Studies on sulfinatodehalogenation: XVII. The sulfinatodehalogenation of primary perfluoroalkyl iodides and bromides by Rongalite

Using acetonitrile or DMF as cosolvent, both perfluoroalkyl iodides such as Cl(CF₂)_nI (n = 4,6,8, la—lc ), CF₃ (CF₂)_n I (n = 5,6,7, ld—lf ), I (CF₂)_n O (CF₂) SO₃ Na(n = 2,4,6, lg—li ) and perfluoroalkyl bromides such as Cl (CF₂)_n Br (n = 4,6, 3a—3b ) and C₇F₁₅ Br (3e) reacted with Rongalite in aqueous solution to give the corresponding sulfinates Cl (CF₂)_n SO₂ Na (n = 4,6,8, 2a—2c ), CF₃-(CF₂)_nSO₂Na (n = 5,6,7, 2d—2f ) and NaO₂S(CF₂)_nO(CF₂)₂SO₃Na (n = 2,4,6, 2g—2i ) in moderate yields. 1 H-perfluoroalkanes were formed as the main products when other solvents such as ethanol. iso-propanol, 1,4-dioxane and morpholine were used.     

Decarboxylative difluoromethylation of aldehydes with PhSO2CF2COOK: A facile and efficient access to difluoromethylated carbinols

A novel decarboxylative difluoromethylation reaction of PhSO₂CF₂COOK with aldehydes under metal- and ligand-free conditions has been developed. The reaction is very mild and tolerates a wide range of aldehydes (both enolizable and non-enolizable aldehydes), providing a facile and efficient method for the synthesis of structurally diverse difluoromethylated carbinols in moderate to excellent yields.     

Inorganic base-mediated stereoselective hydroamination of arylalkynes with imidazole: An efficient access to N-vinylimidazoles

A metal-free inorganic base-mediated highly stereoselective hydroamination of arylalkynes with imidazoles has been developed, and the corresponding N-vinylimidazoles were obtained in good yields and with moderate to excellent stereoselectivities (up to 99:1). For the electron rich alkynes, the reaction system of CsOH·H₂O/NMP/140?°C led to the predominant formation of E-addition products, while the reaction system of KOH/NMP/90?°C afforded the Z-isomers as the major product. The electron deficient alkynes furnished predominantly the E-addition products in both reaction systems. This study essentially provides a general and an efficient protocol for the synthesis of E-isomer of the N-vinylimidazoles.     

Temperature effect on the ease of aggregation

The effect of temperature on the critical aggregate concentration (CAgC) has been investigated for the first time, by measurement of the hydrolytic rate constants of p-nitrophenyl dodecanoate (C12) and hexadecanoate (C16) at different temperatures in the 30:70 V/V (Φ=0.30) and 40:60 V/V (Φ= 0.40) dioxane (DX)-H2O systems. The CAgC values of C12 and C16 increase with the increase of the temperature, i.e., high temperatures disfavor aggregation. Activation energies for the hydrolysis of C12 in the monomeric and aggregated concentration domains have also been discussed.     

二级胺及水对氟烷基联烯砜的共轭加成

由氟烷基亚磺酰氯制备得到氟烷基联烯砜，并对其和胺及水的加成反应进行了研究。室温下，二级胺可以和联烯砜反应得到相应的烯胺加成产物，该产物在甲苯中加热回流可重排得到共轭的烯胺。二乙胺在对γ－甲基－γ－乙基氟烷基联烯砜进行加成时，反应有很好的立体选择性。在回流的乙腈中水也可与氟烷基联烯砜发生类似的加成反应。     

水泵水轮机泵工况小流量区压力脉动预测

为了研究水泵水轮机偏工况下的导叶内部的压力脉动特征,本文比较分析了非定常雷诺平均模拟方法URANS和脱体涡模拟方法DES两种方法预测压力脉动特征的可行性,结果表明,DES可以用来预测压力脉动特征,最后,重点对泵工况Q/QD=0.15工况点的压力脉动的时域和频域特征进行了分析,得到固定导叶和活动导叶内部的压力脉动主要是低频成分,为转轮通过频率的11.27%。此外,固定导叶内部的压力脉动没有受到转轮内部的影响,而活动导叶内部则含有转轮通过频率成分。     

合成左旋和右旋丙叉甘油醇的新方法

Salen-CoⅢ;环氧氯丙烷;左旋;右旋;丙叉甘油醇;合成     

微乳液法制备球形氧化锆粉体及其分散特性的研究

以水/环己烷/曲拉通-100/正己醇四元油包水微乳体系中的微乳液滴为纳米微反应器，通过微反应器中增溶的锆盐和沉淀剂发生反应，可以制备出基本无团聚、球形度较好的纳米级氧化锆粉体，粉体粒径为30～40 nm且呈单峰分布。通过分析粉体中可溶性离子的含量及其在水中的电动行为以及悬浮体的流变特性，说明粉体具有良好的分散特性。     

AC等离子体辅助CH4低温氧化的分子激发作用

本文采用实验测量和数值模拟结合的方法,对AC放电下He/CH4/O2混合气中激发态对甲烷裂解和低温氧化的动力学贡献进行研究。基于HP-Mech,增加反应物的放电机理以及激发态参与的化学反应及其驰豫反应,建立CH4低温氧化机理。采用化学反应动力学求解器CHEMKIN中的两段式Plasma-PSR模型模拟放电过程及化学反应过程。该动力学模型能较好地预测反应物的消耗和主要产物的生成,反应路径分析表明激发态物质CH4(v),O2(v),O2(a^1△g)等通过链式反应CH4(v)+OH→CH3+H2O,O2(v)+H→OH+O,O2(a^1△g)+H→OH+O促进活性自由基和产物的生成。