An efficient synthesis of δ-glyconolactams by intramolecular Schmidt–Boyer reaction under microwave radiation

δ-Glyconolactams were first synthesized by the intramolecular Schmidt–Boyer reaction using corresponding δ-azidosugars as starting material. The reaction could be efficiently performed in good yields of 61–69% under microwave radiation in acid condition, providing an alternative protocol to iminosugar δ-lactam.     

Direct transition metal-free C-S bond formation: synthesis of 2-aminobenzothiazole derivatives via base-mediated approach

A general, efficient, and more practical protocol for the base-mediated intermolecular or intramolecular S-arylation leading to the 2-aminobenzothiazole derivatives is reported. Remarkably, all reactions were carried out under transition-metal-free conditions with good to excellent yields, rendering the methodology presented herein highly valuable from both environmental and economic points of view.     

FTIR investigation of the O-H[middle dot][middle dot][middle dot]Xe interaction in simple carboxylic acids in solid xenon

The O-H stretching region of the infrared spectra of a series of carboxylic acids in Xe matrices was investigated as a function of temperature. Upon increasing the temperature, the νO-H band site-components undergo reversible frequency blue-shifts, which are larger for the lowest-frequency components. This unprecedented observation indicates both that different types of O-H[middle dot][middle dot][middle dot]Xe specific interactions occur, depending on different trapping sites, and the prevalence of stronger interactions of this type for molecules trapped in sites corresponding to lower frequency νO-H band site-components. These results are in agreement with previous investigations pointing to an increased stabilization and larger νO-H frequency red-shifts in carboxylic acid∕Xe complexes bearing a specific H-bond like O-H[middle dot][middle dot][middle dot]Xe interaction. O-H[middle dot][middle dot][middle dot]Xe interaction energies were obtained theoretically and also estimated from the spectroscopic data. Changes in the interaction energies upon temperature variation were also evaluated.     

Synthesis of tetrasubstituted thiophenes from pyridinium 1,4-zwitterionic thiolates and modified activated alkynes

Pyridinium 1,4-zwitterionic thiolates were applied to a formal [3 + 2] annulation reaction with modified activated alkynes, affording various tetrasubstituted thiophenes with aryl, alkenyl, alkyl or silyl group at the special position. The structural modification of alkyne substrates enabled the synthesis of diverse thiophenes to be achieved using the pyridinium 1,4-zwitterionic thiolates as the sulfur-containing building blocks. This approach is metal-free and catalyst-free.     

一种生物柴油代用品在HZSM-5分子筛催化剂上的催化热解

为了深入了解生物柴油在ZSM-5沸石上的催化反应机理,在常压的流动反应器中进行了生物柴油代用品丁酸甲酯在氢型ZSM-5(HZSM-5)催化剂上的热解和催化热解. 热解产物使用气相色谱-质谱法定性和定量测量. 动力学模型和实验表明,气相中氢提取反应是热解过程中丁酸甲酯分解的主要途径,但在HZSM-5上,丁酸甲酯则主要通过解离生成烯酮和甲醇消耗;与无催化反应相比,丁酸甲酯在HZSM-5上的初始分解温度降低了约300 K. 并且通过Arrhenius方程获得了在催化热解和均相热解条件下丁酸甲酯消耗的表观活化能. 明显降低的表观活化能证实了HZSM-5对丁酸甲酯热解的催化性能. 此外催化剂的活化温度对HZSM-5的某些催化性能具有一定的影响. 该研究对进一步的实际生物柴油燃料的催化燃烧具有一定的指导意义.     

团簇Aun+1-1、AunCr-1 (n=1-10)吸附CO的密度泛函理论研究

采用密度泛函理论对CO在阴离子团簇Aun+1-1、AunCr-1(n=1-10))表面的吸附做了系统研究.结果表明,团簇Aun+1CO-1、AunCrCO-1的基态结构是在团簇Aun+1-1、AunCr-1最低能量结构的基础上吸附CO形成; 吸附后的CO键长变长,振动频率减小,表明CO分子被活化;取值相同时,AunCrCO-1的平均结合能高,表明团簇Aun+1CO-1掺杂Cr后稳定性升高.HOMO-LOMO能隙结果表明Aun+1CO-1替代掺杂Cr原子后团簇的化学活性得到了提升,AunCrCO-1、Aun+1CO-1团簇能隙具有奇偶振荡的现象;轨道电荷分析表明CO与团簇相互作用实质是C原子与成键Au原子或Cr原子间转移电荷,CO在与团簇相互作用过程中O原子轨道电荷分布几乎没有发生变化.     

GI／G／1单重休假随机服务系统的马氏骨架方法

文献[1]引入一类具有广泛应用前景的随机过程-Markov骨架过程。借助Markov骨架过程的方法研究GI/G/1单重休假服务系统队长，及t时刻到达顾客等待时间的瞬时概率分布。