Oxidative dimerization of aromatic amines using tBuOI: entry to unsymmetric aromatic azo compounds

It's all the hype: An oxidative dimerization reaction of aromatic amines utilizing tert-butyl hypoiodite (tBuOI) under mild reaction conditions leads to aromatic azo compounds. The method allows access to unsymmetric aromatic azo compounds, which are difficult to prepare by conventional synthetic methods, in a selective manner.     

Surface-relief-grating formation behavior of two hyperbranched azo polymers

In this work,surface-relief-grating formation behavior was studied by using two hyperbranched azo polymers.The hyperbranched polymers containing pseudo-stilbene type azo chromophores throughout the hyperbranched structure were synthesized by step-growth polycondensation of AB₂ type monomers.The AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）-phenylazo） benzoic acid（BAA）,was prepared through azo-coupling reaction between N,N’-bis（2-chloroethyl）aniline and 4- aminobenzenic acid.The another AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）phenylazo）-3-nitro-benzoic acid（BANA）, was prepared through azo-coupling reaction between N,N-bis（2-chloroethyl）aniline and 3-nitro-4-aminobenzcnic acid.The hyperbranched polymers（PBAA and PBANA） were prepared through nucleophilic substitution reaction of BAA and BANA, respectively.The polymers synthesized were characterized by using spectroscopic methods and thermal analysis.The photoinduced dichroism and photo-induced surface-relief-grating（SRG） formation of the hyperbranched polymers were investigated upon irradiation with Ar⁺ laser at 488 nm.PBAA shows typical photoinduced dichroism SRG formation behavior.On the contrary,PBANA does not show the photoresponsive properties.The results indicate that the nitro at the ortho position of azo group of PBANA shows the effect of inhibiting the photoinduced variations.The effect can be attributed to the blockage of the trans-cis isomerization of the azobenzene moieties by the steric hindrance.     

Synthesis and polymerizability of CN monomers

The synthesis and polymerizability of imine C?N monomers is surveyed. The investigated imines were either far more reactive than similarly substituted C?C or C?O monomers, or too stable to polymerize. Imines with electron‐attracting substituents on N favor polymerization by anionic mechanism, but led only to low molecular weight polymers. Imines with a donor substituent on N, such as N‐arylmethyleneimines, polymerized by cationic or anionic mechanism. 1‐ and 2‐Aza‐1,3‐butadienes were also rather unstable and polymerized to oligomers. The symmetrically substituted 2,3‐diaza‐1,3‐butadienes could be purified and polymerized successfully using anionic initiators, resulting in both 1,4‐ and 1,2‐structures in the polymer backbone, depending on the substituents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Pyrazole-based azo-metal(II) complexes as potential bioactive agents: synthesis,characterization, antimicrobial,anti-tuberculosis,and DNA interaction studies

Abstract

In the present investigation, the bioactive azo-dye ligand 1,5-dimethyl-4-[(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)diazenyl]-2-phenyl-1,2-dihydro-3H-pyrazol-3-one (L) and its transition metal complexes have been synthesized and characterized by various physical and spectroscopic techniques to elucidate their geometrical structures. The molar conductivity measurements confirmed the non-electrolytic nature of the complexes. EPR spectroscopy indicated that the metal complexes are monomeric in nature and exhibited octahedral geometry. The redox behavior of the copper complex was studied by the cyclic voltammetric technique in DMF solution and the complex showed well-established redox behavior at a scan rate of 0.05 V s^?1. The antimicrobial activity of the ligand and its metal complexes were screened against Escherichia coli, Bacillus subtilis, Aspergillus niger, and Candida albicans, and the results indicated increased activity after coordination of the ligand to the metal ions. The metal complexes exhibited enhanced antitubercular activity after chelation against M. tuberculosis. The DNA-binding experiments showed that the ligand and its metal complexes showed effective binding properties through intercalative mode against CT-DNA. All the synthesized molecules showed partial cleavage of supercoiled plasmid pUC18 DNA.     

Spectrophotometric Determination of Nitrite in Water Samples with 4‐(1‐Methyl‐1‐Mesitylcyclobutane‐3‐yl)‐2‐Aminothiazole

Abstract

A simple, sensitive, and specific spectrophotometric method for the measurement of nitrite in water has been developed and optimum reaction conditions along with other analytical parameters have been evaluated. The azo dye, 4‐(1‐methyl‐1‐mesitylcylobutane‐3‐yl)‐2‐(p‐N,N‐dimethylazobenzene)‐1,3‐thiazole was synthesized with the reaction of 4‐(1‐methyl‐1‐mesitylcylobutane‐3‐yl)‐2‐aminothiazole and N,N‐dimethyl aniline in acidic medium. Obtained azo dye has been characterized by infrared (IR), ¹H nuclear magnetic resonance (NMR), and microanalysis methods. The dye shows an absorption maximum at 482 nm. The method is optimized for acid concentration, pH, amount of reagents required, time, and interfering species. All the determinations were carried out at this wavelength throughout the work. At an analytical wavelength of 482 nm, Beer's law is obeyed over the concentration range 0.05 to 2.00 µg nitrite per mL analyte. The molar absorptivity, Sandell's sensitivity, and relative standard deviation are 2.03×10⁴ L mol^?1 cm^?1±251.3 (95%), 2.28×10^?3 µg cm^?2, and 2.74% (n=10), respectively. The detection limit of the method is 0.012 µg ml^?1 of nitrite ion. The method was succesfully applied to the determination of nitrite in tap water and lake water.     

