一种1, 10-菲啰啉-5, 6-二酮及其单肟的高效合成方法

1,10-菲啰啉-5,6-二酮(2)与1,10-菲啰啉-5,6-二酮单肟(3)作为稠杂环共轭配体,既具有良好的配位特性,又是重要的有机合成反应中间体.由化合物2和它的衍生物与金属离子形成的配合物可以用于抗肿瘤药物、DNA探针、非线性光学材料、超分子组装分子骨架、自旋交叉配合物等许多领域.化合物3则用于有机光致变色化合物螺噁嗪的合成.     

1,10-邻菲啰啉-5,6-二酮修饰碳糊电极测定水中镉

以1,10-邻菲啰啉-5,6-二酮(phendio)修饰碳糊电极为工作电极,在0.05mol/L HAc-NaAc(pH4.74)电解液中,于-1.30V(vs.SCE)处Cd2 以Cd-1,10-邻菲啰啉-5,6-二酮络合物的形式吸附到电极上,再经过阳极溶出,从而建立了一种测定水样中痕量镉的新方法。本法于-0.69V处产生一个灵敏的溶出峰,其二阶导数峰电流与Cd2 的浓度在2.4×10-7~6.0×10-9mol/L范围内呈良好的线性关系;检出限为3.0×10-10mol/L(S/N=3)。应用本方法测定水样中的Cd2 ,结果令人满意。     

采用Miyaura反应合成新型邻菲啰啉衍生物

以2,9-二氯-1,10-邻菲啰啉-5,6-二酮为原料,与2-硝基丙烷反应得双酮被保护的2,9-二氯-5,6-O-异丙叉基-1,10-邻菲啰啉(2);2与频哪醇硼酸酯在PdCl2(dppf)催化下经Miyaure反应合成了新化合物———9,9'-二氯-5,6;5',6'-二(O-异丙叉基)-2,2'-联邻菲啰啉,其结构经1H NMR,IR和MALDI-TOF-Mass表征。     

1,10-邻菲咯啉衍生物的合成及其晶体结构

以1,10-邻菲咯啉为原料,经氧化反应合成了1,10-邻菲咯啉-5,6-二酮(1);1与对氟苯甲醛反应合成了2-苯基(4-氟)-咪唑[4,5]-1,10-邻啡咯啉(2).1和2的结构经1H NMR,MS和X-射线单晶衍射表征.1为正交晶系,Pna21空间群,晶胞参数为:a=14.329 0(4)(A),b=12.370 0(3)(A),c=6.395 6(16)(A),α=90°,β=90°,γ=90°,V=1 133.5(5)(A)~3,Z=14,Dc=2.521 g·cm~(-3),μ=12.430 mm~(-1),F(000)=789,最终偏离因子R=0.039 8,wR=0.114 7.2为单斜晶系,P21/n,空间群晶胞参数为:a=9.810 0(4)(A),b=10.951 0(4)(A),c=17.3670(7)(A),α=90.000°,β=99.042(5)°,γ=90.000°,V=1 842.5(12)(A)~3,Z=4,Dc=1.292 g·cm~(-3),μ=0.095mm~(-1),F(000)=732,最终偏离因子R=0.091 2,wR=0.334 9.     

菲啰啉吡咯的合成工艺改进

1,10-邻菲啰啉经硝化反应制得5-硝基-1,10-邻菲啰啉(1).以无水乙醇为溶剂,1与异氰基乙酸乙酯在K2CD3的催化下通过Barton-Zardon反应合成了一种稠合菲啰啉环并吡咯衍生物2.较佳的反应条件为:1 10mmol,n(1):n(异氰基乙酸乙酯):n(K2CO3)=1.0:1.0:1.1,于室温反应24...     

铜(Ⅱ)-邻菲咯啉-(邻菲咯啉-5,6-二酮)络合物的合成及其同脱氧核糖核酸的作用

以邻菲咯啉（phen)、邻菲咯啉－5，6－二酮（dione)为配体首次合成了高氯酸邻菲咯啉－邻菲咯啉－5，6－二酮（Ⅱ）。用荧光光谱，摩尔比，粘度，MLCT减色效应，平衡常数以及荧光能量转移研究了各合物与鱼精子DNA的结合情况，证实了该络合物与DNA存在插入作用。基于络合物对DNA能量转移造成荧光量子产率比值（Φλ/Φ320）的降低，解释了不同波长激发光下，荧光发射峰在加入DNA后产生猝灭和增强两种绝然不同的现象。     

4,7-二苯基-1,10-菲啰啉的合成研究

以4-苯基-8-硝基喹啉为起始原料,经还原得到4-苯基-8-氨基喹啉,再以I2/KI为氧化剂,在乙酸和盐酸的存在下,用Skraup法合成了4,7-二苯基-1,10-菲啰啉.化合物结构经IR和1H NMR得到了证实.实验研究得到了最佳的合成条件为:n(3-氯苯丙酮)∶n(4-苯基-8-氨基喹啉)=1.5∶1,I2/KI用量为8%,反应温度120℃,反应时间2.5 h.产品收率可达82%.     

