共查询到20条相似文献,搜索用时 93 毫秒
1.
2.
3.
利用核磁共振方法研究了取代吡唑对炔基Fischer卡宾化合物的Michael加成的动力学行为,该反应为典型的二级反应。当吡唑的3,5-位由较大基团取代时,反应速率常数变小,而活化焓和活化熵明显增大。利用密度泛函理论研究了炔基钨卡宾为底物的Michael加成反应机理,发现吡唑上取代基团的增大可以导致第三步反应的活化能大于第一步,从而使反应的决速步骤由原来的第一步转变为第三步。 相似文献
4.
5.
6.
7.
8.
10.
11.
苯在四氯化碳溶剂中以硝酸和疏酸的混合酸为硝化剂在温和条件下进行硝化,硝基苯的产率高,硫酸可以回收再利用。例如,在带有搅拌器、滴液漏斗、温度计和冷凝器的四颈烧瓶中,加入44.4毫升苯和40毫升四氯化碳,将39.5毫升浓硝酸和41.5毫升浓硫酸混合后从滴液漏斗中滴加,维持温度在15~55℃之间,约40分钟滴完后,在55~62℃继续反应30分钟。有机层分别用水、10%氢氧化钠溶液、水洗涤,干燥、蒸馏,先蒸出溶剂可再用。然后收集204~210.8℃的馏份,得硝基苯60.6克,产率98.53%。废硫酸通过蒸馏浓缩后,可重新用于硝化反应。 相似文献
12.
谷胱甘肽和Ebselen对胰岛素硝化的抑制及其相互作用机理的研究 总被引:3,自引:0,他引:3
生物体内NO和超氧阴离子快速反应生成的过氧亚硝酸根离子(ONOO-,peroxynitrite)是一种强细胞毒性物质,它诱导蛋白质酪氨酸残基硝化是其损伤生物系统的重要途径之一。为了探讨谷胱甘肽和ebselen对胰岛素硝化的抑制及其相互作用机理,采用UV-Vis、HPLC和ESI-MS等方法,研究了ONOO-对胰岛素的硝化作用、小分子抗氧化剂谷胱甘肽(GSH)和ebselen对ONOO-硝化胰岛素的影响以及它们之间的相互作用。结果表明单独的GSH和ebselen对ONOO--引发的胰岛素硝化均有明显的抑制,而作为谷胱甘肽过氧化物酶(GPx)的底物GSH 与GPx的模型化合物ebselen之间存在相互拮抗作用,经过对其产物分析,确定其机理是GSH和ebselen能够直接反应生成一种加合物,从而抑制了GSH和ebselen各自的抗硝化能力。 相似文献
13.
Tanaka M Muro E Ando H Xu Q Fujiwara M Souma Y Yamaguchi Y 《The Journal of organic chemistry》2000,65(10):2972-2978
The nitration of methylnaphthalenes with NO(2)BF(4) and NOBF(4) was examined in order to shed light on the controversial aromatic nitration mechanism, electrophilic vs charge-transfer process. The NO(2)(+) nitration of 1,8-dimethylnaphthalene showed a drastic regioselectivity change depending on the reaction temperature, where ortho-regioselectivity at -78 degrees C and para-regioselectivity at 0 degrees C were considered to reflect the electrophilic and the direct or alternative charge-transfer process, respectively, because the NO(+) nitration through the same reaction intermediates as in the NO(2)(+) nitration via a charge-transfer process resulted in para-regioselectivity regardless of the reaction temperature. The NO(2)(+) nitration of redox potential methylnaphthalenes higher than 1,8-dimethylnaphthalene gave a similar ortho-regioselectivity enhancement to 1,8-dimethylnaphthalene at lower temperature, thus reflecting the electrophilic process. On the other hand, the NO(2)(+) nitration of redox potential methylnaphthalenes lower than 1,8-dimethylnaphthalene showed para-regioselectivity similar to the NO(+) nitration, indicating the direct or alternative charge-transfer process. In the presence of strong acids where the direct charge-transfer process will be suppressed by protonation, the ortho-regioselectivity enhancement was observed in the NO(2)(+) nitration of 1,8-dimethylnaphthalene, suggesting that the direct charge-transfer process could be the main process to show para-regioselectivity. These experimental results imply that the NO(2)(+) nitration proceeds via not only electrophilic but also direct charge-transfer processes, which has been considered to be unlikely because of the high energy demanding process of a bond coordination change between NO(2)(+) and NO(2). Theoretical studies at the MP2/6-31G(d) level predicted ortho- and para-regioselectivity for the NO(2)(+) nitration via electrophilic and charge-transfer processes, respectively, and the preference of the direct charge-transfer process over the alternative one, which support the experimental conclusion 相似文献
14.
