三烃基锡二茂铁甲酸酯的合成、表征及其生物活性

谱学表征;三烃基锡二茂铁甲酸酯的合成、表征及其生物活性     

一维链状三(邻氟苄基)锡二茂铁甲酸酯的合成、结构和量子化学研究

二茂铁甲酸与μ-氧-双[三(邻氟苄基)锡]反应合成了一维链状三(邻氟苄基)锡二茂铁甲酸酯，经X射线衍射方法测定了化合物的晶体结构。化合物晶体属单斜晶系，空间群为P2₁/n，晶体学参数：a=1.592 4(6) nm，b=1.013 4(4) nm，c=1.748 2(7) nm，β=91.920(7)°，V=2.819 4(19) nm³，Z=4，D_c=1.590 g·cm^-3，μ(Mo Kα)=14.48 cm^-1，F(000)=1 352，R₁=0.041 8，wR₂=0.078 5；锡原子呈五配位为畸变三角双锥构型，通过二茂铁甲酸羧基桥联形成一维链状结构。对其单元结构进行量子化学从头计算，探讨了化合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。     

1,1′-二硒取代二茂铁衍生物的合成

由1,2,3-三硒[3]桥二茂铁(Ferrocenophane)经LiAlH_4还原生成二硒酚,不经分离直接与一亲电试剂在三乙胺存在下反应,得到7种1,1′-二硒醚二茂铁,4种1,n-二硒[n]桥二茂铁(n=3～5)和1种螺形化合物[Fe(C_5H_4Se)_2]_2Sn。这12种化合物中有7种尚未见文献报道,对其中几种产物进行了~(77)Se NMR谱及质谱分析。讨论了影响产率的因素和核磁共振图谱。     

(2,2-双二茂铁基丙烷)-6-甲酸酯的合成与表征

以2,2-双二茂铁基丙烷作为母体制得对应的甲酸,并以此合成了一系列未见文献报道的（2,2-双二茂铁基丙烷）-6．甲酸酯,其结构经1^H NMR,IR及元素分析表征。     

四(邻氟苄基)锡及一维链状三苄基锡二茂铁甲酸酯的合成、结构及性质

合成了四(邻氟苄基)锡(1)和一维链状三苄基锡二茂铁甲酸酯(2),经X射线衍射方法测定了化合物的晶体结构.化合物1属为四方晶系,空间群I4₁/a,晶体学参数a=1.967 94(16) nm,b=1.967 94(16) nm,c=0.593 16(5) nm,V=2.297 2(3) nm³,Z=4,D_c=1. 605 g·cm^-3,μ(Mo Kα)=11.58 cm^-1,F(000)=1 112,R₁=0.020 8,wR₂=0.057 6.化合物2属单斜晶系,空间群为P2₁/n,晶体学参数:a=1.593 54(12) nm,b=1.007 23(8) nm,c=1.700 26(13)56 nm,β=91.001(10)°,V=2.728 6(4) nm³,Z=4,D_c=1.521 g·cm^-3,μ(Mo Kα)=14.74 cm^-1,F(000)=1 256,R₁=0.038 4,wR₂=0.095 2.晶体的中心锡原子分别呈四配位畸变四面体构型和五配位畸变三角双锥构型.对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征.测定了配合物的热稳定性和体外抗癌活性.     

四(邻氟苄基)锡及一维链状三苄基锡二茂铁甲酸酯的合成、结构及性质

合成了四(邻氟苄基)锡(1)和一维链状三苄基锡二茂铁甲酸酯(2),经X射线衍射方法测定了化合物的晶体结构。化合物1属四方晶系,空间群I4₁/a,晶体学参数a=1.96794(16)nm,b=1.96794(16)nm,c=0.59316(5)nm,V=2.2972(3)nm³,Z=4,D_c=1.605g·cm^-3,μ(MoKα)=11.58cm^-1,F(000)=1112,R₁=0.0208,wR₂=0.0576。化合物2属单斜晶系,空间群为P2₁/n,晶体学参数:a=1.59354(12)nm,b=1.00723(8)nm,c=1.70026(13)nm,β=91.001(10)°,V=2.7286(4)nm³,Z=4,D_c=1.521g·cm^-3,μ(MoKα)=14.74cm^-1,F(000)=1256,R₁=0.0384,wR₂=0.0952。晶体的中心锡原子分别呈四配位畸变四面体构型和五配位畸变三角双锥构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了配合物的热稳定性和体外抗癌活性。     

