Synthesis of two novel ring systems via photocyclization: Thieno[2′,3′:4,5]thieno[2,3-c][1,10]phenanthroline and thieno[3′,2′:4,5]thieno[2,3-c][1,10]phenanthroline

The synthesis of thieno[2′,3′:4,5]thieno[2,3-c][1,10]phenanthroline ( 5 ) and thieno[3′,2′:4,5]thieno-[2,3-c][1,10]phenanthroline ( 10 ) are described. Each compound was obtained in four steps from known starting materials. The basic skeleton of the molecule and of the phenanthroline ring were formed via photocyclization. The total assignment of ¹H-nmr spectra was accomplished with the aid of two-dimensional nmr methods.     

Bis(4,4′‐dimethyl‐2,2′‐bipyridine) ruthenium (II) Complexes Containing 2‐Arylimidazo‐ [4,5‐f] [1,10] phenanthroline: Syntheses,Characterization and Third‐order Nonlinear Optical Properties

Four novel mononuclear ruthenium(II) complexes [Ru(dmb)₂L]²⁺ [dmb = 4,4′‐dimethyl‐2,2′‐bipyridine, L = imidazo‐[4,5‐f][1,10]phenanthroline (IP), 2‐phenylimidazo‐[4,5‐f][1,10]phenanthroline (PIP), 2‐(4′‐hydroxyphenyl)imidazo‐[4,5‐f] [1,10] phenanthroline (HOP), 2‐(4′‐dimethylaminophenyl) imidazo‐[4, 5‐f] [1,10] phenanthroline (DMNP)] were synthesized and characterized by ES‐MS, ¹H NMR, UV‐vis and electrochemistry. The nonlinear optical properties of the ruthenium(II) complexes were investigated by Z‐scan techniques with 12 ns laser pulse at 540 nm, and all of them exhibit both nonlinear optical (NLO) absorption and self‐defocusing effect. The corresponding effective NLO susceptibility |x³| of the complexes is in the range of 2.68 × 10^?12‐4.57 × 10^?12 esu.     

Synthesis of Pyridophenanthrolines via a Three‐Component Reaction Involving 1,10‐Phenanthrolin‐5‐Amine

A facile and efficient method for the synthesis of benzo[b ]pyrido[3,2‐f ][1,7]phenanthrolines and dipyrido[4,3‐b :3′,2′‐f ][1,7]phenanthrolines has been developed in high yields. Using EtOH as a solvent without any additionally basic catalysts, the three‐component reaction of aromatic aldehyde, 1,10‐phenanthrolin‐5‐amine, and dimedone or piperidine‐2,4‐dione affords two novel classes of fused phentacyclic heterocycles containing both pyridine and phenanthroline moieties.     

Solvent-free synthesis of dibenzo[b,j][1,10]phenanthroline derivatives using Eaton’s reagent as catalyst

A new class of dibenzo[b,j][1,10]phenanthrolines has been prepared. The synthon acridones were achieved in very good yield by a one-pot reaction of 2-amino-5-chloro or 2′-chloro/flouro-substituted benzophenones with 1,2-cyclohexanedione in the presence of freshly prepared Eaton’s reagent (phosphorus pentoxide–methanesulfonic acid) without solvent, through Friedländer synthesis. Then these intermediates were reacted with 2-amino-3,5-dibromobenzaldehyde to afford 1,3-dibromo-10-chloro-8-aryl-6,7-dihydrodibenzo[b,j][1,10]phenanthroline. Also an one-pot reaction between 2?mol of 2-amino-5-chloro aryl benzophenones with 1?mol of 1,2-cyclohexanedione to get 3,10-dichloro-5,8-diaryl-6,7-dihydrodibenzo[b,j][1,10]phenanthroline has also been reported. The newly synthesized structures of the compounds were deduced by spectroscopic techniques.     

Green Synthesis of Benzo or Cyclopenta[j][1,7]phenanthroline Derivatives in EtOH under Catalyst‐free Conditions

A total of 25 benzo[j ][1,7]phenanthroline and cyclopenta[j ][1,7]phenanthroline derivatives were synthesized in EtOH under catalyst‐free conditions. This procedure included a three‐component reaction of aromatic aldehydes, quinolin‐7‐amine, and active methylene compounds and provided an efficient and green access to the synthesis of [1,7]phenanthrolines in high yields.     