新型亲脂性菲啰啉衍生物的合成及其自组装性能

以1,10-菲啰啉为起始原料,经溴代、氧化、Suzuki偶联等反应合成了新型亲脂性菲啰啉衍生物——3,8-二(4-联苯基)-5,6-二(十二烷氧基)-1,10-菲啰啉(1),总收率11.24%,其结构经1H NMR,13C NMR和MALDITOF-MS表征。自组装性能研究结果表明,1的自组装体呈规整的微米球状结构。     

新型邻菲啰啉衍生物的合成

以2-［2-（2-甲氧基乙氧基）乙氧基］乙基-4-甲基苯磺酸为原料,经2步反应制得中间体2,2′-【2,5-二｛2-［2-（2-甲氧基乙氧基）乙氧基］｝1,4-二（4,4,5,5-四甲基）-1,3,2-二氧硼基】苯（6）; 3-溴-1,10-邻菲啰啉和6经Suzuki偶联反应合成了一个新型的邻菲啰啉衍生物--3,3′-【2,5-二｛2-［2-（2-甲氧基乙氧基）乙氧基］｝-1,4-二（1,10-菲啰啉基）】苯,其结构经¹H NMR和MALDI-TOF-MS表征。     

稀土苦味酸盐与1,10-菲啰啉-N-氧化物配合物的合成

在非水介质中合成出稀土苦味酸盐与PhenNO的配合物,RE(PhenNO)_2(Pic)_3(RE=La,Pr,Nd,Sm～Tb,Er,Y)。通过元素分析、摩尔电导、红外光谱、拉曼光谱、电子光谱、荧光光谱、DTA-TG及~1H NMR谱等对配合物进行了表征。     

1,10-邻菲咯啉-5,6-二酮制备反应中副产物的形成与控制

由1,10-邻菲咯啉合成1,10-邻菲咯啉-5,6-二酮反应的副产物的形成与控制研究表明,1,10-邻菲咯啉在5,6位二酮化反应中的副反应产物及主产物分离时产生的副产物均为4,5-二氮杂芴-9-酮,二酮化反应条件(包括作为氧化剂的强混合酸H2SO4/HNO3的加入量、时间和温度)和主产物分离时体系的酸度对副产物的形成有重要影响,优化了二酮化反应条件和产物分离时的体系pH控制范围。在此优化条件下,可有效控制副产物的形成,使主产物1,10-邻菲咯啉-5,6-二酮的收率达到92%以上。     

Efficient Synthesis of 1,10-Phenantroline-5,6-dione

Russian Journal of General Chemistry - A method for the synthesis of 1,10-phenanthroline-5,6-dione via oxidation of 1,10-phenanthroline in the Br2-H2SO4-HNO3 system has been elaborated.     

Synthesis and Crystal Structure of the Copper(Ⅱ) Complex with 1,10-Phenanthroline-5,6-dione

<正>The complex Cu(phon)(NO3)2(CH3CN) (phon = 1,10-phenanthroline-5,6-dione) has been synthesized and characterized by elemental analysis, infrared and UV-Vis spectra. X-ray diffraction analysis at room temperature indicates that the complex crystallizes in orthorhombic system, space group P212121 with a = 8.353(1), b = 11.299(2), c = 17.764(2) A, V= 1676.5(4) A3, Z = 4, C14H9CuN5O8, Mr = 438.8, Dc = 1.739 g/cm3, F(000) = 884 and μ(MoKα) = 1.361 mm-1. The final R and wR factors for the observed reflections with I > 2σ(I) are 0.0353 and 0.0855, respectively. R = 0.0432 and wR = 0.0899 for all data. The structure of the title complex consists of a neutral mononuclear entity. The central Cu (II) atom is five-coordinated by two nitrogen donors of one ligand, two unidentate NO3- ions and one CH3CN molecule. The coordination geometry of Cu (II) can be considered as a distorted trigonal bipyramidal configuration. The complex ability of the NO3-ion has more effect than that of the ClO4- ion on the structure of th     

Sensitive and Low-background Electrochemical Immunosensor Employing Glucose Dehydrogenase and 1,10-Phenanthroline-5,6-dione

We report a sensitive electrochemical immunosensor with a low electrochemical background level, which results from electrochemical-enzymatic (EN) redox cycling based on mediated electrochemical oxidation of an electro-inactive reductant (glucose) at 0.0 V. The EN redox cycling employs flavin adenine dinucleotide-dependent glucose dehydrogenase and 1,10-phenanthroline-5,6-dione (PD). When PD was compared with five common quinone-based electron mediators, PD enabled the highest signal-to-background ratio, due to a very low electrochemical background level. When EN redox cycling was applied to a sandwich-type immunosensor, parathyroid hormone (PTH) in serum could be detected with a very low detection limit of ∼0.1 pg/mL.     

