Base‐dependent selectivity of an SNAr reaction

A detailed kinetic analysis and computational study of an S_NAr reaction between 2,5,6‐trifluoronicotinonitrile, 2 , and the ambident 3‐isopropoxy‐1H‐pyrazol‐5‐amine, 3 , is presented. The selectivity with respect to the reaction at the primary amino group of 2 , to give the desired product, 2,5‐difluoro‐6‐[(3‐isopropoxy‐1H‐pyrazol‐5‐yl)amino]nicotinonitrile, 1 , is strongly dependent upon reaction conditions. Reaction is found to proceed via both uncatalysed and base catalysed routes, and selectivity towards 1 is strongly enhanced in the presence of the base diazabicyclo[2,2,2]octane (DABCO). Computational studies in tetrahydrofuran solution at the B3LYP/6‐31G* level of theory have provided valuable insight into alternative kinetically indistinguishable reaction pathways. The results suggest that for reaction at the primary amino group, proton removal by DABCO accompanying amine addition allows avoidance of a high‐energy, zwitterionic Meisenheimer intermediate. Reactions at the alternative pyrazole nitrogen atoms are less sensitive to the presence of base because of stabilisation of the Meisenheimer zwitterions by intramolecular hydrogen bonding. Copyright © 2010 John Wiley & Sons, Ltd.     

Deterministic joint remote preparation of arbitrary multi-qudit states

In this Letter, we put forward a new nontrivial three-step strategy for joint remote preparation of arbitrary two-qudit states (JRSP) in a deterministic manner from a spatially separated multi-sender to one receiver. The scheme is then extended to the arbitrary multi-qudit case. In our schemes, various partially entangled GHZ-like states with arbitrary complex parameters are used as the quantum channels. It overcomes state preparation failure leading to the loss of valuable quantum channel resource and ensures the prepared data available for the remote terminals under extreme conditions such as limited number of quantum channels and limited quantum information processing technologies.     

The SN3–SN2 spectrum. Rate constants and product selectivities for solvolyses of benzenesulfonyl chlorides in aqueous alcohols

Rate constants for a wide range of binary aqueous mixtures and product selectivities (S) in ethanol–water (EW) and methanol–water (MW) mixtures, are reported at 25 °C for solvolyses of benzenesulfonyl chloride and the 4‐chloro‐derivative. S is defined as follows using molar concentrations: S = ([ester product]/[acid product]) × ([water solvent]/[alcohol solvent]). Additional selectivity data are reported for solvolyses of 4‐Z‐substituted sulfonyl chlorides (Z = OMe, Me, H, Cl and NO₂) in 2,2,2‐trifluoroethanol–water. To explain these results and previously published data on kinetic solvent isotope effects (KSIEs) and on other solvolyses of 4‐nitro and 4‐methoxybenzenesulfonyl chloride, a mechanistic spectrum involving a change from third order to second order is proposed. The molecularity of these reactions is discussed, along with new term ‘S_N3–S_N2 spectrum’ and its connection with the better established term ‘S_N2–S_N1 spectrum’. Copyright © 2009 John Wiley & Sons, Ltd.     

时基反馈控制的Tesla变压器初级电源

LC谐振充电是Tesla变压器常用的初级电容充电技术,但存在对控制时序要求高、易受电磁干扰和不具备故障保护能力等缺陷。针对这个问题,提出了一种时基反馈控制的LC谐振充电电源。该电源与传统LC谐振电源的主要区别在于,采用特殊设计的时基反馈电路取代多路时基控制器,将能量回收开关反向阻断瞬间的电压突变调制为谐振晶闸管触发信号,从而在能量回收结束时刻启动谐振充电,实现各工作回路准确按照预定时序运行。时基反馈电路由高压元件构成,不易受电磁干扰,且在原理上具备负载短路保护能力。该技术已经应用于CKP1000,CKP5000等多台Tesla型超宽谱脉冲源。实验结果表明,在强脉冲辐射环境下,该电源能够1000 Hz重频稳定运行,且能够在Tesla变压器初级短路故障时进行快速自动保护。     

适于遥感图像实时压缩的小波基的选择

遥感图像相关性弱,纹理细节丰富,故对其采用基于小波变换的图像编码方法进行编码压缩,而在对图像进行小波变换时,小波基的选取是至关重要的,它直接影响到变换速度和编码效率。在详细分析小波基的基本性质及其与图像编码的关系的基础上,选出数种典型小波基进行实验比较。实验结果表明D5/3双正交小波基最适合于遥感图像实时压缩,最后经实验验证其选取是合理的。     

Mesogenic Schiff base esters with benzothiazole core: synthesis and phase transition studies

A series of new rod-shaped mesomorphic compounds, 6-ethoxy-2-(4-alkanoyloxybenzylidenamino)benzothiazoles, consisting of a 2,6-disubstituted benzothiazole core and a Schiff base central linkage, were synthesized and their structures were ascertained via elemental analysis and spectroscopic techniques. Their mesomorphic properties were studied using differential scanning calorimetry (DSC), polarized optical microscopy (POM) and X-ray diffraction (XRD) analysis. All compounds showed enantiotropic mesomorphism. Whilst the lower members of the series, hexanoyloxy and octanoyloxy derivatives exhibited nematic phase, the higher members (decanoyloxy, dodecanoyloxy, tetradecanoyloxy, hexadecanoyloxy and octadecanoyloxy derivatives) exhibited nematic and smectic C phases.     

新型氧钒(IV)席夫碱配合物［VO(dtbsal-met)(phen)和VO(naph-met)(phen)］的合成及其抗肿瘤活性

以L-蛋氨酸（met）, 1,10-邻菲啰啉（phen）和3,5-二叔丁基水杨醛（dbsal）［或2-羟基-1-萘醛（naph）］为原料,经胺醛缩合反应合成了两个新型的氧钒(IV)席夫碱配合物［VO(dtbsal-met)(phen)（1）和VO(naph-met)(phen)（2）］,其结构经IR, HR-ESI-MS,摩尔电导和X-射线单晶衍射表征。1（CCDC：1 429 158）和2（CCDC：1 429 159）分别属单斜晶系和三斜晶系。用MTT法研究了1和2对人肺腺癌细胞（A549）和人源肝癌细胞（HepG2）的体外抗肿瘤活性。结果表明：1和2对A549和HepG2均表现出一定的抑制活性。     

水杨醛缩L-天冬氨酸过渡金属配合物的合成及表征

合成了新的水杨醛天冬氨酸席夫碱配体及其铜、锌、钴、镍配合物,并利用元素分析、摩尔电导、热分析、红外光谱、电子光谱及顺磁共振等手段进行表征,确定配合物的化学组成为K［ML］·nH₂O,式中L=C₁₁H₇NO, M=Cu²⁺、Zn²⁺、Co²⁺、Ni²⁺,相应地n=2、2、3、7/2。     

双环[2，2，1]庚-5-烯-2-甲酰基芳香醛腙的合成和生物活性

合成了七个未见文献报道的双环[2，2，1]庚-5-烯-2-甲酰基芳香醛腙席夫碱 类化合物。用核磁共振氢谱、红外光谱和元素分析对新化合物进行了表征，考察了 它们的生物活性。结果表明某些化合物具有除草作用、抗菌作用和植物生长调节作 用。     

Sequential Alkylation of Tröger's Base. An Approach to New Chiral Ligands

Heterocycles derived from Tröger's base were shown to complex with metal salts in 2:1 ligand:salt ratios as monodentate or bidentate ligands depending on structure.