Synthesis and total 1H-NMR assignment of naphtho[1′,2′:4,5]thieno[2,3-c][1,10]phenanthroline and naphtho[2′,1′:4,5]-thieno[2,3-c] [1,10]phenanthroline

Naphtho[1′,2′:4,5]thieno[2,3-c][1,10]phenanthroline and naphtho[2′,1′:4,5]thieno[2,3-c][1,10]phenanthroline, two novel polycyclic heterocyclic ring systems, have been synthesized in four steps from known starting materials. The total ¹H nmr spectral assignments were made using a COSY experiment to identify the spin systems.     

Highly regioselective synthesis of dicyano-8a,10,11-trihydropyrrolo[1,2-a][1,10]phenanthrolines via a domino-Knoevenagel-cyclization

1,10-Phenanthrolinium N-ylides,can react with malonitrile and aromatic aldehydes via a domino-Knoevenagel cyclization to afford a new class of trihydropyrrolo[1,2-a][l,10]phenanthroline derivatives as stable helical compounds in a simple,mild,and efficient protocol in excellent yields.     

Synthesis of Cyano‐pyrrolo[1,2‐a][1,10]phenanthroline Derivatives Using a Multicomponent Condensation

1,10‐Phenanthroline reacts with malonitrile and aldehydes in the presence of isocyanides as domino‐Knoevenagel‐nucleophilic cycloaddition for generation of a new class of 10‐(aryl)‐11‐(alkyl‐ or arylamino‐)pyrrolo[1,2‐a][1,10]phenanthroline‐9‐carbonitrile compounds in excellent yield. All compounds are fully characterized with one structurally authenticated by a single X‐ray diffraction study.     

Synthesis and Characterization of Heteroleptic Ru(II) Complexes Based on 4,4′‐Bis((E)‐styryl)‐2,2′‐bipyridine as Ancillary Ligand and Application for Dye‐Sensitized Solar Cells

Heteroleptic Ru(II) complexes were designed based on 4,4′‐bis((E)‐styryl)‐2,2′‐bipyridine (bsbpy) as an ancillary ligand for dye‐sensitized solar cells (DSSCs), and those Ru(II) sensitizers, [Ru(L)(bsbpy)(NCS)₂][TBA] (TBA; tetrabutylammonium), were synthesized according to a typical one‐pot reaction of [RuCl₂(p‐cymene)]₂ with the corresponding anchoring ligands (where L = 4,4′‐dicarboxy‐2,2′‐bipyridine (dcbpy), 4,4′‐bis((E)‐carboxyvinyl)‐2,2′‐bipyridine (dcvbpy), 4,7‐dicarboxy‐1,10‐phenanthroline (dcphen), or 4,7‐bis((E)‐carboxyvinyl)‐1,10‐phenanthroline (dcvphen)). The new Ru(II) dyes, [Ru(L)(bsbpy)(NCS)₂][TBA] that incorporated vinyl spacer(s) into ancillary and/or anchoring ligand displayed red‐shifted bands over the overall UV/VIS region relative to the absorption spectra of N719 . A combination of bsbpy ancillary and dcphen anchoring ligand showed the best result for the overall power conversion efficiency (η); i.e., a DSSC fabricated with [Ru(dcphen)(bsbpy)(NCS)₂][TBA] exhibited a power conversion efficiency (η) of 2.98% (compare to N719 , 4.82%).     

Diversity‐Oriented Synthesis of Novel 2′‐Aminospiro[11H‐indeno[1,2‐b]quinoxaline‐11,4′‐[4H]pyran] Derivatives via a One‐Pot Four‐Component Reaction

A sequential one‐pot four‐component reaction for the efficient synthesis of novel 2′‐aminospiro[11H‐indeno[1,2‐b]quinoxaline‐11,4′‐[4H]pyran] derivatives 5 in the presence of AcONH₄ as a neutral, inexpensive, and dually activating catalyst is described (Scheme 1). The syntheses are achieved by reacting ninhydrin ( 1 ) with benzene‐1,2‐diamines 2 to give indenoquinoxalines, which are trapped in situ by malono derivatives 2 and various α‐methylenecarbonyl compounds 4 through cyclization, providing the multifunctionalized 2′‐aminospiro[11H‐indeno[1,2‐b]quinoxaline‐11,4′‐[4H]pyran] analogs 5 . This chemistry provides an efficient and promising synthetic way of proceeding for the diversity‐oriented construction of the spiro[indenoquinoxalino‐pyran] skeleton.     

