Highly efficient aza-Baylis-Hillman reaction of N-tosylated imines with MVK, acrolein, and phenyl acrylate or alpha-naphthyl acrylate: Lewis base effects and a convenient method to synthesize alpha,beta-unsaturated beta-amino carbonyl compounds

This paper describes several highly efficient aza-Baylis-Hillman reactions of N-tosylated imines with MVK, acrolein, and phenyl acrylate or alpha-naphthyl acrylate in the presence of a Lewis base. In most cases, the reaction can be completed within 1 h using the appropriate Lewis base catalyst. An efficient method to synthesize beta-amino ketones, aldehydes and esters in high yields and short reaction time has been developed.     

Bentone-34/OV-1毛细管柱的研制及其分离性能

自行研制了Bentone-34/OV-1高效石英毛细管气相色谱柱,并利用该柱分别对二甲苯、二氯苯和二氯甲苯异构体3种体系进行分析.在选用的色谱条件下,难分离物质对二甲苯和间二甲苯分离度达3;间二氯苯和对二氯苯分离度达1 3.结果表明该柱具有分离效果好,分析速度快的优点.     

QSAR Studies on the COX-2 Inhibition by 3,4-Diarylcycloxazolones Based on MEDV Descriptor

Selective inhibition of cyclooxygenase-2 (COX-2) might avoid the side effects of current available nonsteroidal antiinflammatory drugs while retaining their therapeutic efficacy. A novel variable selection and modeling method based on prediction is developed to construct the quantitative structure-activity relationships (QSAR) between the molecular electronegativity distance vector (MEDV) based on 13 atomic types and the biological activities of a set of selective cyclooxygenase-2 inhibitory molecules, 3,4-diarylcycloxazolones (DAA) plus indomethacin,naproxen, and celecoxib. Using multiple linear regression, a 5-variable linear model is developed with the calibrated correlation coefficient of 0.9271 and root mean square error of 0.17 in modeling stage and the validated correlation coefficient of 0.9030 and root mean square error of 0.20 in leave-one-out validation step, respectively. To further test the predictive ability of the model, 20 DAA compounds are picked up to construct a training set which is used to build a QSAR model and then the model is employed to predict the biological activities of the balance compounds. The predicted correlation coefficient and root mean square error are 0.9332 and 0.19, respectively.     

超高效液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查染发剂中32种染料成分

建立了超高效液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查和分析染发剂中32种禁限用染料的分析方法。样品经甲醇-2 g/L抗坏血酸水溶液溶解提取,正己烷净化,用ZORBAX Eclipse Plus C_(18)(3.0 mm×100 mm,1.8μm)色谱柱分离,以甲醇-5 mmol/L乙酸铵水溶液为流动相进行梯度洗脱,采用正、负离子切换同时测定了32种染料成分,显著提高了检测通量。以全扫描模式下提取的保留时间和一级母离子精确质量数以及同位素丰度比,实现对染发剂中多种染料成分的快速筛查;以自动触发采集的二级碎片离子精确质量数进行确证。32种染料在相应的质量浓度范围内线性关系良好,相关系数(r~2)均大于0.99;定量下限(LOQ)为0.2～40μg/g,回收率为81.0%～110%,相对标准偏差(RSD)为3.3%～9.9%。该方法简单、准确、快速,适用于染发剂中多种禁限用染料成分的高通量快速定性筛查和定量分析。     

5-氨基-1,10-菲咯啉：可异构化杂环螯合荧光载体作为比例计量型锌离子荧光探针的一种原型

5-amino-l,10-phenanthroline （5-AP）, as a tautomeric heterocyclic aromatic chelating fluorophore （THACF）, can sense Zn^2＋ selectively by shifting emission from 495 to 564 nm upon Zn^2＋ addition in ethanol. The ratiometric fluorescent sensing behavior has been correlated to the tautomerization of 5-AP affected by solvents and metal chelation. The strategy using THACF as ratiometric fluorescent sensor for Zn^2＋ not only simplifies the synthetic procedure but also gives a promising alternative for Zn^2＋ ratiometric fluorescent sensor design.     

