二茂铁基环氧衍生物

王建军, 丁恒春, 倪沛红, 戴礼兴, 高强

doi:10.7536/PC141234

化学进展 ›› 2015, Vol. 27 ›› Issue (7) :853-860 DOI: 10.7536/PC141234

综述与评论

扫码查看或转发全文

二茂铁基环氧衍生物

王建军, 丁恒春, 倪沛红, 戴礼兴, 高强

作者信息 +

Ferrocene-Based Epoxy Derivatives

Wang Jianjun, Ding Hengchun, Ni Peihong, Dai Lixing, Gao Qiang

Author information +

文章历史 +

摘要

二茂铁基环氧的分子结构中同时含有环氧和二茂铁,是一类兼具化学活性和多功能性的特殊材料。这类材料具有单体结构多样性和聚合物的多功能性,近年来对其制备方法和应用的研究受到广泛关注。研究者们已利用二茂铁醛、酮、烯、氯醇、双醇、乙酰氯等为中间体,制备出二十多种小分子化合物。采用二茂铁接枝环氧聚合物或含烯单体自由基聚合,分别得到多种结构的聚合物。本文在综述二茂铁基环氧制备方法的基础上,进一步讨论了这类材料的结构稳定性。研究发现,当二茂铁处于环氧的邻位时,极易形成卡宾结构,使得环氧开环并重排成醛。通过列举典型研究实例,阐明其在功能材料、传感介质、燃速催化、催化剂配体以及药物合成等方面的应用,并就其在材料表界面的发展趋势进行了展望。

Abstract

Ferrocene-based epoxy of the special chemical structure is composed of epoxy and ferrocene. These materials behave as structurally diverse monomers and multifunctional polymers. In recent years, more attention is focused on synthetic approaches and applications due to their high chemical activity and multifunctionality. More than twenty small molecules of ferrocene-based epoxy have been synthesized via ferrocenyl aldehydes, ketones, alkene, chlorohydrins, diols, or chloroacetyl intermediates, and polymerized derivatives have also been developed by ferrocene-modified epoxy polymers or free radical copolymerization of glycidyl ether and vinylferrocene. This review intends to offer relevant synthetic strategies for the preparation of covalent systems based on epoxy and ferrocene. Particular attention has been paid to understand the fundamental stability of these systems. The vicinal epoxy facilitates the formation of ferrocenyl carbonium ions, and is labile toward ring opening and consequent isomerization to the aldehyde. A variety of architectures have a wide range of potential applications in areas such as functional materials, biomedical mediators, chiral ferrocenyl ligands, burn-rate catalysts and antitumor agents, among others. Detailed examples with different chemical structures of polymers are provided to illustrate about their applications. Finally, the future development at the surface and interface of materials is prospected.

Contents
1 Introduction
2 Stability of ferrocene-based epoxys
3 Synthesis of ferrocene-based epoxys
3.1 Base catalysis chlorohydrins
3.2 Corey-Chayovsky reaction
3.3 Sulphur ylide-mediated epoxidation
3.4 Dimethyldioxirane oxidation
3.5 Vicinal diols dehydration
3.6 Darzens reaction
4 Applications of ferrocene-based epoxys
4.1 Functional polymers or resins
4.2 Biomedical mediators
4.3 Chiral ferrocenyl ligands
4.4 Burn-rate catalysts
4.5 Antitumor agents
5 Conclusion

Graphical abstract

关键词

二茂铁 / 环氧 / 功能性聚合物 / 燃速催化剂

Key words

ferrocene / epoxy / functional polymers / burning rate catalysts

引用本文

引用格式 ▾

王建军, 丁恒春, 倪沛红, 戴礼兴, 高强. 二茂铁基环氧衍生物[J]. 化学进展, 2015, 27(7): 853-860 DOI:10.7536/PC141234

Wang Jianjun, Ding Hengchun, Ni Peihong, Dai Lixing, Gao Qiang. Ferrocene-Based Epoxy Derivatives[J]. Progress in Chemistry, 2015, 27(7): 853-860 DOI:10.7536/PC141234

