二茂铁及其衍生物作为电化学传感器的研究进展

本文对近二十年来国内外对二茂铁及其衍生物作为电化学传感器的研究进展做了较全面的综述。主要讨论了二茂铁及其衍生物修饰电极的制备、表征,介绍了二茂铁及其衍生物作为电化学传感器的应用情况,并探讨了今后的研究方向。     

1，1’-二茂铁二甲醛的合成研究

半个世纪以来，由于二茂铁及其衍生物表现出特有的芳香性、稳定性、氧化还原性及生物活性等，使得它们在材料、航天、医疗等领域得到了广泛的应用。醛基取代二茂铁衍生物是其中的重要一种，除了具有二茂铁的特性外，还具有醛基的还原性以及羰基和Cp环的共轭特征，使其成为重要的中间体或起始原料，例如：Wright课题组首次合成了主链含二茂铁的二阶非线形金属有机聚合物，     

几个新型二茂铁衍生物的合成

二茂铁及其衍生物作为油类消烟剂、燃速催化剂等已得到应用,在药物、合成材料等方面亦具有应用前景。文献曾报道含二茂铁基β-二酮的合成及以它为配体的金属配合物。此类配合物均含两个以上金属原子,它们在有机合成中具有独特的催化活性。 我们将二茂铁甲酰丙酮分别与水扬酰肼、异菸肼、乙二胺及硫代氨基脲在甲醇或甲醇-水介质中进行缩合反应,合成了4个新型二茂铁衍生物,它们含有三个或四个配位功能基团,可作为多齿配体用于金属有机配合物的合成。衍生物的合成路线如下:     

双(烷基二茂铁基)丙烷的合成及其燃速催化性质

双(烷基二茂铁基)丙烷的合成及其燃速催化性质;二茂铁衍生物;燃速催化剂     

1'-碘代二茂铁甲醛合成的新方法

二茂铁甲醛是有机合成化学中一个重要的中间体,利用它可以合成各种功能二茂铁衍生物.然而异环取代的二茂铁甲醛因合成难度较大使其应用受到限制,1'-碘代二茂铁甲醛分子内因为有较多的反应活性点,从而被广泛应用到功能金属有机分子的设计合成中.合成该物质的传统方法不仅路线长,且需要使用昂贵的金属有机试剂.我们利用改进后的合成方法,以二茂铁为起始原料经三步反应合成了1'-碘代二茂铁甲醛.该方法不仅缩短了合成路线,简化了反应条件,且避免使用苛刻的反应条件和贵重的有机锂(锡)试剂,是目前合成该化合物最简单的方法.     

酰基二茂铁在液相中的电子传递性质

酰基二茂铁在液相中的电子传递性质蒋朝阳邰子厚＊季斌（南京大学配位化学国家重点实验室，南京２１００９３）关键词：酰基二茂铁三相氧化还原体系电子传递二茂铁及其衍生物在生物模拟和光电材料中有着极高的应用价值［１－４］。本文合成了一系列的酰基二茂铁ＦｃＸ（Ｘ...     

二茂铁酰基衍生物的研究进展

综述了近年来二茂铁酰基衍生物如二茂铁甲醛、二茂铁酮和二茂铁甲酸的合成及反应的研究进展，简要介绍了它在生物学、医学和电化学等领域的应用。参考文献７３篇。     

胺烷基二茂铁衍生物的合成方法

胺烷基二茂铁衍生物由于在有机合成中的特殊用途而受到化学家们的重视，成为二茂铁衍生物中的一个重要研究领域。本文介绍从不同起始原料出发，合成胺烷基二茂铁衍生物的方法。     

两种新型二茂铁衍生物的合成及其电化学性质

以二茂铁甲醛和三羟甲氨基甲烷为原料,经缩合,脱水和还原反应合成了两种新型的二茂铁衍生物,其结构经1H NMR, IR和MS表征,并利用循环伏安法研究了它们的电化学性质.     

二茂铁及其衍生物的电化学特性与结构理论研究

研究了二茂铁及其衍生物(甲酰二茂铁,乙酰二茂铁,甲醇二茂铁和乙酸二茂铁)的电化学行为,运用结构理论给出了二茂铁D5点群群轨道能级图与二茂铁衍生物的前线轨道能级图,得出在二茂铁分子结构中1e2(dx2-y2,dxy)与3a1(dz2,4s)分别属于分子前线轨道中的HOMO和LUMO。同时用密度泛函理论(DFT)在LANL2DZ基组水平上对其结构进行了全优化,得到了二茂铁及其衍生物前线最高被占轨道(HOMO)能量值,Fe原子净电荷,对其电化学行为与前线轨道能级相对大小进行了验证。     

Progress on the synthesis and catalytic and anti‐migration properties of ferrocene‐based burning rate catalysts

Burning rate catalysts are of great importance in solid composite propellants for their unique property of accelerating combustion speed. Among various kinds of burning rate catalysts, ferrocene and its derivatives exhibit excellent catalytic effects and have become the most widely used burning rate catalysts. However, these simple ferrocenyl compounds trend to migrate in solid composite propellants during storage, which causes great damage to the propellants, equipment and environment and can even affect personal safety. The exploration of novel anti‐migratory ferrocene‐based compounds has become an advanced research hotspot in the field of burning rate catalysis. This review focuses on recent progress on the synthesis and catalytic properties of ferrocene‐based polymers and ferrocene derivatives as burning rate catalysts. Two main aspects of anti‐migratory exploration, i.e. synthesis of ferrocene‐based polymers and modification of the side groups of ferrocene, are summarized. Ferrocene‐based polymers can be obtained via condensation polymerization, addition polymerization, ring‐opening polymerization, polymer reactions, etc. Ferrocenyl compounds with active groups and ferrocene‐based metal coordination compounds were developed instead of the methods of lengthening the carbon chain of side groups and improving molecular polarity. Also, possible mechanisms of burning rate catalytic activity and migration are discussed and analyzed. Finally, the key points of the development of ferrocene‐based burning rate catalysts and solid composite propellants are proposed. Copyright © 2016 John Wiley & Sons, Ltd.     

