Nitration of Bio-related Compounds with Peroxynitrite Mechanistic Implications to Biological Nitration

过氧亚硝酸盐对生物相关化合物的硝化对生物硝化的机理影响

• 批准号: 12640576
• 负责人: SUZUKI Hitomi
• 金额: $ 2.24万
• 依托单位: Kwansei Gakuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640576/
• 关键词: Peroxynitrite; Nitration; Hydroxylation; Reaction mechanism; Aromatic compound; Oxidation

In order to get insight into the mechanism of biological nitration, the reaction of peroxynitrite with some bio-related model compounds has been investigated in buffered aqueous solutions and acetonitrile. The compounds employed included phenols, N, N- i dimethylanline and activated olefines such as stilbene, 1, 4-diphenylbutadiene and 1, 4- diphenylbutenyne. Peroxynitrite was generated by the oxidation of sodium azide with ozone in aqueous alkaline solution.With phenols, concurrent nitration and hydroxylation took place on aromatic ring and the product distribution pattern showed a typical electrophilic nature. Side products included quinones and cyclohexadienes. A^A^-Dimethylaniline underwent extensive demethylation, which suggested involvement of the nitrosonium ion as active species. Stilbene afforded benzil, stilbene epoxide and benzaldehyde, together with some ring nitration products. The mechanism of oxidative cleavage of the carbon-carbon bond is not clear at present, since stilbene oxide, 1, 2-diphenylethanediol and diphenylhy＆roxyethanone were all found to be inert toward peroxynitrite. Under similar conditions, diphenylacetyle afforded benzil as the main product along with ring nitration products ; strangely enough, the substitution pattern of which was only ortho and meta. The olefinic bond was more reactive than the acetylenic one, but the difference was not so large as expected from the electrophilic process. The difference in relative reactivity between the olefinic and polyenic bonds was not so large, either.

为了深入了解生物硝化的机理，过氧亚硝酸盐与某些生物相关模型化合物的反应已投资于缓冲水溶液和乙腈。所采用的化合物包括苯酚，N，N- I二甲基line和活化的烯烃，例如Stilbene，1，4-二苯基丁二烯和1，4-二苯基丁烯。过氧亚硝酸盐是通过在水性合金溶液中用臭氧的叠氮化钠氧化而产生的。酚，并发硝化和羟基化发生在芳环上，产物分布模式显示出典型的亲电性质。副产品包括喹酮和环己二烯。 A^a^ - 二甲基氨酸接受了广泛的脱甲基化，这表明硝基离子作为活性物种参与。 Stilbene提供了苯甲，西尔宾环氧化物和苯甲醛，以及一些环硝化产物。目前尚不清楚碳碳键的氧化清洁机制，因为发现氧化二苯甲酸，1、2-二苯基乙基甲基二醇和二苯基乙醇和二甲醇均被发现对过氧硝酸盐施加惰性。在类似的条件下，二苯基甲甲基甲甲与环硝化产物一起提供了苯兹甲甲甲基的主要产品。奇怪的是，其替代模式只有正骨和元。烯烃键比乙酰基键具有更具反应性，但是差异不如​​亲电过程所预期的那么大。烯烃和多位键之间的相对反应性差异也不那么大。

项目成果

K.Uehata, T.Kawakami, H.Suzuki: "A Straightforward Synthesis of Some Fused Aza-arenes via Nucleophilic Displacement of a Ring Hydrogen Atom in Nitroarenes by Aromatic Hydrazone Anions"J.Chem.Soc., Perkin Trans.I. 696-702 (2002)

K.Uehata、T.Kawakami、H.Suzuki：“通过芳香腙阴离子亲核置换硝基芳烃中的环氢原子，直接合成一些稠合氮杂芳烃”J.Chem.Soc.，Perkin Trans.I.

K.Uehara, T.Kawakanmi, and H.Suzuki: "A Straightforward Synthesis of Some Fused Aza-arenes via Nuclephilic Dispalecement of a Ring Hydroen Atom in Nitroarenes by Aromatic Hydrazone Anions"J. Chem. Soc., Perkin Trans. 696-702. 696-702 (2002)

K.Uehara、T.Kawakanmi 和 H.Suzuki：“通过芳香腙阴离子对硝基芳烃中环氢原子的亲核置换，直接合成一些稠合氮杂芳烃”J。

H.Suzuki, Y.Matano: "Organobismuth Chemistry"Elsevier Science(Amsterdam). 620 (2001)

H.Suzuki，Y.Matano：“有机铋化学”Elsevier Science（阿姆斯特丹）。

N.Nonoyama, H.Oshima, C.Shoda, and H.Suzuki: "The Reaction of Peroxyniteite with Orgaanic Molecules Bearing a Functionality of Biological Significance, The Multipicity of Reaction Modesas Exemplified by Hydroxylation, Nitration, Nitrosation Dealkylation,

N.Nonoyama、H.Oshima、C.Shoda 和 H.Suzuki：“过氧亚硝酸盐与具有生物学意义的功能的有机分子的反应，反应模式的多样性，例如羟基化、硝化、亚硝化、脱烷基化、

H.Peng, H.Suzuki and C.Lu: "Zeolite-assisted Nitration of Neat Toulune and Chlorobenzene with a Nitrogen Dioxide-Molecular Oxygen System.Remarkable Enhancement of para-Selectivity"Tetrahedron Lett. 42. 4357-4359 (2001)

H.Peng、H.Suzuki 和 C.Lu：“用二氧化氮-分子氧系统对纯土鲁恩和氯苯进行沸石辅助硝化。对位选择性的显着增强”Tetrahedron Lett。