登录浏览全文

4963

注册一个新账户忘记密码

参考文献

原文顺序 | 出版日期 | 本文引用

[1] 陈平(Chen P),刘胜平(Liu S P). 环氧树脂(Epoxy Resins). 北京:化学工业出版社(Beijing:Chemical Industry Press), 1999.
[2] Chen S, Chen W, Shi W, Ma H. Chem. Eur. J., 2012, 18(3): 925.
[3] Werner H. Angew. Chem. Int. Ed., 2012, 51(25): 6052.
[4] Shvekhgeimer M G A. Russ. Chem. Rev., 1996, 65(1): 41.
[5] Moyano A, Rios R. Synlett, 2009, (12): 1863.
[6] 王建军(Wang J J), 王立(Wang L), 王学杰(Wang X J). 化学进展(Progress in Chemistry), 2003, 15(5): 409.
[7] White J E, Silvis H C, Winkler M S, Glass T W, Kirkpatrick D E. Adv. Mater., 2000, 12(23): 1791.
[8] Auvergne R, Caillol S, David G, Boutevin B, Pascault J P. Chem. Rev., 2014, 114(2): 1082.
[9] Egger H, Schlögl K. J. Organomet. Chem., 1964, 2(5): 398.
[10] Hill E A, Richards J H. J. Am. Chem. Soc., 1961, 83(20): 4216.
[11] Gokel G W, Marquarding D, Ugi I K. J. Org. Chem., 1972, 37(20): 3052.
[12] Kilway K V, Streitwieser A. J. Org. Chem., 1999, 64(14): 5315.
[13] Catasús M, Bueno A, Moyano A, Maestro M A, Mahía J. J. Organomet. Chem., 2002, 642(1/2): 212.
[14] Schwink L, Knochel P, Eberle T, Okuda J. Organometallics, 1998, 17(1): 7.
[15] Monlina P, Tárraga A, Curiel D, Velasco M D. J. Organomet. Chem., 2001, 637/639: 258.
[16] Pla D? uk D, Zakrzewski J. J. Organomet. Chem., 2006, 691(3): 287.
[17] Gu L, Jin C, Zhang H, Zhang L. J. Org. Chem., 2014, 79(17): 8453.
[18] Catasús M, Moyano A, Aggarwal V K. Tetrahedron Lett., 2002, 43(19): 3475.
[19] Hata K, Motoyama I, Watanabe H. Bull. Chem. Soc. Jpn., 1963, 36(12): 1698.
[20] Patti A, Nicolosi G. Tetrahedron: Asymmetry, 2000, 11(3): 815.
[21] Gilman H, Hofferth B, Honeycutt J B. J. Am. Chem. Soc., 1952, 74(6): 1594.
[22] Watanabe H, Motoyama I, Hata K. Bull. Chem. Soc. Jpn., 1966, 39(4): 784.
[23] Sosin S L, Alekseeva V P, Litvinova M D, Korshak V V, Zhigach A F. Vysokomol. Soedin. Ser. B, 1976, 18: 703.
[24] Lindvall M K, Koskinen A M P. J. Org. Chem., 1999, 64(13): 4596.
[25] Sevenair J P, Lewis D H, Ponder B W. J. Org. Chem., 1972, 37(25): 4061.
[26] Aggarwal V K, Abdel-Rahman H, Jones R V H, Lee H Y, Reid B D. J. Am. Chem. Soc., 1994, 116(13): 5973.
[27] Goldberg S I, Loeble W D. J. Org. Chem., 1968, 33(7): 2971.
[28] Adam W, Schuhmann R M. J. Organomet. Chem., 1995, 487(1/2): 273.
[29] Patti A, Nicolosi G. Tetrahedron: Asymmetry, 1999, 10(14): 2651.
[30] Patti A, Nicolosi G. Tetrahedron: Asymmetry, 2000, 11(18): 3687.
[31] Dagli D J, Yu P S, Wemple J. J. Org. Chem., 1975, 40(22): 3173.
[32] Arai S, Shirai Y, Ishida T, Shioiri T. Tetrahedron, 1999, 55(20), 6375.
[33] Ma F, Li X, Lan T, Ma Y, Chen B, Song Q. Synthesis, 2005, (12): 1945.
[34] Cangönül A, Behlendorf M, Gansäuer A, van Gastel M. Inorg. Chem., 2013, 52(20): 11859.
