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Anodic oxidation of aromatic hydrocarbons and olefins in acetonitrile containing silver nitrite, has been studied.With aromatic hydrocarbons the better yields in mononitro compounds were obtained with anthracene and methoxybenzene. The orientation is discussed: the site of substitution is the unsubstituted position with most important spin density in the radical cation (from substrate oxidation).Diphenyl ethylene and paramethoxystyrene yields nitroolefins; the 2-phenylpropene produce a mixture of nitroolefin and nitro alcohol. Trans stilbene gave a mixture of 1,2 addition products containing the nitrato group. In order to explain the formation of the products we proposed a mechanism consistent with the ambidentate character of the nitrite ion. 相似文献
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Rosalía Sánchez-Fernández Dr. Agustín Sánchez-Temprano Prof. David Esteban-Gómez Dr. Elena Pazos 《Chembiochem : a European journal of chemical biology》2023,24(13):e202300072
Tyrosine nitration, a post-translational modification (PTM) that takes place under nitrosative stress conditions, occurs through a non-enzymatic peroxynitrite-mediated reaction. Although protein nitration has long been considered an irreversible PTM involved in nitrosative stress-associated diseases, it has also been suggested to be a regulatory mechanism of signal transduction. Therefore, the development of tools that help to understand this protein modification is of great interest. Herein, we explore a TbIII-chelating metallopeptide to monitor tyrosine nitration. The luminescence of this probe decreases significantly between its non-nitrated and nitrated states, and this reduction in the luminescence intensity is directly related to the degree of tyrosine nitration after treatment with peroxynitrite. Remarkably, the luminescence intensity changes after nitration are not affected in the presence of complex biological media, which makes it a promising tool for understanding this protein modification. 相似文献
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The sequence of formation of silicon nitride phases inside the volume of an initial silicon grain heated in a gaseous nitrogen medium is studied. Technologies for making ceramics articles based on silicon nitride are proposed. 相似文献
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以3-氟甲苯为原料,用三种不同硝化反应制备了5-氟-2-硝基甲苯。采用混酸硝化(在溶剂中,36.2ml浓硝酸、14.8ml浓硫酸、0℃~5℃、90g3-氟甲苯),5-氟-2-硝基甲苯的选择性为59.8%;68%,的浓硝酸/多聚磷酸硝化(28.0ml 68%硝酸、0℃~5℃、35g多聚磷酸、16.5g3-氟甲苯)5-氟-2-硝基甲苯的选择性为80.0%;浓硝酸硝化(96.5ml浓硝酸、200g3-氟甲苯、50℃~55℃、8小时、真空蒸馏)5-氟-2-硝基甲苯的选择性为79.9%,应用H-MR和IR对产品进行了表征。 相似文献
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Abstract The formation of methanol during treatment of wood meal with nitrogen dioxide is favored by the presence of oxygen and suppressed by addition of sodium sulfate. With 0.5% of added nitrogen dioxide large amounts of methanol were produced at 70°C when kraft lignin was impregnated with 0.5M nitric acid. A markedly increased formation of methanol and nitro groups in the lignin occurred when sodium nitrate was added. At low acidity the effect of sodium nitrate was insignificant. In a solution which was 0.5 molal with respect to nitric acid and 0.8 molal with respect to sodium nitrate, appreciable amounts of methanol and nitro groups were produced even when no nitrogen dioxide was added. This is explained by a generation of nitrogen dioxide from nitric acid in a autocatalytic process favored by high concentrations of nitrate and hydrogen ions. 相似文献
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Some aromatic compounds containing the imino group (NH) were nitrated in acetic acid or anhydride, and the ortho/para ratios were measured. N-Methyl derivatives of the aforementioned compounds are much less reactive when nitrated under comparable conditions and give significantly lower o/p ratios. These results along with the literature data support the hypothesis that the acetanilide-type compounds are nitrated via N-nitro intermediates. 相似文献
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硝化反应大多为快速强放热反应,要求硝化反应器应同时具备优良的混合和传热性能。采用新型螺旋盘管反应器并以混酸硝化苯作为工作体系进行了硝化工艺研究,考察了循环流量、混酸流量、混酸组成、反应温度等因素对苯转化率和硝化反应选择性的影响规律,并与螺旋盘管直径和长度相同的直管硝化工艺进行了对比研究。结果表明,在实验考察范围内,反应温度或物料循环流量提高时,硝基苯的选择性提高,但苯的转化率有所降低。增大混酸流量或混酸中硫酸摩尔比时,可提高苯的转化率,但由于增大了酸局部过量的几率,副产物亦随之增加。与直径和长度相同的直管相比,螺旋盘管反应器硝化过程中苯的转化率和硝基苯的选择性均有所提高。 相似文献
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介绍了硝基烷烃气相硝化的发展历程。综述了低碳烷烃、脂肪醇、羧酸、醛和酮类均相气相硝化制备方法。并对最新的高压硝化法制备硝基烷烃进行了简介。随着气相硝化技术的不断发展,硝基烷烃将得到更为广泛的应用。 相似文献
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Yasuto Fujimaki Minoru Takekawa Akira Uchida Shigeru Ohshima Isao Oonishi Shoji Fujisawa 《Polycyclic Aromatic Compounds》2013,33(1-4):189-197
Nitration of three isomeric dibenzanthrones, 13H-dibenzo[a,de]-anthracene-13-one(3), 7H-benzo[hi]chrysene-7-one(4), and 7H-dibenzo[a,kl]anthracene-7-one(5), with concentrated nitric acid was studied under various conditions. The nitration of (3) at 15 °C in 1,1,2,2-tetrachloroethane gave the 5-nitro derivative. The nitration of (4) in boiling acetic acid produced the 9-nitro derivative. The nitration of (5) at 70 °C in acetic acid gave the 5-nitro derivative. These nitro compounds are very useful in synthesizing undecacyclic aromatic hydrocarbons. 相似文献