Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

“普世价值”思潮对大学生的影响及对策

以民主、自由、人权为核心的“普世价值”思潮具有极强的迷惑性,论述了其对当代大学生的价值观念、政治认同所产生的不可忽视的影响。提出高校思想政治教育工作者必须准确把握“普世价值”思潮的内容和实质,批判其理论根基和价值基础,坚持“疏”“导”结合,强化社会主义核心价值观教育,不断提高大学生抵制错误思潮的能力。     

半潜式钻井平台螺旋桨修复技术的应用研究进展

针对半潜式海洋钻井平台推进器螺旋桨面临的空泡腐蚀、电化学腐蚀以及海洋生物附着污损等问题，综述了焊接、粘接、热喷涂、冷喷涂修复技术的应用研究进展。认为目前的螺旋桨修复再制造技术普遍存在着修复层应力集中、结合强度低、孔隙率高、高温导致材料变性等缺陷，今后的研究工作应向着避免应力集中、增大修复层结合强度、降低作业温度、减小孔隙率的方向发展，以期能够制备更加致密均匀的修复层。     

微信公众平台在大学生安全教育中的应用

阐述微信公众平台的优势,分析利用微信公众平台开展大学生安全教育的可行性,通过突出信息推送功能、以案讲案、引导大学生参与平台建设等措施发挥微信公众平台载体作用,提出转变传统的安全教育观念、开发信息反馈功能、需要优秀编辑人员等完善微信公众平台运营的建议。     

集成系统中工艺卡片填写与工序图绘制的研究

利用VBA实现CAD和CAPP系统集成，讨论了基于Word平台进行工艺卡填写，并在此基础上进行工艺卡填写和工序图并行输出的一般问题。工艺文件的填写是在CAPP数据库的支持下，直接读取CAD所提供的CAPP工艺数据文件，经推理机推理自动生产工艺过程；工序图绘制是在特征图表级和参数化绘图原理的基础上进行的。     

SBIRS-HIGH对导弹上升段位置测量精度及中末段位置预报精度的分析

根据目前的技术水平分析了高空天基红外系统(SBIRS-HIGH)的技术参数;理论上计算了SBIRS-HIGH对导弹上升段的位置测量精度以及中末段任意时刻飞行位置的预报精度;研究了SBIRS-HIGH对中段和末端导弹拦截系统的导引能力。     

基于RL&SM通用夹具系统的主动寻位技术及其实现方法

介绍了RL&SM通用夹具的寻位系统 ,描述了主动寻位与制造信息转换问题 ,提出和实现了相应的控制方法及其系统实现中的关键技术。理论分析与实验结果表明 ,提出的解决方法和技术是可行的 ,为RL&SM通用夹具系统的实际应用奠定了理论基础和技术支持     

Schrödinger Uncertainty Relations and Physical Features of Correlated-Coherent States

We show that the difference between the Schrödinger uncertainty relations (UR) and the Heisenberg UR is fundamental. We propose a modified version of stochastic mechanics that allows clearly demonstrating that the contributions from the anticommutator and the commutator to the Schrödinger UR are equally important. A classification of quantum states minimizing the Schrödinger UR at an arbitrary instant is proposed. We show that the correlation of the coordinate and momentum fluctuations in such correlated-coherent states (CCS) is largely determined by the contributions from not only the commutator but also the anticommutator of the corresponding operators. We demonstrate that the character of this correlation changes qualitatively in time from the antiphase correlation typical for the Heisenberg UR to the inphase correlation for which the contribution from the anticommutator is decisive. We comparatively analyze properties of a free microparticle and a quantum oscillator in CCS and show that the CCS correspond to traveling-standing de Broglie waves in both models.     

高精度回转工作平台方案与动态精度分析

动态高精度回转工作平台是网络搜索和跟踪系统的多功能工作平台,受控制系统的作用实现水平回转和高低俯仰的精确传动和定位,并起支撑作用。文章重点分析高精度回转工作平台的方案和动态精度。