应的可能机理。
BaseHX
B一少
{Pd
备
可
H·[Pd]一X
R一IPd]X
、人R、:Pd卜x少分
ProPosed meehanism for Heck reaction catalyzed
by Polymer一suPPorted eycloPalladated imine comPounds
1. In this thesis, four series, Twenty-seven polymer-supported cyclopalladated inline compounds have been prepared and characterized by IR and E.A.
compounds A1-A9 compounds B1-B8
compounds C1-C9 compounds
2. The catalytic properties of the four series polymer-supported cyclopalladated compounds in the Heck reaction have been studied as follows:
a. The results obtained indicated that all of the catalysts studied could catalyze the coupling reaction of iodobenzene with acrylates. The TON and TOP were as high as 104-105 and 21000, respectively. Compounds A1-A9 were used as catalysts to catalyze the coupling reaction of iodobenzene with butyl acrylate in different solvent, such as DMF or CH3CN, in which the coupling reactions could be completed at 100癈 in short time.
b. The catalysts A1-A9 were also used to catalyze the coupling reaction of iodobenzene with styrene. About 10/1 of trans-stilbene/l,l-diphenylethylene were obtained .The activity of the catalysts catalyzing this Heck reaction was almost the same as the homocatalyst analogues reported in the literature.
c. The coupling reactions of aryl bromides and aryl chlorides with butyl acrylate catalyzed by catalyst A8 were also studied. It was found that the catalyst was also efficient to catalyzed the Heck reaction in the case of aryl bromides and aryl chlorides. But their activities were much lower than the corresponding aryl iodides.
d. The catalyst A8 used to catalyze the coupling of indobenzene with butyl acrylate could be reused at least five times.
e. The coordination of coupling reaction was followed by GC. According to the results and the properties of the polymer-supported cyclopalladated compounds, the mechanism based ori Pd(0) /Pd( II) circle was proposed.
Proposed mechanism for Heck reaction catalyzed by polymer-supported cyclopalladated imine compounds
引文
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2． Letsinger.R.L., and Dornet.M.J.,J.Am.Chem.Soc.1963, 55, 3045
3． Merrifield, R.B.J.Am.Chem.Soc.1963, 55, 2149．
4． Seneci, P.Solid-Phase Synthesis and Combinatorial Techniques;John Wiley:New York.2001．
5． Burgess, K.Solid-Phase Organic Synthesis;John Wiley;New York.2000．
6． Pomogailo, A.D.Catalysis by Polymer-Immobilized Immobilized Metal Complixes;Gordon and Breacg:Australia, 1998．
7． Kobayashi, 5． Chem.Soc.Rev.1998, 28, 1
8． Kobayashi, S.Curr.Opin.Chem.Boil.2000, 4,338．
9． Senkan, S.Angew.Chem.Int.Ed.2001, 40, 312．
10． Reetz, M.T.Angew.Chem.Int.Ed.2001, 40, 284．
11． Dahmen, S., Brase, S.Synthesis 2001, 10, 1431．
12． Clapham, B., Reger, T.S., Janda, K.D.Tetrahedron 2001, 57, 4637．
13． de Miguel, Y.R.J.Chem.Soc., Terkin Trans.2000, 1, 4213．
14． de Miguel, Y.R., Brule, E., Margue, R.G.J.Chem.Soc., Perkin Trans.2001, 1,3085．
15． Saluzzo, C., ter Halle, R., Touchard, F., Fache, F., Schulz, E., Lemaire, M.J.Organomet.Chem.2000, 603, 30．
16． Shuttleworth, S.J., Allin, S.M., Sharma, P.K.Synthesis 1997,11, 1217．
17． Shuttleworth, S.F., Allin, S.M., Wilson, R.D., Nasturica, D.Synthesis 2000, 8,1035．
18． Eames, J., Watkinwon, M.Eur.J.Org.Chem.2001, 7, 1213．
19． Nicholas E.Leadbeater, and Maria Marco.Chem.Rev.2002, 702, 3217．
20． Pittmann, C.U., Jr.In Comprehensive Organometallic Chemmistry, Silkinson, G, Stone, F.G.A., Abel, E.W, Eds.Pergamon Press:Oxford, 1982, Vol.8．
21． Bailey, K.C., Langer, S.H.Chem.Rev.1981, 81, 109．
22． Farrall, M.J., Frechet, J.M.J.J.Org.chem., 1976, 41, 3877．
23． Pittman, C.J.Jr., Wuu, S.K., Jacobson, S.E.J.Catal 1976, 44, 87．
24． Trost, B.M, Keinan, E.J.Am.Chem.Soc.1978,100, 7779．
25． Fenger, I., Le Drian, C.Tetrahedron Lett.1998, 39, 4287．
26． Zhang, T.Y., Allen, M.J.Tetrahedron Lett.1999, 40, 5813．
27． Parrish, C.A., Buchwald, S.L.J.Org.Chem.2001, 66, 3820．
28． Still J.K.;Su, H.;Hill, K.H.;Schneider, P.;Tanaka, M.;Morrison, D.L.;Hegedus.L.S.Organometallics 1991,145． 221．
29． Judkins.C.M.G, Knights, K.A., Jongson.B.F.G.de Miguel.Y.R..Raja.R..Thomas.J.M.Chem.Comnnm.2001, 2624．
30． Dumont.W., Puolin, J.-C., Dang, T.-P, Kagan, H.B.J.Am.Chem.Soc.1973． 95,8295．
31． "Polymer-supported BINAP" is commercially available from Evotec-LAI, Alethough the ligand described in the literature has an amide linkage,the commercially available one has an ether linkage.
32． Bayston, K.J., Fraser, J.L., Ashton, M.R., Baxter, A.D., Polyvvka, M.E.C., Moses, E.J.Org.Chem.1998, 63, 3137．
33． Fujii,A., Sodeoka, M.Tetrahedron Lett.1999,40,8011．
34． Park, H.-J., Han, J.W., Seo, H., Jang, H.-Y., Chung, Y.K., Suh, J.J.Mol.Catal.A:chem.2001, 174, 151．
35． Pu, L.Chem.Rew.1998, 98,2405．
36． Sellner, H., Faber, C., Rheiner, P.B., Seebach, D.Chem.-Eur.J.2000, 6, 3692．
37． Meunier, B.Chem.Rev.1992, 92, 1411．
38． Puhlaman, P., Pretsch, E., Bakker, R.Chem.Rev.1998, 98, 1593．
39． Mathew, T., Padmanabhan, M., Kuriakose, S.J.Apple.Polym.Sci.1996, 59,23．
40． Wang, R.M., Wang, Y.P., Lei, Z.Q.Rev.Roum.Chim.Soc.1998, 43, 51．
41． Hlatky, G.C.Chem.Rev.2000,100, 1347．
42． For recent reviews of the use of supports other than polystyrene, see (a) Alt, H.G.J.Chem.Soc., Daton Trans.1999, 1703． (b) Imanishi, Y, Naga, M.Prog.Polym.Sci.2001,26, 1147．
43． Raspolli Galletti, A.M., Geri, G, Sbrana, G, Marchionna, M., Ferrarini, P.J.Mol.
Catal.A:Chem.1996, 777, 273．
44． Hong, S.C., Ban, H.T., Kishi, N., Jin, J.Z., Uozumi, T., Soga, K.Macromol.Chem.Phys.1998, 799,1393．
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