排序方式: 共有74条查询结果,搜索用时 15 毫秒
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Cs2CO3 was found to efficiently catalyze the reaction of β-cyclodextrin and N-tosylimidazole. Stirring β-cyclodextrin and N-tosylimidazole in 1/1.2 molar ratio in DMF in the presence of catalytic amount of Cs2CO3 at rt for 1.5 h afforded 2A-mono(O-tosyl)-β-cyclodextrin in 32% yield. The 2A,2B-, 2A,2C- and 2A,2D-ditosylates were isolated in ca. 6-7% yields, respectively, when β-cyclodextrin and N-tosylimidazole were used in 1/2.5 molar ratio. The charge of excess (10 equiv) of N-tosylimidazole ensured a one-step direct (protection-free) synthesis of the per(2-O-tosyl)-β-cyclodextrin in 5% isolated yield. N-(m-Nitrobenzenesulfonyl)imidazole even allowed a much faster access to the corresponding persulfonate in only 1 h reaction. 相似文献
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LIU Yong-Dong ZHONG Ru-Gang 《结构化学》2008,27(2):171-176
The conversion of peroxynitrite (ONOO-) to nitrate (NO3-) mediated by peroxynitrous acid (ONOOH) has been investigated at the CCSD/6-311G(d)//B3LYP/6-31 1+G(d,p) level. Two kinds of pathways for the title reaction were found. The results show that the energy barrier of isomerization through pathway 1 is around 25 kcal/mol in the gas phase. This value is significantly lower than that of isomerization without any catalysts. Thus, it indicates that ONOOH definitely makes the conversion from ONOO- to NO3- feasible. Although pathway 2 does not decrease the energy barrier of this isomerization, peroxynitric acid (O2NOOH) was obtained; moreover, this is a new pathway for this formation. In view of the results that peroxynitrate anion can decompose into nitrite and dioxygen, we conclude that our results are consistent with the experimental observation that nitrate, nitrite, and dioxygen are the main final products of the decay of peroxynitrite around pH 7. 相似文献
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利用紫外-可见分光光度计在乙醇介质中研究了合成的4种对位取代四苯基钴卟啉对过亚硝酸根分解的催化作用. 首次发现钴卟啉可以催化ONOO-分解, 且对位带吸电子基团的钴卟啉比对位带供电子基团的钴卟啉催化活性高. TPPCoCl, T(p-CH3)PPCoCl, T(p-OCH3)PPCoCl和T(p-Cl)PPCoCl在乙醇中的kcat分别为1.69×102, 1.52×102, 1.43×102和1.20×103 mol-1•L•s-1. 动力学曲线和时间分辨谱证明这些钴卟啉是通过形成中间体催化过亚硝酸根分解的. 相似文献
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Yi Yuan Zong-Lin Jiang Jia-Ming Yan Ge Gao Albert S. C. Chan Ru-Gang Xie 《合成通讯》2013,43(24):4555-4561
Two new macrobicyclic imidazolium and benzimidazolium phanes were synthesized by direct quaternization of the corresponding tripodal azacycles with tribromide under high dilution condition in excellent yields. The cyclophanes were identified by 1H-NMR, 13C-NMR, FAB-MS, IR, elemental analysis and X-ray diffraction analysis. 相似文献
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Yang Jiang Ru-Gang Zhong Bo Tan Yan-Mei Li Yu-Fen Zhao 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):831-837
The reactivity of N -phosphoryl f -alanine differs from N -phosphoryl g -alanine and N -phosphoryl n -amino butyric acid enormously. N -phospho- f -alanine could self-activate to yield N -phosphopeptides either in aqueous or nonaqueous media, but not g - or n -amino acid analogues. The mechanism of the reaction is discussed. 相似文献
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用密度泛函理论(DFT)研究了过氧亚硝酸与酪氨酸的反应机理. 在B3LYP/6-311G(d,p)水平上对该反应体系的反应物、中间体、过渡态和产物进行了几何构型优化并计算了振动频率和能量. 计算结果表明, 过氧亚硝酸不易直接与酪氨酸反应, 而是先分解产生自由基(·OH和·NO2), 而后再与酪氨酸分步作用. 过氧亚硝酸与酪氨酸的反应生成两种主要产物, 分别为3-羟基酪氨酸和3-硝基酪氨酸, 这一结论与实验所得到的结果一致. 此外在同一计算水平上采用SCRF(PCM)方法计算了溶剂化效应, 结果表明, 极性溶剂可以增加自由基结合的稳定化能, 并降低反应通道的活化能, 有利于反应的进行. 相似文献
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Reactive nitrogen oxygen species(RNOS) implicate damage in biological systems,especially leading to inflammation,neurodegenerative and cardiovascular diseases,and cancer by altering the functions of biomolecules through the N-nitrosation and N-nitration reactions.The mechanisms of N-nitrosation and N-nitration reactions of ammonia and dimethylamine by RNOS,i.e.,N2O3,N2O4,N2O5 and ONOOH,were investigated at the CBS-QB3 level of theory.The computational results indicate that the N-nitrosation reaction prefers a concerted mechanism,in which a H-abstraction and ON-addition occur simultaneously,whereas a stepwise mechanism(also called a free radical mechanism) is more favorable for most nitrating agents in the N-nitration reaction,where NO2 first abstracts a hydrogen atom from the nitrogen of amines and then the induced intermediate reacts with NO2 once more to form the nitration products.However,the concerted pathway is still a feasible process for some nitrating agents such as N2O5.In addition,the relationship between the structures of different RNOS and their nitrosating or nitrating abilities was also investigated. 相似文献
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采用量子化学计算研究了磷酰化氨基酸的反应性质,包括N-磷酰氨基酸成肽反应、成酯反应、磷上酯交换反应和磷上的N→O迁移反应的机理以及计算模型和计算方法的选择,并从理论上解释了自然界选择α-氨基酸而不是β,γ-氨基酸的实验事实. 相似文献
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