Sum-over-states calculation of the specific rotations of some substituted oxiranes, chloropropionitrile, ethane, and norbornenone

A sum-over-states approach has been applied to the calculation of the specific rotations of several substituted oxiranes, 2-chloropropionitrile, and 30 degrees-rotated ethane. In each case, the first few excited states proved to have only a relatively small effect on the calculated specific rotation. It was necessary to use a very large number of excited states in order to achieve convergence with the results of the more direct linear response method. However, the latter does not give information on which excited states are important in determining the specific rotation. Norbornenone is unique in that its greatly enhanced specific rotation as compared to norbornanone is associated with the low-energy n-pi* transition. The C=C bond orbitals interact with the C=O in the LUMO, and a density difference plot for going from the ground state to the first excited state clearly shows the perturbation of the C=C.     

An exploration of electronic structure and nuclear dynamics in tropolone. I. The X 1A1 ground state

The ground electronic state (X 1A1) of tropolone has been examined theoretically by exploiting extensive sets of basis functions [e.g., 6-311++G(d,p) and aug-cc-pVDZ] in conjunction with the high levels of electron correlation made possible by density functional (DFT/B3LYP), Moller-Plesset perturbation (MP2), and coupled-cluster [CCSD and CCSD(T)] methods. Unconstrained MP2 and CCSD optimization procedures performed with the reference 6-311++G(d,p) basis predict a slightly nonplanar equilibrium structure characterized by a small barrier to skeletal inversion (< or =10 cm(-1) magnitude). Complementary harmonic frequency analyses have shown this nonplanarity to be a computational artifact arising from adversely tuned carbon d-orbital exponents embodied in the standard definitions of several Pople-type basis sets. Correlation-consistent bases such as Dunning's aug-cc-pVDZ are less susceptible to these effects and were employed to confirm that the X 1A1 hypersurface supports a rigorously planar global minimum. The fully optimized geometries and vibrational force fields obtained by applying potent coupled-cluster schemes to the relaxed-equilibrium (Cs) and transition-state (C2v) conformers of tropolone afford a trenchant glimpse of the key features that mediate intramolecular hydron exchange in this model system. By incorporating perturbative triples corrections at the substantial CCSD(T) level of theory, an interoxygen distance of r(O...O)=2.528 A was determined for the minimum-energy configuration, with the accompanying proton-transfer reaction being hindered by a barrier of 2557.0 cm(-1) height. The potential energy landscape in tropolone, as well as the nature of the attendant hydron migration process, is discussed within the framework of the encompassing G4 molecular symmetry group.     

Diels-Alder reactions of 3-substituted coumarins in water and under high-pressure condition. An uncatalyzed route to tetrahydro-6H-benzo[c]chromen-6-ones

[reaction: see text] Diels-Alder reactions of 3-substituted coumarins 1a-g with methyl-1,3-butadienes 2a-c carried out in water alone and in CH2Cl2 under 9 kbar pressure are reported. In aqueous medium satisfactory results were obtained by operating at 150 degrees C, whereas under high pressure the cycloadditions were complete at 60-70 degrees C with excellent yields (85-95%). The reactions with isoprene (2b) always resulted in the exclusive formation of para cycloadducts, whereas with (E)-piperylene (2c) only ortho products were detected. The cycloaddition of 3-phenylsulfonylcoumarin (1a) with (E)-piperylene (2c) allowed the endo adduct to be obtained exclusively, whereas 3-carboxycoumarin (1b) reacted with 2c to give a mixture of the corresponding endo/exo adducts in a 58:42 ratio in water and in a 45:55 ratio under high-pressure condition.     

A catalytic approach to the base-promoted reaction of epoxides with activated methylenes

This contribution reports the results obtained in the definition of a catalytic method for the nucleophilic ring opening of epoxides by activated methylenes promoted by a polymer-supported base. The attention has been focused on the use of polymer supported bases and the best results have been obtained by using 4-(dimethylamino)pyridine (PS-DMAP) and 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine both on polystyrene (PS-BEMP). Solvent-free conditions has been essential for reaching a sufficient reactivity to realize this process, in fact when a reaction medium is used, the processes are almost unfeasible.     

聚苯基硅氧烷与聚甲基苯基硅氧烷改性环氧树脂的合成与性能比较

热熔法制备了一系列聚苯基甲氧基硅氧烷(PPMS)、聚甲基苯基甲氧基硅氧烷(PMPS)改性环氧树脂,通过环氧值、红外光谱(IR)分析表明聚硅氧烷接枝了E-20环氧树脂且环氧基保持不变.探讨了有机硅含量对改性树脂固化体系耐热性能及韧性的影响.实验表明,当E-20环氧树脂与PPMS、PMPS的质量比为7∶3时,改性树脂固化体系的耐热性能明显提高,玻璃化转变温度(Tg)为95.8、88.3℃,分别比改性前提高了9.0℃和1.5℃;质量损失50%时的热分解温度(Td)为476.5、487.8℃,分别比改性前提高了58.3℃和69.5℃.与ED-30固化体系相比,EPMS-30固化物的耐热性能,韧性等力学性能提高的更加明显,并且还具有优良的涂膜性能.     

铝球弹丸高速斜撞击铝Whipple防护结构时后板的损伤特性

 为了研究空间碎片对航天器防护结构的高速斜撞击损伤特性,采用二级轻气炮发射铝球弹丸,对铝Whipple防护结构进行高速斜撞击实验。弹丸直径为3.97 mm,撞击速度为1.14～5.35 km/s,撞击角度为0°～70°。实验得到了铝Whipple防护结构在不同撞击速度区间的后板损伤模式,分析了后板撞击损伤及弹坑分布特性,建立了预测铝球弹丸高速斜撞击铝Whipple防护结构时后板弹坑分布的经验公式。结果表明：在大角度斜撞击条件下,对于一定的撞击速度,铝Whipple防护结构的后板弹坑分布会出现两个区域;弹丸的撞击破碎临界速度将影响后板损伤随撞击角的变化关系;对于铝Whipple防护结构,存在使后板撞击损伤最严重的临界撞击角。     

治疗胃炎伴糜烂蒙药中多种微量元素的ICP-AES法测定

蒙药含有多种氨基酸和丰富的微量元素,特别是人体必需的微量元素含量相对高,而对人体有害的重金属元素含量相对低。采用微波消解ICP-AES法同时测定了治疗胃炎伴糜烂组合蒙药(1#:如达-6、2#:巴特日-7(Ⅱ))中Ca、Mg、Al、Fe、Mn、Sr、Cu、Zn、Pb等15种微量元素。加标回收率在94.9%~106.2%之间,相对标准偏差RSD≤3.2%,检出限在≤0.009μg/L。实验结果表明:1#、2#为不同类型的蒙药,其微量元素含量有所不同。     

ChemInform Abstract: Azidopentazole is Probably the Lowest-Energy N8 Species - A Theoretical Study.

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