1,4-cyclohexanedione mono-2,2-dimethyltrimethylene ketal N-tert-butyldimethylsilylhydrazone | 690275-04-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,4-cyclohexanedione mono-2,2-dimethyltrimethylene ketal N-tert-butyldimethylsilylhydrazone
• 英文别名: 9-[[Tert-butyl(dimethyl)silyl]hydrazinylidene]-3,3-dimethyl-1,5-dioxaspiro[5.5]undecane；9-[[tert-butyl(dimethyl)silyl]hydrazinylidene]-3,3-dimethyl-1,5-dioxaspiro[5.5]undecane
• CAS: 690275-04-8
• 化学式: C₁₇H₃₄N₂O₂Si
• 分子量: 326.555
• InChiKey: WPPXUPPOEGBLQI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.28
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  42.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4-cyclohexanedione mono-2,2-dimethyltrimethylene ketal N-tert-butyldimethylsilylhydrazone 在 三乙胺 、 copper(ll) bromide 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以76%的产率得到1,1-dibromo-4-cyclohexanone 2,2-dimethyltrimethylene ketal
  参考文献：
  名称：

  Practical Procedures for the Preparation of N-tert-Butyldimethylsilylhydrazones and Their Use in Modified Wolff−Kishner Reductions and in the Synthesis of Vinyl Halides and gem-Dihalides

  摘要：

  In this work we develop practical chemistry for the preparation of N-tert-butyldimethylsilylhydrazone (TBSH) derivatives from carbonyl-containing compounds and show that these products serve as superior alternatives to simple hydrazones in Wolff-Kishner-type reduction reactions, in the Barton vinyl iodide preparation, in the synthesis of vinyl bromides, and in the synthesis of gem-diiodides, gem-dibromides, and gem-dichlorides. In our new procedure for silyl hydrazone synthesis, aliphatic and aromatic ketones and aldehydes are shown to undergo highly efficient coupling (typically >95% yield) to form the corresponding TBSH derivatives when combined with equimolar amounts of 1,2-bis(tert-butyldimethylsilyl)hydrazine (BTBSH) and a catalytic quantity of scandium trifluoromethanesulfonate (typically, 0.01 mol %), neat, or in solvent. Optimized procedures are provided for the use of TBSH derivatives in a Wolff-Kishner-type reduction protocol that proceeds at low temperature (23-100 degreesC) and in a single reaction flask. Similarly, protocols for the use of TBSH derivatives as precursors to vinyl halides and gem-dihalides are described in detail.

  DOI：

  10.1021/ja049694s
• 作为产物：
  描述：

  1,2-双(叔丁基二甲基硅烷基)肼 、 3,3-二甲基-1,5-二氧杂螺[5.5]十一烷-9-酮 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成 1,4-cyclohexanedione mono-2,2-dimethyltrimethylene ketal N-tert-butyldimethylsilylhydrazone
  参考文献：
  名称：

  用（二氟碘）苯氧化 N-叔丁基二甲基甲硅烷基腙原位生成的重氮烷烃酯化羧酸的一般程序

  摘要：

  羧酸与重氮烷烃形成酯的双分子反应是最温和和最有效的有机转化之一，但除了重要的甲基酯化反应外，很少用于合成。这在很大程度上是由于作为底物的高级重氮烷烃难以接近且稳定性差的结果。在这项工作中，我们描述了一种通过用（二氟碘）苯氧化 N-叔丁基二甲基甲硅烷基腙 (TBSH) 来合成重氮烷烃的新方法，这是一种迄今为止未在腙氧化的背景下探索的试剂。当在羧酸底物存在下进行时，氧化导致有效的原位酯化。除了大大扩展了现在可用于酯化的重氮烷烃的范围之外，

  DOI：

  10.1021/ja0459779

文献信息

• A General Procedure for the Esterification of Carboxylic Acids with Diazoalkanes Generated in Situ by the Oxidation of <i>N</i>-<i>tert</i>-Butyldimethylsilylhydrazones with (Difluoroiodo)benzene
  作者：Michael E. Furrow、Andrew G. Myers

  DOI：10.1021/ja0459779

  日期：2004.10.1

  bimolecular reaction of carboxylic acids with diazoalkanes to form esters is among the mildest and most efficient of organic transformations but is seldom used in synthesis beyond the important case of methyl esterification. This is largely a consequence of the inaccessibility and poor stability of higher diazoalkanes as substrates. In this work we describe a new method for the synthesis of diazoalkanes by

  羧酸与重氮烷烃形成酯的双分子反应是最温和和最有效的有机转化之一，但除了重要的甲基酯化反应外，很少用于合成。这在很大程度上是由于作为底物的高级重氮烷烃难以接近且稳定性差的结果。在这项工作中，我们描述了一种通过用（二氟碘）苯氧化 N-叔丁基二甲基甲硅烷基腙 (TBSH) 来合成重氮烷烃的新方法，这是一种迄今为止未在腙氧化的背景下探索的试剂。当在羧酸底物存在下进行时，氧化导致有效的原位酯化。除了大大扩展了现在可用于酯化的重氮烷烃的范围之外，
• Practical Procedures for the Preparation of <i>N</i>-<i>tert</i>-Butyldimethylsilylhydrazones and Their Use in Modified Wolff−Kishner Reductions and in the Synthesis of Vinyl Halides and <i>g</i><i>em</i>-Dihalides
  作者：Michael E. Furrow、Andrew G. Myers

  DOI：10.1021/ja049694s

  日期：2004.5.1

  In this work we develop practical chemistry for the preparation of N-tert-butyldimethylsilylhydrazone (TBSH) derivatives from carbonyl-containing compounds and show that these products serve as superior alternatives to simple hydrazones in Wolff-Kishner-type reduction reactions, in the Barton vinyl iodide preparation, in the synthesis of vinyl bromides, and in the synthesis of gem-diiodides, gem-dibromides, and gem-dichlorides. In our new procedure for silyl hydrazone synthesis, aliphatic and aromatic ketones and aldehydes are shown to undergo highly efficient coupling (typically >95% yield) to form the corresponding TBSH derivatives when combined with equimolar amounts of 1,2-bis(tert-butyldimethylsilyl)hydrazine (BTBSH) and a catalytic quantity of scandium trifluoromethanesulfonate (typically, 0.01 mol %), neat, or in solvent. Optimized procedures are provided for the use of TBSH derivatives in a Wolff-Kishner-type reduction protocol that proceeds at low temperature (23-100 degreesC) and in a single reaction flask. Similarly, protocols for the use of TBSH derivatives as precursors to vinyl halides and gem-dihalides are described in detail.