Complexes of (bpy)2Ru(II) and (Ph2bpy)2Ru(II) with a series of thienophenanthroline ligands: synthesis,characterization, and electronic spectra

A series of complexes (bpy)₂LRu(II) and (Ph₂bpy)₂LRu(II), where bpy is 2,2′-bipyridine, Ph₂bpy is 4,4′-diphenyl-2,2′-bipyridine and L is 1,10-phenanthroline (phen), [1]benzothieno[2,3-c][1,10]phenanthroline (btp), naphtho[1′,2′?:?5,4]thieno[2,3-c][1,10]phenanthroline [ntpl, l=linear], and naphtho[1′,2′?:?4,5]thieno[2,3-c][1,10]phenanthroline (ntph, h=helical) were synthesized and characterized using 2D COSY NMR spectra. The UV spectra were assigned to study their metal to ligand charge transfer (MLCT) excited states. Complexes of (bpy)₂LRu(II) showed identical absorption wavelengths (λ _max) for the MLCT of all four members of the series with the only variation being the intensity (log _ε ) for each. The MLCT of (Ph₂bpy)₂LRu(II) showed the similar behavior only with different wavelengths showing that in this heteroleptic series of complexes the MLCT is exclusively to the bpy ligands with none to thienophenanthroline (btp, ntpl, or ntph).     

微波辅助合成菲并咪唑衍生物及微波非热效应

以1,10-邻菲啰啉5,6-二酮及苯甲醛(或取代苯甲醛)为原料, 在微波辐射条件下制备了一系列菲并咪唑类衍生物, 考察了温度、 时间以及投料比对微波辅助合成菲并咪唑类衍生物的影响, 并进一步探讨了微波非热效应的影响. 设计正交实验优化了反应条件; 使用SiC管作为反应容器屏蔽微波对反应的影响; 通过元素分析、 核磁共振波谱、 质谱及红外光谱等对化合物进行了表征. 结果表明, 微波辅助反应的最佳反应条件为: 1,10-邻菲啰啉-5,6-二酮与苯甲醛(或取代苯甲醛)的投料比为1: 1.5, 反应温度为100℃, 反应时间为20 min; 并且发现SiC管中反应的产率明显低于石英管反应容器. 与传统制备方法相比, 微波辅助合成方法可在更短时间内快速方便地制得菲并咪唑类衍生物; 反应温度、 反应时间以及投料比对微波辅助合成反应有明显影响; 微波非热效应有助于提高反应产率.     

Facile Two‐Step Synthesis of 1,10‐Phenanthroline‐Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency

A facile two‐step synthesis of aza[7]helicenes possessing a 6‐5‐6‐6‐6‐5‐6 skeleton from commercially available 2,9‐dichloro‐1,10‐phenanthroline via double amination with aniline derivatives followed by hypervalent iodine reagent‐mediated intramolecular double‐NH/CH couplings was developed. Single‐crystal X‐ray analyses of the helicenes revealed unique structures, including both a significantly twisted center and planar terminals of the skeleton. The azahelicenes show high fluorescent quantum yields (Φ s) under both neutral (Φ : 0.25–0.55) and acidic conditions (Φ : up to 0.80). An enantiomerically pure aza[7]helicene showed high circularly polarized luminescence (CPL) activity under both neutral and acidic conditions (g _lum: up to 0.009).     

Synthesis,Modification, and Anticonvulsant Activity of 3′‐R1‐Spiro[indoline‐3,6′‐[1,2,4]triazino[2,3‐c]quinazolin]‐2,2′(7′H)‐diones Derivatives

Previously unknown 3′‐R¹‐5‐R²‐spiro[indoline‐3,6′‐[1,2,4]triazino[2,3‐c]quinazoline]‐2,2′‐(7′H)‐diones and their N‐substituted analogues were obtained via reaction of 6‐R¹‐3‐(2‐aminophenyl)‐1,2,4‐triazin‐5‐ones with isatin and its substituted derivatives. It was shown that alkylation of 3′‐R¹‐5‐R²‐spiro[indoline‐3,6′‐[1,2,4]triazino[2,3‐c]quinazolin]‐2,2′‐(7′H)‐diones by N‐R³‐chloroacetamides or chloroacetonitrile in the presence of а base proceeds by N‐1 atom of isatin fragment. The spectral properties (¹H and ¹³C NMR spectra) of synthesized compounds were studied, and features of spectral patterns were discussed. The high‐effective anticonvulsant and radical scavenging agents among 3′‐R¹‐5‐R²‐spiro[indoline‐3,6′‐[1,2,4]triazino[2,3‐c]quinazolin]‐2,2′(7′H)‐diones and their N‐substituted derivatives were detected. It was shown that compounds 2.2 , 2.8 , and 3.1 exceed or compete the activity of the most widely used in modern neurology drug—lamotrigine on the pentylenetetrazole‐induced seizures model. The aforementioned fact may be considered as a reason for further profound study of synthesized compounds using other pathology models.     