[35] Sudo A, Suzuki A, Endo T. J. Polym. Sci. Part A: Polym. Chem., 2013, 51(19): 4213.
[36] Shisodia S U, Auricchio S, Citterio A, Grassi M, Sebastiano R. Tetrahedron lett., 2014, 55(4): 869.
[37] Wang J J, Dai L X, Gao Q, Wu P F, Wang X B. Eur. Polym. J., 2008, 44(3): 602.
[38] Tonhauser C, Alkan A, Schömer M, Dingels C, Ritz S, Mailänder V, Frey H, Wurm F R. Macromolecules, 2013, 46(3): 647.
[39] Alkan A, Natalello A, Wagner M, Frey H, Wurm F R. Macromolecules, 2014, 47(7): 2242.
[40] Chuo T W, Wei T C, Liu Y L. J. Polym. Sci., Part A: Polym. Chem., 2013, 51(16): 3395.
[41] Wright M E, Laub J, Stafford P R, Norris W P. J. Organomet. Chem., 2001, 637/639: 837.
[42] Sriyudthsak M, Cholapranee T, Sawadsaringkarn M, Yupongchaey N, Jaiwang P. Biosens. Bioelectron., 1996, 11(8): 735.
[43] Nagel B, Warsinke A, Katterle M. Langmuir, 2007, 23(12): 6807.
[44] Zhang Z B, Yuan S J, Zhu X L, Neoha K G, Kang E T. Biosens. Bioelectron., 2010, 25(5): 1102.
[45] Tripathi V S, Kandimalla V B, Ju H. Biosens. Bioelectron., 2006, 21(8): 1529.
[46] ?enel M, Abasíyaník M F. Electroanal., 2010, 22(15): 1765.
[47] Çevik E, ?enel M, Abasíyaník M F. Curr. Appl. Phys., 2010, 10(5): 1313.
[48] ?enel M, Çevik E, Abasíyaník M F. Sens. Actuators B, 2010, 145(1): 444.
[49] ?enel M, Çevik E, Abasíyaník M F. Anal. Bioanal. Electrochem., 2011, 3(1): 14.
[50] Dursun F, Ozoner S K, Demirci A, Gorur M, Yilmazb F, Erhan E. J. Chem. Technol. Biotechnol., 2012, 87(1): 95.
[51] Patti A, Pedotti S. Tetrahedron: Asymmetry, 2003, 14(5): 597.
[52] Patti A, Lotz M, Knochel P. Tetrahedron: Asymmetry, 2001, 12(24): 3375.
[53] Kishore K, Pai Verneker V R, Dharumaraj G V. J. Polym. Sci.: Polym. Lett. Ed., 1984, 22(11): 607.
[54] Pedotti S, Patti A. Tetrahedron, 2012, 68(16): 3300.
[55] Ma L, Wang L, Tan Q, Yu H, Huo J, Ma Z, Hu H, Chen Z. Electrochim. Acta, 2009, 54(23): 5413.
[56] Yu H, Wang L, Huo J, Tan Q, Gao J. Des. Monomers Polym., 2008, 11(4): 347.
[57] Yu H, Wang L, Huo J, Ding J, Tan Q. J. Appl. Polym. Sci., 2008, 110(3): 1594.
[58] Yu H, Wang L, Huo J, Li C, Tan Q. Des. Monomers Polym., 2009, 12(4): 305.
[59] Gao J, Wang L, Yu H, Xiao A, Ding W. Propellants Explos. Pyrotech., 2011, 36(5): 404.
[60] 张岩(Zhang Y), 高国新(Gao G X), 韩婷婷(Han T T), 郑元锁(Zheng Y S). 化学推进剂与高分子材料(Chemical Propellants & Polymeric Material), 2011, 9(1): 78, 99.
[61] 王建军(Wang J J), 赵春正(Zhao C Z), 孙君(Sun J),谢浩俊(Xie H J), 张英(Zhang Y), 戴礼兴(Dai L X). ZL 201210188076.2, 2014.
[62] Ornelas C. New J. Chem., 2011, 35: 1973.
[63] Shen S L, Zhu J, Li M, Zhao B X, Miao J Y. Eur. J. Med. Chem., 2012, 54: 287.
[64] Shen S L, Shao J H, Luo J Z, Liu J T, Miao J Y, Zhao B X. Eur. J. Med. Chem., 2013, 63: 256.
[65] Li M, Zhao B X. Eur. J. Med. Chem., 2014, 85: 311.