轴向取代邻苯二氧-四-α-(戊氧基)钛酞菁配合物的合成

以1-氯萘为溶剂,3-戊氧基邻苯二甲腈与TICl4经高温缩合反应制备四-α-(戊氧基)钛氧酞菁(2);2与邻苯二酚反应合成了新型轴向取代邻苯二氧-四-α-(戊氧基)钛酞菁配合物,其结构经荧光光谱,UV-Vis,1H NMR,IR,MS和元素分析表征.     

非水溶剂中八丁氧基2，3－萘酞菁氯锰（Ⅲ）的电化学研究

非水溶剂中八丁氧基２,３ 萘酞菁氯锰（Ⅲ）的电化学研究①杨素苓刘尔生陈耐生黄金陵（福州大学化学系,福州３５０００２）王晓玉卜平段武彪吴谊群左霞（黑龙江大学化学系,哈尔滨１５００８０）金属萘酞菁配合物由于含有比相应的酞菁配合物更大的π 共轭体系,因而具...     

含氮芳氧基取代酞菁金属配合物光敏产生1O2

采用以2,5-二甲基呋喃(DMFU)为探针,通过气相色谱内标法测定了4种中心金属(Zn(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ))、4种取代基及α位或β位取代的28种含氮芳氧基取代酞菁金属配合物新物种光敏产生单线态氧(1O2)的速率常数。讨论了中心金属电子结构、取代基类型及取代位置对酞菁金属配合物光敏产生1O2能力的影响。结果表明,它们产生1O2的能力有很大差异:(1)相同取代基在相同位置取代情况下,中心金属为锌的酞菁配合物光敏产生1O2的能力均好于中心金属为铜、钴、镍的酞菁配合物;(2)氮杂芳氧基取代酞菁锌光敏产生1O2的速率常数显著大于相应位置氨基苯氧基取代酞菁锌的;(3)α位氮杂芳氧基取代酞菁锌光敏产生1O2的速率常数均大于相应取代基β位取代酞菁锌的。     

四-β -(8-喹啉氧基)取代酞菁金属配合物的合成、表征及其荧光性质研究

本文利用DBU催化法合成得到4种四-β-(8-喹啉氧基)取代酞菁金属配合物(金属分别为钴、镍、铜、锌)，同时分别进行了元素分析、UV-Vis、IR光谱、质谱表征。还对四-β-(8-喹啉氧基)取代酞菁金属配合物进行了荧光性质研究，为其进一步应用提供依据。     

二-吡啶氧基-轴向取代-四-α-(3-戊氧基)锡(IV)酞菁的合成与表征

以3-硝基邻苯二甲腈为起始原料,与正戊醇反应合成3-戊氧基邻苯二甲腈(1),然后在高温溶剂1-氯萘中经缩聚反应合成二氯-轴向取代-四-α-(3-戊氧基)锡酞菁(2),2进一步与2-羟基吡啶在N,N-二甲基甲酰胺中合成二-吡啶氧基-轴向取代-四-α-(3-戊氧基)锡酞菁配合物3,同时对相关化合物分别进行了元素分析,IR,1HNMR,UV/Vis,荧光和质谱表征.     

可溶性多氟烷氧基取代金属酞菁 :新型肿瘤光动力治疗光敏剂(英文)

合成了 9个新的多氟烷氧基取代的金属酞菁衍生物 ,它们均可溶于多数有机溶剂 .光氧化能力和对DNA的光切断活性的研究表明 ,中心金属离子为锌和铝的酞菁衍生物 ,具有较好的产生单重态氧的能力 .在乳化剂F68的存在下 ,锌酞菁衍生物 2a对离体杂交瘤细胞表现出良好的光灭活作用     

酞菁钴吡啶轴向配合物的合成及表征

从4-硝基邻苯二腈出发，首先合成了酞菁钴的衍生物——对称的四取代烷基苯氧基酞菁钴，并以此为基础，采用溶剂热的方法合成了与吡啶形成的无取代轴向配合物，对相关化合物进行了红外、紫外、质谱的表征．初步尝试了由溶剂热的方法制备金属酞菁轴向配合物．     

