氧化亚氮-15N同位素 | 20509-24-4

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 其他非金属有机物
• 中文名称: 氧化亚氮-15N同位素
• 中文别名: 氧化亚氮-15N
• 英文名称: (14,15)NO
• CAS: 20509-24-4
• 化学式: N₂O
• 分子量: 45.0061
• InChiKey: GQPLMRYTRLFLPF-VQEHIDDOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  19.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  [(15)N]nitrosyl iron tetraphenyl porphine 、 氧化亚氮 在 三苯基膦 作用下， 以 氯仿 为溶剂， 生成 氧化亚氮-15N同位素
  参考文献：
  名称：

  O Atom Transfer from Nitric Oxide Catalyzed by Fe(TPP)

  摘要：

  The reaction of NO-Fe(TPP) with low pressures of NO gas proceeds through three distinct transformations, the first of which we suggest is the formation of an N-N-coupled, (NO)(2) adduct intermediate. The subsequent formation of NO(NO2)Fe(TPP), which under these conditions readily loses NO, suggests that it is formed by addition of free NO2 to the starting nitrosyl, A mechanism is proposed which implies that the addition of a competitive O atom acceptor would lead to catalytic production of N2O. In agreement with the proposed mechanism, the formation of N2O is decoupled from the formation of the nitrite by using PPh3 as the competitive acceptor. The mechanism of O atom transfer was examined by cross-labeling experiments, which show that both O atoms in the intermediate are equivalent, even under catalytic conditions. The formation of an intermediate was confirmed by IR spectroscopy of the heterogeneous reaction of an NO:Fe(TPP) film with gaseous NO, in which transient, isotope-sensitive nu (NO) bands are seen prior to NO(NO2)Fe(TPP) formation. Mixed N-14/N-15 label experiments demonstrate coupling between the two bound nitrosyls in the transient species.

  DOI：

  10.1021/ja993643r

文献信息

• Lewis Acid Activation of the Ferrous Heme–NO Fragment toward the N–N Coupling Reaction with NO To Generate N₂O
  作者：Erwin G. Abucayon、Rahul L. Khade、Douglas R. Powell、Yong Zhang、George B. Richter-Addo

  DOI：10.1021/jacs.7b13681

  日期：2018.3.28

  (OEP)Fe(NO) activates it toward N-N bond formation with NO to generate N2O. 15N-isotopic labeling reveals a reversible nitrosyl exchange reaction and follow-up N-O bond cleavage in the N2O formation step. Other Lewis acids (B(C6F5)3 and K+) also promote the NO coupling reaction with (OEP)Fe(NO). These results, complemented by DFT calculations, provide experimental support for the cis: b3 pathway in bacNOR

  细菌 NO 还原酶 (bacNOR) 酶利用血红素/非血红素活性位点将两个 NO 分子与 N2O 偶联。我们表明，BF3 与 (OEP)Fe(NO) 中亚硝酰基 O 原子的配位将其激活，使其与 NO 形成 NN 键以生成 N2O。15N 同位素标记揭示了在 N2O 形成步骤中可逆的亚硝酰基交换反应和后续的 NO 键断裂。其他路易斯酸（B(C6F5)3 和 K+）也促进 NO 与 (OEP)Fe(NO) 的偶联反应。这些结果与 DFT 计算相辅相成，为 bacNOR 中的 cis: b3 通路提供了实验支持。
• Carbon–Nitrogen and Nitrogen–Nitrogen Bond Formation from Nucleophilic Attack at Coordinated Nitrosyls in Fe and Ru Heme Models
  作者：Erwin G. Abucayon、Douglas R. Powell、George B. Richter-Addo

  DOI：10.1021/jacs.7b05209

  日期：2017.7.19

  whereas the reaction with azide results in N2O formation; these products derive from attack of the nucleophiles on the bound NO groups. These results provide the first demonstrations of C–N and N–N bond formation from attack of C-based and N-based nucleophiles on synthetic ferric-NO hemes.