新型环蕃二茂铁二甲酸二羟乙苯胺酯的合成及表征

以二茂铁为原料, 通过合成1,1'-二乙酰基二茂铁、1,1'-二茂铁二甲酸、1,1'-二茂铁二甲酰氯, 在高度稀释条件下与4种二羟乙基苯胺进行酯化反应得到了1,9-二羰基-2,8-二氧-5-(4-氟)苯基氮[9]二茂铁酯环蕃a, 1,9-二羰基-2,8-二氧-5-(4-甲基)苯基氮[9]二茂铁酯环蕃b, 1,9-二羰基-2,8-二氧-5-(4-甲氧基)苯基氮[9]二茂铁酯环蕃c, 1,9-二羰基-2,8-二氧-5-(4-硝基)苯基氮[9]二茂铁酯环蕃d. 用UV、¹H NMR、FT-IR、元素分析和基质辅助激光解析电离-飞行时间质谱(MALDI-TOF)对这些化合物进行了表征. 培养了二茂铁酯环蕃a的单晶, 并对其结构进行了解析.     

PTC法合成对羧基苯甲酰二茂铁四乙酰葡萄糖酯

前文[1]报道了邻羧基苯甲酰二茂铁四乙酰葡萄糖基酯的合成及其抗贫血活性研究 ,发现邻羧基苯甲酰二茂铁及其四乙酰葡萄糖基酯具有较好的抗贫血性能,有望成为一类新型的补铁剂.     

二茂铁甲酸(三邻氯苄基)锡配合物的合成、结构和量子化学研究

The novel complex tri(o-chlorobenzyl)tin ferrocenecarboxylate have been synthesized.The crystal structure of the complex has been determined by X-ray diffraction.The crystal belong to orthorhombic with space group Pbca with a=0.1242(5), b=1.7242(7), c=3.0583(13)nm, V=5.928(4)nm³,Z=8, D_c=1.623g·cm^-3,μ(MoKα)= 0.1631cm^-1,F(000)=2896,R₁=0.0461,wR₂=0.0931. The bond lengths of Sn-C is 0.2148(4), 0.2152(6) and 0.2176(5)nm, respectively. The Sn-O is 0.2073(4)nm. The tin atom has a distorted tetrahedral geometry. The study on title complex has been performed,with quantum chemistry calculation by means of G98W package and taking Lanl2dz basis set. The stability of the complex, some frontier molecular orbital energies, the populations of the atomic net charges in complex and composition characteristics of some frontier molecular orbitals have been investigated. CCDC: 184267.     

Synthesis of tetracyanoethylene‐substituted ferrocene and its device properties

Small organic molecules are promising candidates for cheaper, flexible and good‐performance sources for organic solar cells (OSCs) due to their easy fabrication, low cost and slightly cheaper processing. However, the lower power conversion efficiency of OSCs is the main problem for their applications. Ferrocene structures could be the best candidates for the active layers of OSCs due to their unique properties such as thermal and chemical stability. The electrochemical, electro‐optical and solar cell performances of 2,5‐dicyano‐3‐ferrocenyl‐4‐ferrocenylethynylhexa‐2,4‐dienedinitrile (DiCN‐Fc) structures were investigated. First, the electrochemical and electro‐optical properties were examined for finding the highest occupied and lowest unoccupied molecular orbital values and bandgap of DiCN‐Fc. The best photovoltaic performance was obtained with 7 wt% of DiCN‐Fc loading, with a power conversion efficiency of about 4.27%. In the light of our investigations, ferrocenyl‐substituted small organic molecules could contribute to the development of organic photovoltaic devices.     

Synthesis of liquid crystal ferrocene derivatives and their complexes with Cu2+

A series of liquid crystal ferrocene-containing Schiff bases of general formula C₅H₅FeC₅H₄-C₆H₄-N=CN-(X)C₆H₃-O(O)-C₆H₄-OC_nH_2n+1 (X=H, OH, n=3–12) was obtained, together with several analogs, 1,1-bis-substituted at the ferrocene fragment, having a thermotropic nematic mesophases. Derivatives with X=OH were used to obtain Cu²⁺ chelate complexes, of which the compounds with n=10 and n=12 displayed nematic liquid crystalline properties.Physicotechnical Institute, Kazan Scientific Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 402–407, February, 1992.     

