新型含吡啶基的不对称膦酸酯衍生物的合成与生物活性

通过2-氯-5-氯甲基吡啶与亚磷酸酯的Michaelis-Becker反应合成得到10个新型含吡啶基的不对称膦酸酯衍生物, 并对环状亚磷酸酯与2-氯-5-氯甲基吡啶反应的立体化学进行了研究, 结果表明: 不对称环状亚磷酸酯的电子效应和立体效应对反应的立体化学有着重要影响. 初步的生物活性结果表明, 该类化合物不具有杀虫活性, 但显现出较好的杀菌活性.     

基于拉格朗日乘子法和群论的具有任意位移边界条件的旋转周期对称结构有限元分析

对任意位移边界条件下的旋转周期对称结构,由拉格朗日乘子法建立有限元方程。在对称适应的坐标系下,由结构刚度矩阵的块循环性质,利用群变换给出一种新的求解方法。数值验证给出令人满意的结果。     

循环码计数器的快速综合

本文导出了使用J-K触发器的任意2~n进制循环码计数器激励函数的设计公式,并将逻辑函数修改技术用于任意2N进制循环码计数器的综合。此外,还提出了使用附加触发器时循环码计数器的快速综合法。通过设计实例表明,采用快速综合法设计循环码计数器具有一定的优点和实用意义。     

Catalytic Reduction of Cyclic Ethers with Hydrosilanes

Catalytic reductive transformations of ethers as a synthetic building block are an important class of chemical reactions because a range of essential chemical feedstocks and fuels in contemporary life can be prepared through the key step of ethereal C?O bond cleavage of cellulosic biomass. Although conventional stoichiometric and catalytic methods for sp²‐ and sp³‐C?O bond cleavage of linear ethers and alcohols with hydrosilanes are well established, silylative ring opening of cyclic ethers has been less highlighted in this context. This review outlines catalytic systems for the silylative reduction of a range of cyclic ethers, including epoxides and sugars, leading to the corresponding alcohols and/or hydrocarbons. The chemical reactivity and selectivity of these ring‐opening catalytic processes are discussed with respect to the type of substrates; the representative catalytic working modes are also described.     

Preparation of Polar Ethylene–Norbornene Copolymers by Metallocene Terpolymerization with Triisobutylaluminium‐Protected But‐3‐en‐1‐ol

But‐3‐en‐1‐ol has been pre‐protected by triisobutylaluminium and terpolymerized with ethylene and norbornene by rac‐[Et(Ind)₂]ZrCl₂/MAO catalysts. The strong polarity of diisobutyl(but‐3‐en‐1‐oxy)aluminum causes a slight reduction in the catalyst activity and yields a small fraction of crystallinity. The but‐3‐en‐1‐ol content in the terpolymer is as high as 3.2% and can be readily adjusted by varying the reaction conditions. When the norbornene/ethylene ratio is over 10, the norbornene incorporation efficiency is not affected by the polar monomer and is close to that of the copolymerization. Similar to the ethylene/norbornene copolymers, the thermal properties of the obtained terpolymers are mainly determined by their norbornene contents.

     

Peel-off case failure in thermal explosions observed by the deflagration cylinder test

We have discovered a previously unidentified thermal explosion mode using the Los Alamos deflagration cylinder test (DFCT). The DFCT is a “pipe bomb”-style test similar to the detonation cylinder test (DTCT), which has been used for many years to calibrate detonation product equations of state. The shot is heated in an oven to a uniform test temperature. The pre-heated high explosive (HE) is triggered by a hot wire initiator on one end. The tube is back-illuminated by a bright light source, and its combustion-driven deformation and subsequent break-up are observed by a high-speed framing camera. Like the DTCT, the DFCT tube wall motion provides the primary diagnostic. A variety of reactive responses are possible, including quasi-steady deflagration and deflagration-to-detonation transition. This paper focuses on the behavior of the HMX-based explosive PBX 9501 at 155 °C. Under this condition burning appeared to occur only at the HE/tube interface, causing the tube to peel away from the HE core. Peel-off propagated as a wave that traveled along the tube at 500 m/s. This failure mode resulted in vigorous case venting, but the response was otherwise benign. We derive a steady peel-off-wave model that reproduces the essential observed features for realistic PBX 9501 parameter values.     

循环群诸类问题探

主要探讨:(i)循环群的定义和性质;(ii)循环群及其子群特征;(iii)同构于Vn、(Z+0)及其推广.     

1‐Phenyl‐1,2‐cyclohexadiene: Astoundingly High Enantioselectivities on Generation in a Doering–Moore–Skattebøl Reaction and Interception by Activated Olefins

The resolution of (1α,5α,6α)‐6‐bromo‐6‐fluoro‐1‐phenylbicyclo[3.1.0]hexane (rac‐ 5) provided the enantiomerically pure precursors (?)‐ 5 and (+)‐ 5 of 1‐phenyl‐1,2‐cyclohexadiene. On treatment of (?)‐ 5 with methyllithium in the presence of 2,5‐dimethylfuran, the pure (?)‐enantiomer of the [4+2] cycloadduct of 2,5‐dimethylfuran onto 1‐phenyl‐1,2‐cyclohexadiene was obtained exclusively. From this result, it is concluded that pure (M)‐1‐phenyl‐1,2‐cyclohexadiene ((M)‐ 7 ) emerged from (?)‐ 5 and was enantiospecifically intercepted to give the product. In the case of indene as trap for (M)‐ 7 , the (?)‐ and the (+)‐enantiomer of the [2+2] cycloadduct were formed in the ratio of 95:5. Highly surprising, remarkable enantioselectivities were also observed, when (M)‐ 7 was trapped with styrene to furnish two diastereomeric [2+2] cycloadducts. Hence, the achiral conformation of the diradical conceivable as intermediate cannot play a decisive part. The enantioselective generation of (M)‐ and (P)‐ 7 by the β‐elimination route was tested as well. Accordingly, 1‐bromo‐2‐phenylcyclohexene was exposed to the potassium salt of (?)‐menthol in the presence of 2,5‐dimethylfuran, and the enantiomeric [4+2] cycloadducts of the latter onto (M)‐ and (P)‐ 7 were produced in the ratio of 55:45.     

Mass tranfer of ions and solvent at redox processes in poly-3,4-ethylenedioxythiophene films

The work presents the data on mass transfer at the interface of the poly-3,4-ethylenedioxythiophene film with different propylene carbonate electrolyte solutions (TBAPF₆, LiClO₄, NaClO₄, TBAClO₄, TBABF₄) obtained using the quartz microgravimetry method in combination with cyclic voltammetry. It is shown that two parts of different nature can be observed in the region of electric activity of poly-3,4-ethylenedioxythiophene films on Δm, ΔQ curves. They evidence the change in mass transfer conditions at achieving different film oxidation degrees.     

The new composites,polyacetylene-carbon nanotubes: Electrochemical properties

Polyacetylene- and carbon-nanotube-based composite materials are prepared by the method of polymerization filling for the first time. It is shown that the acetylene polymerization mainly occurs at catalytic centers attached to the carbon nanotubes. It follows from TEM data that in the case of single-wall nanotubes the polyacetylene fibriles are wound up onto the nanotubes. In the case of multi-wall nanotubes, polyacetylene can form separate bodies that are connected to the multi-wall nanotubes. The specific electrochemical capacity of the novel composite materials is nearly twice as large as compared with that of the composite prepared by mechanical mixing; it is by two orders of magnitude larger than the pure polyacetylene capacity. The reversibility of the Li⁺ intercalation-deintercalation electrode reaction appears significantly improved at the polyacetylene-carbon nanotubes composites.