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71.
High-level computations at G3, CBS-Q, and G3B3 levels were conducted, and good-quality C-H and N-H bond dissociation energies (BDEs) were obtained for a variety of saturated and unsaturated strained hydrocarbons and amines for the first time. From detailed NBO analyses, we found that the C-H BDEs of hydrocarbons are determined mainly by the hybridization of the parent compound, the hybridization of the radical, and the extent of spin delocalization of the radical. The ring strain has a significant effect on the C-H BDE because it forces the parent compound and radical to adopt certain undesirable hybridization. A structure-activity relationship equation (i.e., BDE (C-H) = 61.1-227.8 (p(parent)% - 0.75)(2) + 152.9 (p(radical)% - 1.00)(2) + 40.4 spin) was established, and it can predict the C-H BDEs of a variety of saturated and unsaturated strained hydrocarbons fairly well. For the C-H BDEs associated with the bridgehead carbons of the highly rigid strained compounds, we found that the strength of the C-H bond can also be predicted from the H-C-C bond angles of the bridgehead carbon. Finally, we found that N-H BDEs show less dependence on the ring strain than C-H BDEs. 相似文献
72.
73.
A one-pot procedure for the efficient synthesis of a small library of t-RNA inhibitor analogues was developed. Thus,Rh2(OAc)4 catalyzed three-component 1,3-dipolar cycloaddition reactions of carbonyl ylides derived from diazoindan-1,3-dione and aldehydes with other dipolarophiles in 1,1,2,2-tetrachloroethane at 80 ℃ gave ring fused tetrahydrofurans having three stereocenters in good yield. 相似文献
74.
ZHANG Peng-Fei CHEN Zhen-Chu 《有机化学》2003,23(Z1):87-89
During the last few years alkenyl(phenyl)iodonium salts have risen from mere chemical curiosities to valuable synthetic intermediates. [1] Because of an excellent leaving group ability of a phenyliodonyl moiety, alkenyl(phenyl) iodonium salts undergo nucleophilic vinyl substitutions under mild conditions, thus providing a useful route for the synthesis of various kinds of olefins. Recently, some of functionalized alkenyl iodonium salts have been prepared. [2] 相似文献
75.
CHEN Kai ZHU Zhong-liang ZHANG De-jun 《高等学校化学研究》2006,22(4):435-438
IntroductionStudies on reversible kinetic systems are consi-dered as a hotspot of chemical and biochemical kineticresearches[1,2]. Of late, some researches have been fo-cused on the simultaneous optimization of the obverseand reverse rate constants[3,4].H… 相似文献
76.
Seo K Kim C Choi YS Park KA Lee YH Kim B 《Journal of the American Chemical Society》2003,125(46):13946-13947
CO2 molecule chemisorbs selectively on the zigzag tube edge without an activation barrier, whereas it physisorbs on the armchair edge of nanotubes. In addition, carbon nanotubes can be etched by an adsorbed oxygen atom of CO2 molecule. From our results, we suggest a selective etching mechanism for tuning the chirality of the mass-produced carbon nanotubes. 相似文献
77.
Rhodium(II)-catalyzed reactions of cyclic diazodicarbonyl compounds with a variety of halides have been examined. With acid halides, β-acyloxy α-haloenones are produced in good yields. With benzyl halides, β-benzyloxy α-haloenones are obtained in good yields. Reactions with methylene halides yield β-halomethoxy α-haloenones in good yields, whereas reactions with ethyl halides and ethylene dihalides result in β-hydroxy α-haloenones in high yields. These reactions provide a useful and rapid entry to β-substituted α-haloenones. The mechanistic pathway for the formation of these products has been also described in terms of halonium ylides. 相似文献
78.
流动注射电化学发光测定维生素B1的研究 总被引:2,自引:0,他引:2
基于发现在强碱性介质维生素 B1对电生BrO-氧化Luminol的强化学发光有很强的抑制作用, 将在线恒电流电解产生BrO-与流动注射技术结合,建立了流动注射电化学发光测定维生素B1的新方法.该方法测定维生素B1的线性范围为1.0×10-8~6.0×10-6g·ml-1,检出限为3.2×10-9g·ml-1,相对标准偏差为1.2%(n=11).该法具有灵敏度高,可控性强等优点,用于片剂中的维生素B1含量测定,结果满意. 相似文献
79.
离子型溶液聚合速度方程式一般可写成: r=-dM/dθ=kM~mC~n式中M,C分别代表溶液中单体与催化剂的浓度,m,n是两个动力学参数。为了控制聚合过程或设计适当的反应器,必须考虑体系的动力学特性与传热特性的紧密联系。本文 对恒温下分批式聚合操作的各种实施方案进行了讨论。 相似文献
80.
Ying-nan Xuan Yan Gao Yong Huang Xi-gao Jian Laboratory of Cellulose Lignocellulosics Chemistry Guangzhou Institute of Chemistry Chinese Academy of Sciences Guangzhou China Institute of Chemistry Chinese Academy of Sciences Beijing China Department of Polymer Science College of Chemical Engineering Dalian University of Technology Dalian China 《高分子科学》2002,(3):225-229
A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfoneketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)-1(2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin insulfolane in the presence of K_2CO_3 to produce high molecular weight polymers which can be dissolved in some polarsolvents such as chloroform and nitrobenzene at room temperature and can be easily can into flexible, yellowish andtransparent films. PPESK is an amorphous polymer having a decomposition temperature above 400℃, which indicates that ithas high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agentindicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (ΔE) ofthe cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively.Therefore, the cross-linking reaction is approximately a first order reaction. 相似文献