N,N-bis(trimethylsilyloxy)-1E-propen-1-amine | 102588-20-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: N,N-bis(trimethylsilyloxy)-1E-propen-1-amine
• 英文别名: (E)-N-(prop-1-en-1-yl)-O-(trimethylsilyl)-N-((trimethylsilyl)oxy)hydroxylamine；(E)-N,N-bis(trimethylsilyloxy)prop-1-en-1-amine
• CAS: 102588-20-5
• 化学式: C₉H₂₃NO₂Si₂
• 分子量: 233.458
• InChiKey: GKWZSCMIYUHNIH-CMDGGOBGSA-N

物化性质

• 沸点：
  200.9±23.0 °C(Predicted)
• 密度：
  0.890±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N,N-bis(trimethylsilyloxy)-1E-propen-1-amine 在 溴 、 四丁基醋酸铵 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到(1E)-1-硝基-1-丙烯
  参考文献：
  名称：

  N，N-双（甲硅烷氧基）烯胺中间体的卤代反应由硝基烷烃新型合成α-硝基烯烃

  摘要：

  描述了在乙酸四正丁铵存在下通过用溴或碘氧化N，N-双（甲硅烷氧基）烯胺来共轭硝基烯烃的方法。乙酸根离子通过充当温和的去甲硅烷基化试剂发挥关键作用。该新策略允许从相应的硝基烷烃合成α-硝基烯烃。

  DOI：

  10.1016/j.tetlet.2005.05.113
• 作为产物：
  描述：

  三甲基溴硅烷 、 硝基丙烷 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 72.25h， 以85%的产率得到N,N-bis(trimethylsilyloxy)-1E-propen-1-amine
  参考文献：
  名称：

  通过[4 + 1]-环合成战略从硝基烷烃合成异恶唑啉

  摘要：

  利用由脂肪族硝基化合物衍生的N，N-双（甲硅烷氧基）烯胺与α-酮稳定的硫基化合物的[4 + 1]-环化反应，开发了一种新型的异恶唑啉通道。通过一锅催化的N-O氢解/分子内还原胺化序列显示，所得的5-酮基取代的异恶唑啉是多取代的3-羟基吡咯烷的便​​利前体。证明了该方法在默克强力NK 1受体拮抗剂正式合成中的应用。

  DOI：

  10.1002/adsc.201901000

文献信息

• Novel Convenient Method for the Synthesis of N,N-Bis(trimethylsilyloxy)enamines
  作者：A. D. Dilman、A. A. Tishkov、I. M. Lyapkalo、S. L. Ioffe、Yu. A. Strelenko、V. A. Tartakovsky

  DOI：10.1055/s-1998-2019

  日期：1998.2

  Both primary and secondary aliphatic nitro compounds 1 were found to react with two equivalents of bromotrimethylsilane in the presence of triethylamine followed by aqueous workup to give appropriate N,N-bis(trimethylsilyloxy)enamines 3 in good isolated yields. Products 3, starting from some secondary and/or sterically hindered compounds 1, are synthesized from the corresponding silyl nitronates 2.

  研究发现，无论是伯还是仲的脂肪族硝基化合物1都能在三乙胺的存在下，与两当量的溴三甲基硅烷反应，然后通过水洗处理，以良好的产率得到相应的N,N-双(三甲基硅氧基)烯胺3。从某些仲和/或空间位阻的化合物1出发，产物3是通过相应的硅基硝酸盐2合成的。
• The Chemistry of<i>N</i>,<i>N</i>-Bis(siloxy)enamines. Part 8.A General Method for the Preparation of α-Azido Oximes from Aliphatic Nitro Compounds
  作者：Alexey V. Lesiv、Sema L. Ioffe、Alexey Yu. Sukhorokov、Igor V. Bliznets、Yulija A. Khomutova、Yuriy A. Strelenko

  DOI：10.1055/s-2005-861836

  日期：——

  A new convenient procedure for the preparation of a variety of α-hydroxy oximes from available aliphatic nitro compounds via intermediate N,N-bis(siloxy)enamines is presented. The mechanism of the key step, the rearrangement of N,N-bis(siloxy)en­amines, is discussed.

  介绍了一种通过中间体 N,N-双（硅氧基）烯胺从可用的脂肪族硝基化合物制备各种 α-羟基肟的新简便方法。讨论了关键步骤，N,N-双（甲硅烷氧基）烯胺重排的机理。
• Reactions of N,N-bis(silyloxy)enamines with sulfur-centered and sulfur-stabilised electrophiles
  作者：Aleksei V. Ustinov、Alexander D. Dilman、Sema L. Ioffe、Yuri A. Strelenko、William A. Smit、Vladimir A. Tartakovsky

  DOI：10.1070/mc2003v013n02abeh001720

  日期：2003.1

  The coupling of N,N-bis(silyloxy)enamines with arylsulfenyl chlorides and episulfonium cations proceeds as an electrophilic attack at the β-carbon atoms of N,N-bis(silyloxy)enamines and affords functionalised aliphatic compounds.

  N，N-双（甲硅烷氧基）烯胺与芳基亚硫酰氯和epi基阳离子的偶联以亲电方式在N，N-双（甲硅烷氧基）烯胺的β-碳原子上进攻，并提供官能化的脂肪族化合物。
• Chemistry of N,N-bis(silyloxy)enamines 7. Quaternization of tertiary amines and nitrogen-containing heterocycles by N,N-bis(silyloxy)enamines
  作者：A. V. Lesiv、S. L. Ioffe、Yu. A. Strelenko、V. M. Danilenko

  DOI：10.1007/s11172-005-0106-x

  日期：2004.10

  Coupling of N,N-bis(silyloxy)enamines with tertiary amines and nitrogen-containing heterocycles affording the corresponding functionalized ammonium or iminium salts was studied. The area of its application was determined, and optimal procedures for the synthesis of the target products were proposed. The mechanism including the formation of conjugated nitroso alkene or a silylnitrosonium cation as key

  研究了 N,N-双 (甲硅烷氧基) 烯胺与叔胺和含氮杂环的偶联，以提供相应的功能化铵盐或亚胺盐。确定了其应用领域，并提出了合成目标产物的最佳程序。讨论了形成共轭亚硝基烯烃或甲硅烷基亚硝基阳离子作为关键中间体的机制。
• Chemistry of N,N-Bis(silyloxy)enamines, Part 5
  作者：Alexey V. Lesiv、Sema L. Ioffe、Yury A. Strelenko、Vladimir A. Tartakovsky

  DOI：10.1002/1522-2675(200210)85:10<3489::aid-hlca3489>3.0.co;2-6

  日期：2002.10

  Aliphatic nitro compounds can be considered as good precursors of a wide variety of alpha-azolyl-substituted oximes. The double silylation of convenient aliphatic nitro compounds and the subsequent N,C-coupling of the resulting N,N-bis(silyloxy)enamines 3 with N-silylated azoles 4 lead to the formation of the silylated alpha-azolyl-substituted oximes 6, which can be smoothly desilylated to give the target a-azolyl-substituted oximes 5. The mechanism of the key step of this process -N,C-coupling - includes the generation of corresponding conjugated nitrosoalkenes 7 (Schemes 4 and 5). The contribution of the chain mechanism in the overall process is considered as well. The studies of the scope and limitations of this reaction, as well as the optimization of its conditions were accomplished. The configuration of the C=N bond in oximes was established by NMR.