Electrochemical Behavior of Azo Compounds in Liquid Ammonia

Abstract

At -40°C, the behavior of lO compounds, differing widely in their standard potentials, has been investigated in liquid ammonia, using cyclic voltammetry at a smooth platinum electrode. The purpose of this study was the realization of a redox scale with reversible systems. With azobenzene, pyridazine, cin-noline, benzocinnoline and 4,4′-azobis-(pyridine-N-oxide), the first electron transfer is reversible and leads to the formation of the corresponding radical anions which are stable; the second electron transferleads to the ciianions which can be protonated yielding the corresponding hydrazo. Other compounds, such as azoxybenzene, 3-amino-1,2,4-triazine, pyridine-N-oxide, 8-azaadenine and 1H-tetrazole, have an electrochemical behavior which i s more intricate.     

8-羟基喹啉偶氮苯衍生物应用于阴离子及阳离子的识别

研究了系列8-羟基喹啉偶氮苯衍生物与过渡金属离子如Ni2+,Co2+,Zn2+和Cu2+等离子间的相互作用,探讨了主体分子中的不同取代基对其光谱性质的影响及对阳离子识别选择性的影响。结果表明含有强吸电子基团-NO2或-CN的主体分子对阳离子的亲合力大于含有供电子基团-N(CH3)2或-CH3的     

含蒽醌基单偶氮染料光电导性质构效研究

由1-氨基蒽醌和不同偶合基合成了九个含蒽醌基的单偶氮染料,并对其进行了 元素分析、红外光谱和紫外光谱表征。紫外光谱研究结果表明,偶合基酰胺芳环上 取代基对偶氮染料的吸收光谱影响不大。当偶合基由2-羟基-3-氨替酰胺萘酚（ Azol～8)变为2-羟基-11氢-苯并咔唑-3-氨替酰胺萘酚（Azo9)时,偶氮染料的吸收 红移了130 nm,最大吸收出现在662 nm处,成为近红外染料。偶氮染料光电导性质 的研究表,偶合基酰胺芳环上取代基吸电子效应越强,光敏性越好,且与Hammett 常数σ有良好的相关性。值得注意的是萘环上扩大一个咔唑环（Azo9),使偶氮染 料的光敏性提高了几十倍,表明在萘环上扩大共轭环是提高偶氮染料光敏性的一个 良好途径。     

吡啶酮偶氮分散染料光谱性能

吡啶酮分散染料应用性能优异 ,其色谱主要为黄色及橙色 ,尤以黄色为主 [1～ 3]。Cheng和 Peng等 [2 ,3] 对以氨基噻二唑类和苯系芳胺为重氮组分的吡啶酮类染料的可见光谱及互变异构进行了研究 ,Ertan等 [4 ] 研究了以氨基噻唑和氨基苯并噻唑为重氮组分的吡啶酮偶氮染料的可见光谱 ,结果表明上述染料色谱主要仍为黄色。为得到具有更深色谱的吡啶酮类染料 ,我们用不同的重氮组分合成了一系列吡啶酮分散染料 ,研究了其在不同溶剂及不同 p H值下的光谱 ,发现该类染料亦可达到红、甚至蓝色谱 ,其中染料 1 a、1 b及 2 b3个染料结构未见报道。O2 …     

Novel Wormlike Nanostructures Self‐Assembled in a Well Defined Liquid Crystalline Diblock Copolymer with Azobenzene Moieties

Novel wormlike nanostructures were self‐assembled in bulk films of a well defined diblock copolymer with azobenzene moieties, which was prepared by atom transfer radical polymerization (ATRP). For comparison, a homopolymer with almost the same repeat units of azobenzene as those in the copolymer was also prepared. They both had well defined structures and exhibited a smectic liquid crystalline phase. Upon annealing the copolymer films, poly(methyl methacrylate) formed a matrix with excellent optical properties, and the azobenzene segment in the minority phase self‐assembled into a wormlike mesogenic domain in the bulk films. Such block copolymer films exhibited stability and transparency by eliminating the scattering of visible light, indicating their potential application as photoresponsive functional materials. Although wormlike morphologies have been obtained in micelles from block copolymer solutions, to the best of our knowledge, such wormlike nanostructures have never been explored in bulk films.