15.
Jin Ku Cho Young-Tae Kim Young Gyu Kim Yoon-Sik Lee Si-Young Sung Kyoo-Hyun Chung Bon-Su Lee 《Research on Chemical Intermediates》2006,32(8):759-766
A practical neutral aromatic nitration process using nitrogen dioxide in the presence of FeCl3 · 6H2O under 40–100 psig of oxygen was developed, and nitration of several aromatic compounds, including the deactivated nitrobenzene, was performed in a successful manner. The correlation of reaction rate with equivalents nitrogen dioxide, oxygen pressure, amount of catalyst and temperature was investigated through the nitration of benzene. Following the optimization of reaction conditions, the nitration of benzene was scaled up to 476 mol. Furthermore, inorganic solid catalysts with pore size over 5 Å and surface area over 100 m2/g were applied to newly developed neutral nitration. 相似文献
16.
Nakagawa H Sumiki E Takusagawa M Ikota N Matsushima Y Ozawa T 《Chemical & pharmaceutical bulletin》2000,48(2):261-265
The inhibitory effects of various endogenous and synthetic compounds on the nitration and oxidation of L-tyrosine by peroxynitrite were examined. Nitrating and oxidizing activities were monitored by the formation of 3-nitrotyrosine and dityrosine with a HPLC-UV-fluorescence detector system, respectively. Glutathione, serotonin and synthetic sulfur- and selenium-containing compounds inhibited both the nitration and oxidation reaction of L-tyrosine effectively. However, 5-methoxytryptamine, melatonin and alpha-lipoic acid only inhibited the nitration reaction, and enhanced the formation of an oxidation product. This is important evidence that there are different intermediates in the nitrating and oxidizing reactions of L-tyrosine by peroxynitrite. It was suggested that 5-methoxytryptamine, melatonin and alpha-lipoic acid reacted only with the nitrating intermediate of peroxynitrite and inhibited nitration of L-tyrosine. Actually, the DNA strand breakage, which is believed to be a typical reaction of hydroxyl radical-like species, caused by peroxynitrite was not effectively inhibited by 5-methoxytryptamine. 5-Methoxytryptamine, melatonin and alpha-lipoic acid were viewed as useful reagents for investigating the mechanisms of damage by peroxynitrite in vitro. 相似文献
17.
[reaction: see text] Bi(NO(3))(3).5H(2)O was used as an efficient nitrating reagent in the nitration of phenolic compounds to give nitrated phenols in good to high yields. The nitration reaction proceeded smoothly by grinding 1 equiv of phenol, 2-methylphenol, 4-methylphenol, or 4-chlorophenol and Bi(NO(3))(3).5H(2)O, and the nitration of other phenolic compounds could be performed in acetone at ambient temperature (22-30 degrees C). 相似文献
18.
19.
20.
Mikhailov Yu. M. Romanova L. B. Darovskikh A. V. Barinova L. S. 《Russian Journal of Applied Chemistry》2019,92(3):445-452
Russian Journal of Applied Chemistry - The nitration of hyperbranched polyglycidols was studied. It was confirmed that there is no destruction of the polymeric chain when the nitration reaction is... 相似文献