A Novel and Regiospecific Synthesis of 1‐Aryl‐1H‐benzotriazoles via Copper(I)‐Catalyzed Intramolecular Cyclization Reaction

1‐Aryl‐1H‐benzotriazole derivatives were synthesized via intramolecular cyclization of easily obtained triazenes, using CuI as the catalyst, DMSO as the solvent, t‐BuONa as the base, and 1,10‐phenanthroline as the ligand, in up to 97% yield. The synthesis is regiospecific and functional group‐tolerant.     

Two Zinc(II) and Nickel(II)‐based Complexes: Anti Breast Cancer Activity

Two zinc(II) and nickel(II) based coordination polymers, {[Zn(bibp)(MoO₄)](H₂O)₂}_n ( 1 ) [bibp = 4,4′‐bis(imidazol‐1‐yl)‐biphenyl] and [Ni₂(CN)₄(phen)₂]_n ( 2 ) (phen = 1,10‐phenanthroline), were synthesized and structurally characterized under solvothermal conditions. Compound 1 can be viewed as the connection of the 1D W‐type chain [Zn(trans‐bibp)] with the MoO₄^2– anion to form a uninodal 4‐connected net, whereas 2 features one‐dimensional Ni^II cyanide chains decorated either with linear Ni(CN)₄ side chains or with 1,10‐phenanthroline ligands bound directly to the Ni^II sites of the parent chain. In addition, in vitro anticancer activities of compounds 1 and 2 on four human breast cancer cells (MDA‐MB‐231, MDA‐MB‐468, SK‐BR‐3, and MCF7) was further determined.     

2,2‐Bis(methoxy‐NNO‐azoxy)ethyl Derivatives of 4,8‐Dihydro‐bis‐furazano[3,4‐b:3′4′‐e]pyrazine: The Synthesis and X‐ray Investigation

The first synthesis of 4,8‐dihydro‐bis‐furazano[3,4‐b:3′4′‐e]pyrazine bearing 2,2‐bis(methoxy‐NNO‐azoxy)ethyl groups has been developed. These compounds are obtained by aza‐Michael reaction of 1,1‐bis(methoxy‐NNO‐azoxy)ethene or its equivalents, such as 2,2‐bis(methoxy‐NNO‐azoxy)ethanol derivatives, with 4,8‐dihydro‐bis‐furazano[3,4‐b:3′4′‐e]pyrazine.     

Enhancement of Antiangiogenic Efficacy of Iron(II) Complex by Selenium Substitution

Antiangiogenesis therapy is a proven strategy for the treatment of cancers. Herein, we demonstrate that iron(II) complexes containing 1,10‐phenanthroline(phen) derivatives were capable of suppressing angiogenesis in vitro in a dose‐dependent manner. Interestingly, the introduction of selenium into an iron(II) complex ((Fe(phenSe)₃(ClO₄)₂ (phenSe=2‐selenoimidazole[4,5‐f]1,10‐phenanthroline)) could enhance its antiangiogenic efficacy. Mechanistic studies demonstrated that the complex potently induced endothelial cell apoptosis as evidenced by activation of caspases and PARP cleavage. The iron(II) complex activated p53‐mediated mitochondrial dysfunction as can be seen by the upregulation in the expression of p53 and proapoptotic Bcl‐2 family proteins, and downregulation in the expression of Bcl‐2 family proteins. Additionally, the complex inhibited VEGF expression and gave rise to dephosphorylated AKT, which suppressed the transmission of the mitogenic signaling pathway. Taken together, this study could provide a strategy for the rational design of high‐efficacy antivascular agents.     

A Versatile Synthesis,PM3‐Semiempirical,Antibacterial, and Antitumor Evaluation of Some Bioactive Pyrazoles

This research work describes the synthesis and biological properties of some novel isolated or fused heterocyclic ring systems with pyrazole, for example; enaminones containing pyrazolone ring photochromic functional unit, 4‐[(4‐chlorophenylamino)methylene]‐3‐methyl‐1‐phenyl‐1H‐pyrazol‐5(4H)‐one (3) and some analogous derivatives 4, 9, and 10, also as pyrazolo[3,4‐b]pyridine, pyrazolo[3,4‐b]quinoline, pyrazolo[3′,4′:4,5]thieno[2,3‐c]pyrazoline and pyrazolo[3,4‐c]pyrazole were synthesized and characterized. Newly synthesized compounds were characterized by IR, ¹H NMR, ¹³C NMR, mass spectral data and quantum mechanical calculations. Selected products were tested for their antibacterial and antitumor agents.