Thermal stability of ferrocene derivatives and ferrocene-containing polyamides

Thermogravimetric data and the kinetic interpretation of the curves of mass loss for ferrocene, ferrocenecarboxylic and ferrocenedicarboxylic acids and a series of ferrocene-containing polyamides are presented. The results indicate that the degradation process occurred with more than one stage of thermal degradation. The apparent activation energy values and the FTIR spectra of the degradation products suggest that the degradation mechanism occurred by either scission of weak links or by random scission of the chain. Apparently, the N-vicinal methylene group was the primary site of attack of oxygen on the polymer chain. This revised version was published online in August 2006 with corrections to the Cover Date.     

Chiral ferrocene cyanohydrin derivatives—access to novel intermolecularly linked and intramolecularly bridged ferrocene derivatives

By reduction of the cyano group in (R)-(cyanohydroxymethyl)ferrocene and (R,R)-1,1′-bis(cyanohydroxymethyl)ferrocene, amines were obtained giving access to several new diamine and diamide bridged chiral ferrocene derivatives. As a representative for an intramolecularly bridged ferrocene compound bearing two chiral centres (R,R)-8 was obtained with excellent optical purity.     

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。     

Derivatization of valproic acid using ferrocene derivatives: Synthesis,characterization and investigation of optical and electrochemical properties

New ferrocenyl‐based valproic acid (VPA) ester derivatives were designed and synthesized according to the reaction of appropriate haloalkylferrocene derivatives with VPA in the presence of K₂CO₃ and a catalytic amount of 18‐crown‐6 ether. Elemental analyses and Fourier transform infrared, ¹H NMR, ¹³C NMR and mass spectra all well confirmed the predicted molecular structure. This is the first report in which ferrocene has been applied in derivatization of VPA as a chromogenic group. The electrochemical properties of the synthesized compounds were studied using cyclic voltammetry measurements, and energies of the frontier molecular orbitals were determined. In addition, the solubilities of the final compounds were studied in distilled water, phosphate buffer (pH = 7.4) and 0.9% (w/v) NaCl solution.     

Synthesis and biological evaluations of mono‐ and bis‐ferrocene uracil derivatives

Mono‐ ( 3a – 3e and 4a – 4e ) and bis‐ferrocene ( 5a – 5e and 6a – 6e ) conjugated 5‐substituted uracil derivatives that are bridged by 1,2,3‐triazole linker were synthesized. The impact of ferrocene unit and spacer between ferrocene and triazole on radical scavenging potency was observed. Bis‐ferrocenyl uracil derivatives exhibited better antiproliferative activities than their mono‐ferrocenyl analogs. Bis‐ferrocenyl methyl‐ ( 5b ) and halogen‐substituted ( 5e , 6c , and 6d ) uracil derivatives showed pronounced and selective cytostatic activities on colon adenocarcinoma (CaCo‐2) and Burkitt lymphoma (Raji) cells, with higher potency and selectivity than the reference drug 5‐fluorouracil. Generation of reactive oxygen species (ROS) in CaCo‐2 and Raji cells when treated with compounds 5b , 5e , and 6d was observed. Bis‐ferrocenyl 5‐chlorouracil 6c induced significant disruption in mitochondrial membrane potential that is accompanied by activation of apoptosis in CaCo‐2, Raji, and acute lymphoblastic leukemia (CCRF‐CEM) cells, while 6d caused mitochondrial dysfunction and apoptosis induction in CaCo‐2 and Raji cells. Potent antiproliferative activity of 6c and 6d could be associated with mitochondrial membrane potential disruption accompanied by apoptosis induction. Our findings highlighted 6c and 6d with potent and selective antiproliferative activity on CaCo‐2, Raji, and CCRF‐CEM cells that may be associated with targeting cancer cell mitochondria, as a molecular target.     

Novel ferrocenyl phosphonate derivatives. Inhibition of serine hydrolases by ferrocene azaphosphonates

Owing to their unique properties, ferrocene compounds are gaining increasing interest for biological applications, particularly as enzyme inhibitors. Phosphonate derivatives including a ferrocenyl moiety were synthesized by reaction of dimethyl‐ and diphenylphosphite with ferrocenyl methyl maleimide. The ferrocenyl diphenyl phosphonate complex was characterized by X‐ray diffraction. The ability of these organometallic compounds to inhibit the enzymatic activity of the serine esterases acetyl‐ and butyrylcholinesterase was investigated. It appeared that the new ferrocenyl phosphonates inhibited both enzymes by competitive, mixed or non competitve mechanisms with inhibition constants in the range 35–1000 µM. Both compounds also behave as slow time‐dependent inactivators of butyrylcholinesterase. The presence of the ferrocenyl entity seems then to have a dramatic effect on the biochemical behavior of the systems. Copyright © 2010 John Wiley & Sons, Ltd.