Synthesis of 4-halophosphaisocoumarins via halocyclization of 2-(1-alkynyl)phenylphosphonates

A series of 4-halophosphaisocoumarins were prepared with high regioselectivity in good to excellent yields under mild conditions by the reaction of 2-(1-alkynyl)phenylphosphonic acid diesters with I₂ in CHCl₃ or ICl in CH₂Cl₂, or by the reaction of 2-(1-alkynyl)phenylphosphonic acid monoesters with NBS or NCS in DMF. Whether the alkynylphosphonates could cyclize or not was affected by the substituents, reaction solvents and electrophiles. A rationale for this reaction is discussed.     

Chiral Phosphinophenyloxazolines Bearing Alkoxymethyl Substituents: Synthesis and Application in the Palladium Catalyzed Allylic Substitution Reactions

The chiral phosphine‐oxazoline ligands 3 and 4 bearing 4‐alkoxymethyl substituents on the oxazoline ring with (R)‐configuration were prepared from L‐serine methyl ester in 66% and 33% yields, respectively. Along this synthetic pathway, the β‐hydroxylamides derived from L‐serine methyl ester and 2‐halobenzoyl chlorides were expediently converted to the corresponding oxazolines by using diethylaminosulfur trifluoride as the activation agent. Potassium diphenylphosphide was the reagent of choice for replacing the bromine atom on the phenyl ring, giving the desired oxazoline‐phosphine ligands 3 and 4 . Together with [Pd(η³‐allyl)Cl]₂, ligands 3 and 4 induced an enantioselective allylic substitution reaction of 1,3‐diphenyl‐2‐pro‐penyl acetate by dimethyl malonate. Although ligands 3 and 4 exhibit the (R)‐configuration, differing from the (S)‐configuration of Pfaltz‐Helmchen‐Williams phosphine‐oxazoline ligands, all these ligands led to the same enantiotopic preference in the allylic substitution reaction. To facilitate the recovery and reuse of the phosphine‐oxazoline ligand, immobilization on Merrifield resin was attempted, albeit in low loading.     

Sol-gel derived carbon ceramic electrode containing methylene blue-intercalated α-zirconium phosphate micro particles

Methylene blue-intercalated alpha-zirconium phosphate (MBZrP) micro particles in deionized water were deposited onto the surface of graphite powder to prepare graphite powder-supported MBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite. The composite was used as electrode material to fabricate a surface-renewable, rigid, leak-free carbon ceramic composite electrode, bulk-modified with methylene blue (MB). In the configuration, alpha-zirconium phosphate was employed as a solid host for MB, which acted as a catalyst. Graphite powder ensured conductivity by percolation, the silicate provided a rigid porous backbone and the methyl groups endowed hydrophobicity and thus limited the wetting section of the modified electrode. Peak currents of the MBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled at high scan rates. Square-wave voltammetric study revealed that MBZrP immobilized in carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution with pH ranged from 0.44 to 2.94. In addition, the chemically modified electrode showed an electrocatalytic activity toward nitrite reduction at +0.15 V ( vs. Ag/AgCl) in acidic aqueous solution (pH=0.44). The linear range and detection limit are 1x10(-6)-4x10(-3) mol x L(-1) and 1.5x10(-7) mol x L(-1), respectively.     

Redetermination of (6R,7S,9S,11S)‐(–)‐sparteinium monoperchlorate

The structure of the title compound, C₁₅H₂₇N₂⁺·ClO₄^?, consists of a monoprotonated sparteinium cation and a perchlorate anion. The two tertiary N atoms of the cation, one perchlorate O atom and a H atom form a bifurcated hydrogen bond, the four hydrogen‐bonding atoms being nearly in the same plane.     

离子缔合富集明极溶出伏安法测定痕量碘——Ⅰ.以丁基罗丹明B为离子缔合剂

本文提出在0.1mol/LH_2SO_4,7.5×10~(-4)mol/LBr~-和6×10~(-5)mol/L丁基罗丹明B(R~+)的底液中,在+1.0V下,I~-离子于玻璃电极上被氧化生成I_2BrR离子缔合物,藉以阴极溶出伏安法测定碘、I~-离子浓度在1～50ppb范围内与峰电流呈线性关系。用于食盐中痕碘的测定。     

硼酸溶液中氯柱硼镁石的溶解及相转化动力学

对氯柱硼镁石（2MgO•2B2O3•MgCl2•14H2O）在4.5％H3BO3水溶液40 ℃的溶解及相转化过程进行了动力学研究.对不同时间取出的液相的化学分析及不同阶段分离固相的鉴定结果表明,该复盐在溶解阶段出现与前所报导不同的同步溶解，最终产物是库水硼镁石（2MgO•3B2O3•15H2O）.提出了库水硼镁石的形成条件和溶解及相转化动力学机理，利用单纯形优化法配合Runge-Kutta微分方程组数值解法对实验数据进行处理，给出了转化结晶动力学方程.     

Facile Total Synthesis of (±)‐Nimbiol

A facile total synthesis of (±)‐nimbiol 1 has been achieved. In order to decrease the dioxo byproduct 2a , an improved oxidation system of CrO₃/H₂O/HOAc/NaOAc was used.     

辛硫磷在玻碳电极上的伏安行为

在以0.1 mol.L-1氯化钾为支持电解质,pH为2.21的B-R缓冲溶液中辛硫磷于-0.72 V(vs.Ag/AgCl)处产生灵敏的还原峰。当辛硫磷的浓度在4×10-5~8×10-4mol.L-1范围内时,浓度与线性扫描还原峰电流呈线性关系。据此对辛硫磷样品作6次平行测定,测得平均值为3.42%,其RSD为1.7%,回收率为98.6%~103.6%。用线性扫描与循环伏安法探讨了该体系的伏安行为,结果表明,辛硫磷在玻碳电极上的电化学还原机理为不可逆过程。     

阿利新蓝的合成

阿利新蓝 (ＡｌｃｉａｎＢｌｕｅ)是一种从植物中提取出的天然物。于 1 944年由Ｈａｄｄｏｃｋ和Ｗｏｏｄ在实验室通过多次实验后所发现。它的水溶液呈天蓝色 ,着色性好而且吸光系数很大。又因它较好的水溶性。所以可以作为高效的生物染色剂[1,2 ] ,用于粘蛋白染色、细菌染色及聚酯、纤维素等人造和天然纤维的染料[3 ] 。基于它的重大应用前景和较高的商业价值 ,探索出一条合理的工业化合成路线就非常重要了。有关阿利新蓝的应用虽然有很多 ,但始终未见合成阿利新蓝的文献报道。在设计它的有机合成时必然涉及酞菁铜 (ＰｃＣｕ)的氯甲基化反…     

Sensitivity in Supramolecular Architectures of Polyaromatic Salts Containing Two Singly‐Pimerized Bipyridines

Three novel supramolecular arrays of zigzag polyaromatic salts are reported. Both the conformation and disposition of the dications are subjected to various noncovalent interactions. Thus, the presence or absence of the π‐π interacting enclathrated molecules, the efficient packing and the involved hydrogen bonding interactions of anions, as well as the increased hydrophobic property of the dications themselves exert influence.