纳米金刚石粉酸处理前后性能结构的表征

自从1963年爆炸法合成纳米金刚石[1]以来,纳米金刚石已在科研和工业领域得以广泛应用.但是工业合成的纳米金刚石粉由于其工艺的限制存在一些杂质,其中主要包括纳米石墨、非晶碳和爆炸过程中产生的金属离子.因此,在实际科研工作前对纳米金刚石粉进行纯化处理就显得十分重要,以往的研究表明不同的处理方法各有利弊[2].在以下的研究中,我们采用盐酸消解的方法对商业购买的纳米金刚石粉进行纯化处理,通过对比纯化处理前后的IR、Raman以及ICP表征,分析讨论了酸处理方法的纯化效果.     

Catalytic, asymmetric aza-Baylis-Hillman reaction of N-sulfonated imines with activated olefins by quinidine-derived chiral amines

The chiral nitrogen Lewis base, tricyclic cinchona alkaloid derivative TQO, is an effective promoter in the catalytic, asymmetric aza‐Baylis–Hillman reaction of N‐sulfonated imines Ar? CH?NR′ 1 (R′ = Ts, Ms, Ns, SES) with various activated olefins such as methyl vinyl ketone (MVK), ethyl vinyl ketone (EVK), acrolein, methyl acrylate, phenyl acrylate, or α‐naphthyl acrylate to give the corresponding adducts in moderate to good yields with good to high ee (up to 99 %) at ?30 °C or 45 °C in various solvents, including DMF/MeCN (1:1, v/v). The first such reaction of 1 with the simplest Michael acceptor MVK and methyl acrylate has been achieved with excellent enantioselectivity. The adducts derived from MVK and EVK had the opposite absolute configuration to those from acrolein, methyl acrylate, phenyl acrylate, and α‐naphthyl acrylate. A plausible mechanism has been proposed on the basis of previous reports and the authors’ investigations. An effective bifunctional chiral nitrogen Lewis base–Brønsted acid system has been revealed in this type of aza‐Baylis–Hillman reaction.     

大气压旋转螺旋状电极辉光放电等离子体催化甲烷偶联

采用新研制的具有旋转螺旋状电极的大气压辉光放电等离子体反应器催化甲烷偶联制碳二烃. 实验采用铜电极和不锈钢电极分别考察了输入电场峰值电压和甲烷、氢气进料流量等参数对甲烷转化率和碳二烃收率、选择性的影响. 在长时间连续反应无明显积碳的情况下, 最佳试验结果是电极材料为金属铜, 进料流量为60 mL•min^-1, V(CH₄ )/V(H₂)=1的条件下, 输入电场峰值电压为2.3 kV时, 甲烷转化率为70.64%, 碳二烃单程收率及其选择性分别为69.85%和 99.14%.     

Synthesis and Electrospray Ionization Mass Spectra of N-（1,3, 2-Dioxaphosphorinan-2-ylmethyl）thiophosphoramidates

N-（1,3,2-Dioxaphosphorinan-2-ylmethyl）thiophosphoramidates were synthesized and determined by NMR spectra and positive ion electrospray ionization mass spectrometry （ESI-MS） in conjunction with tandem mass spectrometry （MS/MS）. The fragmentation pathways were investigated. The results show that these characteristic ions in ESI mass spectra are useful in the structural determination of N-（1,3,2-dioxaphosphorinan-2-ylmethyl）- thiophosphoramidates.     

新型含二茂铁有机配合物的合成及其电化学性质

以二茂铁为起始原料,经氯汞化反应、溴代反应、Suzuki偶联反应、水解反应和取代反应等5步反应合成了一种新型的含二茂铁结构单元的有机配合物(7),其结构经1H NMR、13C NMR、IR和HR-MS(ESI-TOF)表征。电化学研究结果表明:化合物6的E1/2小于化合物7,具有较高的氧化还原活性。