磺化2,3-萘酞菁锌(Ⅱ)、钴(Ⅱ)的电子吸收光谱和荧光光谱的研究

研究了磺化2，3-萘酞菁锌(Ⅱ)、钴(Ⅱ)在DMF(N，N-二甲基甲酰胺)、DMSO(二甲基亚砜)、乙醇、水等溶剂中的电子吸收光谱和荧光光谱．萘酞菁配合物的Q带与相应的酞菁配合物Q带相比，电子吸收光谱红移80～90nm，荧光光谱红移约100nm，荧光强度也显增加．在金属萘酞菁中引入磺酸基，配合物的电子吸收光谱Q带发生红移，但是影响不大、对于相同中心金属的配合物，改变溶剂的种类对配合物的电子吸收光谱的Q带影响较大．在金属萘酞菁环上引入一个磺酸基时，在相同溶剂中与无取代萘酞菁相比发生荧光光谱Q带红移，荧光强度增大．但在萘酞菁环上继续引入磺酸基时，荧光强度反而减少．磺化萘酞菁钴比磺化萘酞菁锌有较大的荧光强度．不同浓度下的电子吸收光谱和荧光光谱说明金属萘酞菁有集聚倾向、能形成基激缔合物．     

喹啉氧基酞菁金属配合物光敏化氧化色氨酸能力的研究

酞菁金属配合物是光动力治疗的新一代光敏剂,其治疗作用的机理以及引起的生物效应一直是人们研究的热点.本文选用色氨酸作为与喹啉氧基酞菁金属配合物作用的靶分子,讨论了配合物的组成结构与其光敏化氧化色氨酸能力的相关性.结果表明,酞菁环内中心金属离子和环周边取代基的组成结构以及取代位置与数目都影响其光敏化氧化色氨酸能力,中心金属离子为闭壳层电子结构、取代基位于α位以及提高取代基数目均有利于提高光敏化氧化活性,同时显示,取代基的组成结构对靶分子有一定选择性,研究结果可为研发该类光敏剂提供依据.     

固载化金属酞菁(MPc)催化性能的研究——Ⅰ.在NaY上直接合成MPc

固载化的配位催化剂兼具均相和多相催化剂的优点,因此,均相配合物催化剂的固载化是近来很活跃的研究领域。金属酞菁在有机物的均相催化氧化中有不少报导,但对固载化的金属酞菁研究得不多。我们试图把过渡金属酞菁固载化并研究其在氧化反应中的催化行为。本文讨论的是在NaY上直接合成金属酞菁配合物。     

Mesogens containing p-polyfluoro-m-nitrobenzoate and 2,3-difluorotolane groups

A series of 4-(4-n-heptoxy-2,3-difluorophenylethynyl)phenyl 3-nitro-4-polyfluoroalkoxybenzoate liquid crystals was synthesized and their phase transition behaviours were studied by optical polarizing microscopy and DSC. The results show that the mesogens containing long polyfluoroalkoxy chain tend to exhibit the smectic A phase.     

[(Polyfluoroalkoxy)methyl]thiiranes and 2-anilinoethanethiols

By reaction of appropriate oxiranes with thiourea [(polyfluoroalkoxy)methyl]-substituted thiiranes were obtained that are key compounds for the synthesis of perfluoro-containing 1,2-aminopropanethiols.     

Mesogens containing p-polyfluoro-m-nitrobenzoate and 2,3-difluorotolane groups

A series of 4-(4-n-heptoxy-2,3-difluorophenylethynyl)phenyl 3-nitro-4-polyfluoroalkoxybenzoate liquid crystals was synthesized and their phase transition behaviours were studied by optical polarizing microscopy and DSC. The results show that the mesogens containing long polyfluoroalkoxy chain tend to exhibit the smectic A phase.     

A fast radical chain mechanism in the polyfluoroalkoxylation of aromatics through NO2 group displacement. Mechanistic and theoretical studies

Introduction of polyfluoroalkoxy and polyfluoroalkylthio substituents in aromatic rings can be achieved with mild conditions and short times thorough reaction of concentrated solutions of dinitrobenzenes in DMF with polyfluoro alcohols and polyfluoro thiols in moderate excess, in the presence of excess tetrabutylammonium fluoride as a base. Mechanistic studies suggest that under these conditions a fast radical chain mechanism operates. This mechanism is elicited by oxidation of a Meisenheimer complex and proceeds through a radical aromatic substitution with the polyfluoroalkoxy or the polyfluoroalkylthio radicals as key intermediates. At low concentrations, entrainment can be achieved with superoxide anion. A rationale for this effect is discussed. Answers to particular questions about the proposed mechanism are achieved through a theoretical study at the B3LYP/6-31+G(d,p) level. Specifically, the competition between the radical mechanism and the corresponding polar one (classical S(N)Ar reaction) is studied in that way, with the conclusion that the key steps of the radical mechanism in our reaction conditions (polar aprotic solvent) are at least as efficient as the ones of the polar one, thus justifying the observed kinetic advantage for the chain reaction in the conditions where an efficient initiation occurs.     

