trans-di-O-tert-amylhyponitrite | 85972-35-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-di-O-tert-amylhyponitrite
• 英文别名: (E)-bis(2-methylbutan-2-yloxy)diazene
• CAS: 85972-35-6
• 化学式: C₁₀H₂₂N₂O₂
• 分子量: 202.297
• InChiKey: ZHMWMZDQZVBQDR-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-氯代-2-甲基丁烷 在 trans-sodium hyponitrite 、 三氯化铁 作用下， 以 乙醚 为溶剂， 反应 0.33h， 以60%的产率得到trans-di-O-tert-amylhyponitrite
  参考文献：
  名称：

  刘易斯酸催化亚硫酸氢根离子与卤代烷的反应

  摘要：

  在弱路易斯酸的存在下，钠和其他无机反亚硫酸氢盐可从相应的烷基溴化物或氯化物以良好的收率得到叔烷基次亚硝酸盐。

  DOI：

  10.1016/s0040-4039(00)81434-3

文献信息

• Correlation of the Product E/Z Framework Geometry and O/O vs O/N Regioselectivity in the Dialkylation of Hyponitrite
  作者：Navamoney Arulsamy、D. Scott Bohle、Jerome A. Imonigie、Elizabeth S. Sagan

  DOI：10.1021/ja994261o

  日期：2000.6.1

  The products from the alkylation of silver hyponitrite with tert-butyl bromide, tert-amyl bromide, p-tert-butyl benzylbromide, and chlorotriethylsilane have been determined. In the reaction of tert-butyl bromide the formation of three new products, namely, (Z)-N-tert-butyl-N'-tert-butoxydiazene-N-oxide (CH3)(3)CN(O)NOC(CH3)(3)}, 1D, trans-mono-O-tert-butylhyponitrous acid (CH3)(3)CONNOH}, 2A, and (Z)-N-tert-butyl-N'-hydroxydiazene-N-oxide (CH3)(3)CN(O)NNQH}, 2D, is observed together with the formation of the known trans-di-O-tert-butyl hyponitrite (CH3)(3)CONNOC(CH3)(3)}, 1A. The reaction with tert-amyl bromide also yielded the corresponding tert-amyl derivatives. However, from the reactions of p-tert-butylbenzyl bromide and chlorotriethylsilane with silver hyponitrite, the corresponding trans-di-O-tert-alkylhyponitrites were obtained as the only alkylated products. The differential reactivity of the two sets of halides with silver hyponitrite is explained in terms of the higher stability of the cations generated from the former halides in comparison to those generated from the latter halides. The thermal decomposition data and UV-visible spectroscopic data are reported for all of the products. Crystallographic structural data are reported for two of the products, namely, Q-N-tert-butyl-K-tert-butoxydiazene-N-ox, 1D, as its hyponitrous acid adduct, (CH3)(3)CN(O)NOC(CH3)(3). 1/2HONNOH, and trans-di-O-p-tert-butylbenzyl hyponitrite, p(CH3)(3)C}C6H4CH2ONNOCH2C6H4-p-C(CH3)(3)}. Theoretical calculations using ab initio density functional theory (B3LYP) are reported for the hyponitrite dianion, trans-mono-O-methylhyponitrite anion, (Z)-N-methyl-N'-hydroxylatodiazene-N-oxid anion, and for the methylation transition states. On the basis of the products isolated from the reactions of tert-butyl bromide and tert-amyl bromide and the theoretical calculations, a pathway is proposed to account for the observed product distributions where O/O-dialkylation is found in the trans(E) products and O/N-dialkylation is found in the cis(Z) products.
• The lewis acid catalyzed reaction of -hyponitrite ion with alkyl halides
  作者：G. David Mendenhall

  DOI：10.1016/s0040-4039(00)81434-3

  日期：1983.1

  Sodium and other inorganic trans-hyponitrites afford tert-alkyl hyponitrites in good yield from the corresponding alkyl bromide or chloride in the presence of weak Lewis acids.

  在弱路易斯酸的存在下，钠和其他无机反亚硫酸氢盐可从相应的烷基溴化物或氯化物以良好的收率得到叔烷基次亚硝酸盐。