工作场所空气中过氧化丁酮毛细管气相色谱测定方法研究

[目的]建立工作场所空气中过氧化丁酮毛细管气相色谱测定方法。[方法]活性碳管采样,甲醇解吸,FFAP毛细管色谱柱分离,在最佳仪器条件下用气相色谱仪测定,按照《工作场所空气中毒物检测的研制规范》的要求,进行实验室方法研究。[结果]过氧化丁酮在0-970μg/ml之间有良好的线性关系,相关系数0.9999。方法的最低检出量为2.57μg(进样1μl解吸液,以3倍噪音计算),最低检出浓度为1.7-mg/m3(采样体积以1.5L计)。分别测定高、中、低3个浓度的样品,进行6次重复测定,相对标准偏差为0.5%-2.0%,解吸效率为90.40%-99.69%。工作场所空气中与过氧化丁酮共存的苯、甲苯、二甲苯、苯乙烯、丙酮、丁酮、乙醛、邻苯二甲酸二丁酯,对过氧化丁酮测定无干扰。[结论]本方法各项指标达到《工作场所空气中毒物检测的研制规范》的要求,适用于工作场所空气中过氧化丁酮的检测。

Homogeneous and Heterogeneous Performances of Pyridinium Ionic Liquids in the Allylic Oxidation of Ionone-like Dienes

The combination of relatively low-cost ionic liquids, simple copper salt, and terminal oxidant tert-butyl hydroperoxide provided an efficient and environmentally friendly approach to the preparation of ionone-like dienones. Six pyridinium ionic liquids were evaluated in allylic oxidation of α-ionone and β-ionone. The 60%-70% yields of 3-oxo-α-ionone were obtained with 0.02 0.20 mmol of CuCl2·2H2O as catalyst, 3-5 mmol of tert-butyl hydroperoxide as oxidant and 1 g of [Bpy]PF6 as solvent for 4-20 h at 60℃. The facile recovery and recycle of catalyst were also achieved. More significantly, peculiar phase behaviors of [Bpy]PF6 and [Epy]PF6 offered the catalytic system advantages of homogeneous reaction and heterogeneous separation. Scanning electron microscope （SEM） images of [Bpy]PF6 provided evidences for the behaviors. Transmission electron microscope （TEM） micrographs showed copper salt nanoparticles catalyst formed and stabilized in pyridinium ionic liquids.

Intermolecular dearomative oxidative coupling of indoles with ketones and sulfonylhydrazines catalyzed by I2:synthesis of[2,3]-fused indoline tetrahydropyridazines

A convergent construction of [2,3]-fused indoline tetrahydropyridazines via an I2/tert-butyl hydroperoxide(TBHP) catalyzed three-component dearomative oxidative coupling of indoles, hydrazines and acetophenone was established in moderate to good yields. This protocol provides a new approach for the synthesis of these biologically interesting fused indolines.