Free Radical Hydrophosphorylation of Fluoroalkyl Vinyl Ethers: Synthesis of Fluoroalkyl Phosphonates

An effective method for the synthesis of dialkyl [2-(polyfluoroalkoxy)ethyl]phosphonates by free radical hydrophosphorylation of fluoroalkyl vinyl ethers with dialkyl (H)-phosphonates was developed. The reaction proceeds in the presence of catalytic amounts of azabisisobutyric acid dinitrile (AIBN) (150°C, 2 h, portionwise addition of AIBN) to afford the target fluoroalkyl phosphonates in up to 85% isolated yield.     

Kinetics and mechanism of reaction between polyfluorinated alcohols and thionyl chloride

Complexing of polyfluorinated alcohols with triethylamine was studied by means of microcalorimetry, IR and NMR spectroscopy. The reaction kinetics of these polar complexes with thionyl chloride was investigated using calorimetry of heat fluxes applying mathematical simulation procedure. The second order of nucleophilic substitution reaction of chlorine by polyfluoroalkoxy group was established.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11, 2004, pp. 1628–1631.Original Russian Text Copyright © 2004 by Rakhimov, Popov, Vostrikova, Vostrikova, Zauer.     

Activation of weak nucleophiles: polyfluorocarbamates from polyfluoroalcohols via a fast radical reaction

A new fast radical mechanism has been observed for the reaction of polyfluorinated alcohols and phenylisocyanate, very sensitive to the change of solvents and the concentration of reactants. The acidity of polyfluoroalcohols seems to be responsible for the observed new reactivity and evidences from kinetic studies, electron paramagnetic resonance, cyclic voltammetry, and photostimulation suggest that polyfluoroalkoxy radical is the key intermediate in the chain. To the best of our knowledge, it is the first time that a radical mechanism is described for the preparation of carbamates.     

Synthesis and mesomorphic properties of semi-perfluorinated chain liquid crystals

Three homologous series of 4-(n-polyfluoroalkoxycarbonyl)phenyl 4-[(4-n-alkoxyphenyl)ethynyl] benzoates have been synthesized from 1,1,3-trihydroperfluoropropanol, 1,1,5-trihydroperfluoropentanol and 1,1,7-trihydroperfluoroheptanol. Polarizing microscopic textural observations and DSC measurements of the phase transitions of these compounds show that most of them are thermotropic liquid crystals with smectic A and very broad smectic C phases; furthermore, several show very narrow monotropic SmB phases. The effect of the terminal polyfluoroalkoxy and alkoxy groups on the mesomorphic behaviour is also discussed.     

Synthesis of methylvinylpolyfluoroalkoxysilanes by photoinitiated radical reaction of dialkoxy(methyl)vinylsilanes with perfluoro-4-methylpent-2-ene

A new method was elaborated for the synthesis of vinylsilanes with polyfluoroalkoxy substituents at the silicon atom using the photoinitiated radical reaction of dialkoxy(methyl)vinylsilanes with perfluoro-4-metliylpent-2-ene in the presence of di-tert-butyl peroxide at room temperature.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2976–2978, December, 1996,     

Determination of arsenic species in Solanum Lyratum Thunb using capillary electrophoresis with inductively coupled plasma mass spectrometry

A simple and highly efficient interface to couple capillary electrophoresis with inductively coupled plasma mass spectrometry by a microflow polyfluoroalkoxy nebulizer and a quadruple ion deflector was developed in this study. By using this interface, six arsenic species, including arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, were baseline‐separated and determined in a single run within 11 min under the optimized separation conditions. The instrumental detection limit was in the range of 0.02–0.06 ng/mL for the six arsenic compounds. Repeatability expressed as the relative standard deviation (n = 5) of both migration time and peak area were better than 2.5 and 4.3% for six arsenic compounds. The proposed method, combined with a closed‐vessel microwave‐assisted extraction procedure, was successfully applied for the determination of arsenic species in the Solanum Lyratum Thunb samples from Anhui province in China with the relative standard deviations (n = 5) ≤4%, method detection limits of 0.2–0.6 ng As/g and a recovery of 98–104%. The experimental results showed that arsenobetaine was the main speciation of arsenic in the Solanum Lyratum Thunb samples from different provinces in China, with a concentration of 0.42–1.30 μg/g.