1,10-Phenanthroline-5,6-dione and 9,10-phenanthrenequinone as redox mediators for amperometric glucose biosensors

In this study, two ortho-quinoidal compounds, 1,10-phenanthroline-5,6-dione (PD) and 9,10-phenanthrenequinone (PQ), were examined as electron transfer mediators suitable for amperometric glucose biosensors. The dependences of the electrochemical responses of PD- and PQ-based amperometric glucose biosensors on varied concentrations of glucose were investigated under aerobic and anaerobic conditions. The PD-modified graphite rod (GR) electrode revealed a current response seven times higher than that of the PQ-modified GR electrode. The reactivity indices of ortho-quinoidals assessed by means of B3LYP functional method applying 6-311G(D) basis set showed that the electron-accepting potency for PD was markedly higher as compared with that of PQ. Compared to PQ, considerably higher reactivity of PD has been defined in the reactions with NADP⁺-ferredoxin reductase (FNR, EC 1.18.1.2) as a model single-electron transfer FAD-dependent enzyme, which provided an additional evidence for PD as a more efficient mediator compared to PQ. This study illustrates that PD can be applied as a redox mediator for glucose oxidase and it could be more suitable for a reagent-less biosensor design than PQ.     

基于1,10-邻菲罗啉-5,6-二酮和Keggin型多金属氧化物的化合物的水热合成及性质

在水热条件下,用1,10-邻菲罗啉-5,6-二酮(Do)作为中性配体合成了3个基于Keggin型多金属氧化物的化合物(HDo)₆(PW₁₂O₄₀)₂·H₂O(1),[Cu(Do)₂(H₂O)]₂[Cu(Do)₂(PW₁₂O₄₀)(H₂O)](PW₁₂O₄₀)(2)和[Pb(Do)₂(PW₁₂O₄₀)](HDo)(3),并对其进行了元素分析、红外光谱、电感耦合等离子体分析、Ｘ射线光电子能谱、热重分析以及荧光光谱等表征。单晶X射线衍射分析表明化合物1和2为零维结构,化合物3是一维链状结构。     

Synthesis and pH-sensitive redox properties of 1,10-phenanthroline-5,6-dione complexes

Synthesis and pH-sensitive electrochemical properties of three complexes, [Cu(PD)₃] · (ClO₄)₂ · 2.25CH₃CN · 6H₂O (1), [Cu(PD)(DMSO)Cl₂] · DMSO · H₂O (2) and [Co(PD)₃] · (ClO₄)₂ · CH₃CN · 2H₂O (3) (PD=1,10-phenanthroline-5,6-dione), are reported. Single-crystal X-ray diffraction of the complexes suggest that the structure of 1 is orthorhombic, 2 triclinic and 3 orthorhombic. The electrochemical properties of free PD and the three complexes in phosphate buffer solutions in a pH range between 2 and 9 have been investigated using cyclic voltammetry. The redox potentials of these compounds are strongly dependent on the proton concentration in the range ?0.3 V ～ 0.4 V versus SCE (saturated calomel reference electrode). The reduction behavior of PD can be described from quinone species to semiquinone anion then to the fully reduced dianion. At pH < 4, the reduction of PD proceeds via 2e^?/3H⁺ processes, while at pH > 4, the reduction of PD proceeds via 2e^?/2H⁺. For all complexes, the N–N chelate PD ligand is electrochemically active and underwent step reduction via 2e^?/2H⁺.     

Synthesis and Crystal Structure of the Copper(Ⅱ) Complex with Tris- (1,10-phenanthroline-5,6-dione)

The title complex [ CuL3 ] (C1O4)2 · 2H2O· 2CH3CN (L = 1, 10-phenanthroline-5, 6-dione) has been synthesized and characterized by elemental analysis, conductivity, infrared and UV-Vis spectra. X-ray diffraction analysis at room temperature indicates that the complex (C40H28Cl2 CuNsO16, Mr = 1011.14) crystallizes in orthorhombic system, space group P21 21 21 with a = 13. 983(1), b = 14. 310 (1), c =20.890(2) (A。), V = 4179.7(6) (A。)3, Z = 4, Dc= 1.607g/cm3, F(000) = 2026,μ(MoKa) = 0.736 mm-1. The final R and w,R factors are 0.0446 and 0. 1212 respectively with 8545 independent reflections. The title complex is composed of a discrete [CuL3 ]2+ cation, uncoordinated ClO4- anions, H2O and CH3CN molecules. The central Cu(Ⅱ) atom is six-coordinated by six nitrogen donors of three ligands. The coordination geometry of Cu(Ⅱ) could be considered as an approximately ideal octahedral configuration with little static Jahn-Teller distortion (the longest and shortest Cu- N bonds are 2. 102 vs 2. 139 (A。) with the mean length of 2. 122 (A。) ), which is very rare for a six-coordinated Cu(Ⅱ) complex.