  无机NO x物种向有机N化合物的转化是全球N循环的重要组成部分。C型亲核试剂即苯基阴离子与亚铁血红素亚硝酰基[（OEP）Fe（NO）（5-MeIm）] +的反应生成C-亚硝基衍生物（OEP）Fe（PhNO）（ 5-MeIm）和（OEP）Fe（Ph）。与[（OEP）Ru（NO）（5-MeIm）] +的相关反应生成（OEP）Ru（PhNO）（5-MeIm）产物。与基于N的亲核试剂二乙酰胺的反应导致游离二乙基亚硝胺的形成，而与叠氮化物的反应导致N 2O形成；这些产物源自亲核试剂对结合的NO基团的攻击。这些结果首次证明了基于C和N的亲核试剂对合成三价铁血红素的攻击形成了C–N和N–N键。
• Serendipitous Synthesis of (<i>tert</i>-Butyl-<i>NNO</i>-azoxy)acetonitrile: Reduction of an Oxime Moiety to a Methylene Unit
  作者：Michael S. Klenov、Oleg V. Anikin、Alexey A. Guskov、Aleksandr M. Churakov、Yurii A. Strelenko、Ivan V. Ananyev、Ivan S. Bushmarinov、Artem O. Dmitrienko、Konstantin A. Lyssenko、Vladimir A. Tartakovsky

  DOI：10.1002/ejoc.201600584

  日期：2016.8

  (tert-Butyl-NNO-azoxy)acetonitrile (1) is a useful precursor for a number of nitrogen heterocycles. It was found that it could be obtained in good yield by treatment of the salts of (tert-butyl-NNO-azoxy)(hydroxyimino)acetonitrile with NH2OTs. It is the first case of one-step reduction of an oxime group to a methylene unit using an aminating agent. A plausible reaction mechanism is proposed. In addition

  （叔丁基-NNO-偶氮氧基）乙腈 (1) 是许多氮杂环的有用前体。发现通过用NH2OTs处理(叔丁基-NNO-偶氮氧基)(羟基亚氨基)乙腈的盐可以以良好的收率获得它。这是第一个使用胺化剂将肟基团一步还原为亚甲基单元的案例。提出了一个合理的反应机制。此外，还开发了四唑 1-氧化物环结构的新策略。这涉及重氮基团转移到化合物 1 的活性亚甲基单元，然后是偶氮基和重氮基团的分子内偶联。通过X射线衍射分析证实了四唑结构。
• Nickel-mediated N–N bond formation and N₂O liberation <i>via</i> nitrogen oxyanion reduction
  作者：Daniel M. Beagan、Alyssa C. Cabelof、Maren Pink、Veronica Carta、Xinfeng Gao、Kenneth G. Caulton

  DOI：10.1039/d1sc02846d

  日期：——

  The syntheses of (DIM)Ni(NO3)2 and (DIM)Ni(NO2)2, where DIM is a 1,4-diazadiene bidentate donor, are reported to enable testing of bis boryl reduced N-heterocycles for their ability to carry out stepwise deoxygenation of coordinated nitrate and nitrite, forming O(Bpin)2. Single deoxygenation of (DIM)Ni(NO2)2 yields the tetrahedral complex (DIM)Ni(NO)(ONO), with a linear nitrosyl and κ1-ONO. Further

  据报道，(DIM)Ni(NO 3 ) 2和 (DIM)Ni(NO 2 ) 2的合成（其中 DIM 是 1,4-二氮杂二烯二齿供体）能够测试双硼基还原的 N-杂环的能力进行配位硝酸盐和亚硝酸盐的逐步脱氧，形成O(Bpin) 2。(DIM)Ni(NO 2 ) 2 的单次脱氧产生具有线性亚硝酰基和κ 1 -ONO的四面体配合物(DIM)Ni(NO)(ONO) 。(DIM)Ni(NO)(ONO) 的进一步脱氧导致二聚体 [(DIM)Ni(NO)] 2 的形成，其中二聚体通过 Ni-Ni 键连接。损失的还原氮副产物显示为 N 2O，表示在反应过程中形成 N-N 键。同位素标记研究表明，N 2 O的 N-N 键是在双金属 Ni 2中间体中形成的，并且 (DIM)Ni(NO)(ONO) 的两个氮原子在 N-N 键形成之前变得对称。[(DIM)Ni(NO)] 2二聚体容易被AgX（X = NO 3 -、NO
• Catalytic Decomposition of Ammonium Nitrate in Superheated Aqueous Solutions
  作者：Joseph H. MacNeil、Hai-Tao Zhang、Polly Berseth、William C. Trogler

  DOI：10.1021/ja971618k

  日期：1997.10.1

  The decomposition of aqueous ammonium nitrate at elevated temperatures and pressures is examined as a function of chloride, nitrate, and total acidity. Catalysis requiring both chloride and acid wa...

  硝酸铵水溶液在升高的温度和压力下的分解被检查为氯化物、硝酸盐和总酸度的函数。需要氯化物和酸液的催化...