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.     

2017—2019 年北京地区实验动物质量抽检结果分析

摘要:目的 比对分析 2017—2019 年北京地区实验动物微生物及遗传质量监测结果,为实验动物产业发展提供参考。 方法 按照国家和地方现行实验动物检测标准,对北京地区实验动物生产单位进行抽检,并发布检测报告。按照报告数据,对此阶段小鼠、大鼠、豚鼠、地鼠、兔、犬、猴和小型猪共 8 个品种的实验动物按照品种、等级、单位等进行分类,分析质量问题,并与 2014—2016 年同期实验动物质量比对,分析变化趋势。 结果 2017—2019 年分别抽检动物 144、131 和 135 批次,检出不合格批次分别为 30、15 和 17 批。 不合格主要因素为兔、犬及猪免疫不达标(20 批) ,病原感染 20 批,未发现遗传变异。 与 2014—2016 年同期相比,未检出遗传问题相同,免疫不达标状况好转,但病原感染出现上升。 结论 通过质量分析比对,能够为实验动物产业健康发展提供数据支持。     

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.     

洱海区域新石器时代文化概述

根据现有考古资料,从考古学的角度,概述了洱海区域新石器时代文化遗址的分布与类型、文化特征及文化渊源,证实了该区域新石器文化是在古人类文化的基础上而产生,并不断地汲取其它文化因素,形成了自成一体的区域地方性新石器文化.     

山西省吕梁区灌溉用水定额的编制

文章以调查典型县现状年灌溉用水定额为基础 ,以当地灌溉水可利用量为控制条件 ,采用逐级平衡的办法 ,制定吕梁区主要作物的灌溉用水定额     

加强法制建设促进珠江上游经济环保整体发展

珠江上游南、北盘江流域水土流失严重，生态环境不断恶化，严重影响了该地区经济的可持续发展。法制建设在该地区环境保护中起着至关重要的作用，只有通过法律制度的不断创新和完善，才能为该地区的环境治理提供有效的法律保障，最终达到环境保护与经济发展的和谐统一。     

45钢固体粉末法稀土、硼、铬、铝共渗工艺研究

研究了RE_Mg合金对固体粉末法硼、铬、铝共渗层成分、组织和性能的影响 .发现随着RE_Mg合金加入量的增加 ,渗层中Al2 O3的量不断增多 ,当RE_Mg合金加入量为 5 %时 ,渗层中出现连续致密分布的Al2 O3黑区组织 ,对此进行了性能测试和机理探讨     

An Integrated Two Phases Approach to Zn2+ Ions Electroreduction on Hg

The following two numerical models have been applied to zinc cations electroreduction in 1 M NaClO₄ water solution: a classical EE model describing the concentration of involved species in solution (semi infinitive diffusion region), an extended EE model describing both: the concentration of involved species in solution and the concentration of metallic zinc inside mercury drop (in limited area of diffusion). In the latter model the inner part of mercury drop and surrounding solution were treated as dynamic interrelated system. Both models were applied to experimental cyclic voltammetric CV data in 1 M NaClO₄, the results compared and discussed. The concentration profiles of all species including metallic zinc inside mercury drop were performed. The presented integrated model is essential for theoretical and analytical aspects of the electrochemistry of mercury soluble metal cations and amalgams.     

GaN氢化物气相外延生长系统的设计与制作

根据GaN氢化物气相外延生长(HVPE)的原理,设计制作了双温区卧式HVPE系统．根据实际生长中出现的问题和CaN样品的测试情况,对系统进行了逐步的调试和改进．     

Challenging Students to View the Concept of Area in Triangles in a Broad Context: Exploiting the Features of Cabri-II

This study focuses on the constructions in terms of area and perimeter in equivalent triangles developed by students aged 12–15 years-old, using the tools provided by Cabri-Geometry II [Labore (1990). Cabri-Geometry (software), Université de Grenoble]. Twenty-five students participated in a learning experiment where they were asked to construct: (a) pairs of equivalent triangles “in as many ways as possible” and to study their area and their perimeter using any of the tools provided and (b) “any possible sequence of modifications of an original triangle into other equivalent ones”. As regards the concept of area and in contrast to a paper and pencil environment, Cabri provided students with different and potential opportunities in terms of: (a) means of construction, (b) control, (c) variety of representations and (d) linking representations, by exploiting its capability for continuous modifications. By exploiting these opportunities in the context of the given open tasks, students were helped by the tools provided to develop a broader view of the concept of area than the typical view they would construct in a typical paper and pencil environment.