Recent research progress in the synthesis,properties and applications of ferrocene‐based derivatives and polymers with azobenzene

Aromatic azobenzene derivatives are outstanding organic photochromic compounds that possess unique photochemical properties. These compounds are widely used in research and development for various applications, especially in information storage, owing to their ability to isomerize between cis (Z) and trans (E) forms under the influence of light of different wavelengths. On account of these advantages, many efforts have been made to generalize the use of azobenzene derivatives. Furthermore, ferrocene‐based polymers and derivatives are promising candidates for functional materials due to their unique redox properties. By interlinking ferrocene with azobenzene, novel functional materials can be obtained that will integrate the excellent properties of both and will provide new applications in various fields including information storage, ion recognition, molecular devices, etc. This article provides an overview of the synthesis, properties and applications of novel ferrocene‐based polymers and derivatives containing azobenzene units. Copyright © 2015 John Wiley & Sons, Ltd.     

CuI‐Catalyzed coupling reaction of diazophosphonates with ferrocenylacetylenes: an efficient synthesis of ferrocene‐containing allenylphosphonates

An efficient synthesis of ferrocene‐containing allenylphosphonates via CuI‐catalyzed coupling reaction of diazophosphonates with ferrocenylacetylenes in the presence of Et₃N has been reported. This coupling methodology is applicable to a broad scope of substrates, allowing the synthesis of a range of synthetically valuable ferrocene‐containing trisubstituted allene derivatives in moderate to excellent yields.     

Recent advances in the synthesis,biological activities and various applications of ferrocene derivatives

Ferrocene derivatives constitute an important class of organometallic compounds with not only an extensive range of biological activities but also diverse industrial as well as material science applications. These stimulating features of ferrocene derivatives spurred us to review the recent advances in synthesis methods and biological and other applications reported in the latest literature. An effort has been made to summarize the recent developments in synthetic methods providing access to ferrocene scaffolds and the useful medicinal and material applications, including agricultural, catalytic, polymer, conducting, redox mediating, ferrocenyl stationary phase, rocket propellant and ion sensing applications. Ferrocene‐based bulky metallocenes are also discussed.     

Visual detection and removal of mercury ions by a ferrocene derivative

New ferrocene naphthyridine derivatives were successfully synthesized. The di-substituted ferrocene derivative FecDN behaves as a selective visual chemosensor for mercury ions, exhibiting a rapid and clearly visible precipitation with good selectivity (precipitation) and sensitivity (0.01 μM). The interaction of the ferrocene derivatives and metal ions was investigated by ultraviolet–visible spectroscopy (UV–vis), electrochemical methods, ¹H NMR, as well as infrared (IR), and energy dispersive X-ray spectroscopy (EDX). The application of FecDN in the detection and removal of mercury ions is very simple, rapid, and intuitive.     

A Facile Enantioselective Reduction of Acetylferrocene with Chiral Sodium Hydroboro—L—prolinate

IntroductionChiral ferrocene and their derivatives have at-tracted much attention of some researchers workingin the fields of asymmetric synthesis and nonlinearoptical material. In asymmetric catalysis,chiralferrocenyl phosphine and ferrocenyl amine are ex-cellent chiral ligands in the asymmetric hydrogena-tion,asymmetric allylic substration,asymmetricaldol reaction and asymmetric Michael additionetc.[1— 6] . While the starting material used to syn-thesize the chiral ferrocene is optically ac…     

二茂铁甲酸(2-丙烯酰氧乙基)酯的合成及优化

二茂铁类燃速催化剂在使用过程中存在的主要问题是在推进剂贮存过程中易产生迁移和挥发问题。 针对这些不足,对二茂铁衍生物进行改性,在二茂铁的茂环上引入极性基团以增大分子极性。 以二茂铁甲酸(FCA)和2-羟乙基丙烯酸酯(HEA)为反应物,以二环己基碳二亚胺(DCC)为脱水剂,以对二甲氨基吡啶(DMAP)为催化剂,在二氯甲烷(DCM)中合成二茂铁甲酸(2-丙烯酰氧乙基)酯(AEFC),优化各反应条件,确定最佳投料摩尔比为n(FCA):n(HEA):n(DMAP):n(DCC)=20:28:20:24,反应温度为0 ℃,DCC溶液滴加时间为60~75 min,反应时间为15 h,搅拌速率为1000 r/min,在此条件下得到的AEFC的产率为75.1%,纯度为98%。     

含二茂铁的β-内酰胺的研究进展

β-内酰胺类抗生素是目前最具应用价值的抗生素, 其结构特征具有β-内酰胺环的基元结构, 该类化合物的设计、合成和立体化学研究一直是有机合成化学研究的前沿和热点领域. 二茂铁凭借其独特的结构和多样的性质, 在生物和医药方面均有广泛的应用价值. 因此, 二茂铁修饰的β-内酰胺是一类结构新颖且具有潜在生物活性的化合物. 对该类化合物的深入研究, 将对新型抗生素的研发提供重要的指导意义. 综述了近年来青霉烷类和头孢烯类β-内酰胺及单环类β-内酰胺这两大类含二茂铁取代的β-内酰胺衍生物的合成与生物活性的研究进展.