8-[chloro(p-tolylsulfinyl)methyl]-8-[(2-trimethylsilyl)ethynyl]-1,4-dioxaspiro[4.5]decane | 1303963-33-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 8-[chloro(p-tolylsulfinyl)methyl]-8-[(2-trimethylsilyl)ethynyl]-1,4-dioxaspiro[4.5]decane
• CAS: 1303963-33-8
• 化学式: C₂₁H₂₉ClO₃SSi
• 分子量: 425.064
• InChiKey: CBHMEEPVTIVWGE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.85
• 重原子数：
  27.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  8-[chloro(p-tolylsulfinyl)methyl]-8-[(2-trimethylsilyl)ethynyl]-1,4-dioxaspiro[4.5]decane 在 异丙基氯化镁 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以99%的产率得到8-[3-(trimethylsilyl)prop-2-yn-1-yliden]-1,4-dioxaspiro[4.5]decane
  参考文献：
  名称：

  以1,2-CC插入和1,2-CH插入类胡萝卜素为关键反应，由酮和醛合成共轭烯炔

  摘要：

  1-氯乙烯基的加成反应p -甲苯基亚砜，这是从酮和氯甲基衍生的p -甲苯基砜，与锂乙炔化物在中等至良好的产率，得到的加合物。用格氏试剂对加合物进行处理，通过生成的镁类马鞭草中间体的1,2-碳-碳插入（1,2-CC插入）反应，以高至高收率形成了共轭烯炔。另一方面，由醛衍生的1-氯乙烯基对甲苯基亚砜与乙炔化锂的加成反应直接得到带有p的共轭烯炔。通过生成的锂类橡胶中间体的1,2-碳-氢插入（1,2-CH插入）反应在1-位上生成-甲苯基亚磺酰基。这些程序为从酮和醛合成多取代的共轭烯炔提供了一个好方法。

  DOI：

  10.1016/j.tet.2011.02.079
• 作为产物：
  描述：

  8-[Chloro-(toluene-4-sulfinyl)-methylene]-1,4-dioxa-spiro[4.5]decane 、 三甲基乙炔基硅 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以77%的产率得到8-[chloro(p-tolylsulfinyl)methyl]-8-[(2-trimethylsilyl)ethynyl]-1,4-dioxaspiro[4.5]decane
  参考文献：
  名称：

  Synthesis of conjugated enynes by assembly of three components, ketones, chloromethyl p-tolyl sulfoxide, and acetylenes, with the magnesium carbenoid 1,2-CC insertion as the key reaction

  摘要：

  The reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from ketones and chloromethyl p-tolyl sulfoxide, with lithium acetylides gave adducts in moderate to good yields. Treatment of the adducts with Grignard reagents resulted in the formation of magnesium carbenoids by the sulfoxide-magnesium exchange reaction. 1,2-Carbon-carbon insertion (1,2-CC insertion) reaction of the generated magnesium carbenoids took place to afford conjugated enynes in good to high yields. This procedure provides a good method for the synthesis of multi-substituted conjugated enynes. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.11.082

文献信息

• Synthesis of conjugated enynes by assembly of three components, ketones, chloromethyl p-tolyl sulfoxide, and acetylenes, with the magnesium carbenoid 1,2-CC insertion as the key reaction
  作者：Hideki Saitoh、Naoyuki Ishida、Tsuyoshi Satoh

  DOI：10.1016/j.tetlet.2009.11.082

  日期：2010.1

  The reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from ketones and chloromethyl p-tolyl sulfoxide, with lithium acetylides gave adducts in moderate to good yields. Treatment of the adducts with Grignard reagents resulted in the formation of magnesium carbenoids by the sulfoxide-magnesium exchange reaction. 1,2-Carbon-carbon insertion (1,2-CC insertion) reaction of the generated magnesium carbenoids took place to afford conjugated enynes in good to high yields. This procedure provides a good method for the synthesis of multi-substituted conjugated enynes. (C) 2009 Elsevier Ltd. All rights reserved.
• Synthesis of conjugated enynes from ketones and aldehydes by 1,2-CC insertion and 1,2-CH insertion of carbenoids as the key reactions
  作者：Naoyuki Ishida、Hideki Saitoh、Simpei Sugiyama、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2011.02.079

  日期：2011.4

  On the other hand, the addition reactions of 1-chlorovinyl p-tolyl sulfoxides derived from aldehydes with lithium acetylides directly gave conjugated enynes bearing a p-tolyl sulfinyl group at the 1-position through the 1,2-carbon–hydrogen insertion (1,2-CH insertion) reaction of the generated lithium carbenoid intermediates. These procedures provide a good way for the synthesis of multi-substituted

  1-氯乙烯基的加成反应p -甲苯基亚砜，这是从酮和氯甲基衍生的p -甲苯基砜，与锂乙炔化物在中等至良好的产率，得到的加合物。用格氏试剂对加合物进行处理，通过生成的镁类马鞭草中间体的1,2-碳-碳插入（1,2-CC插入）反应，以高至高收率形成了共轭烯炔。另一方面，由醛衍生的1-氯乙烯基对甲苯基亚砜与乙炔化锂的加成反应直接得到带有p的共轭烯炔。通过生成的锂类橡胶中间体的1,2-碳-氢插入（1,2-CH插入）反应在1-位上生成-甲苯基亚磺酰基。这些程序为从酮和醛合成多取代的共轭烯炔提供了一个好方法。