trimethyl(9-methyl-9,10-dihydroanthracen-9-yl)silane | 68573-95-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: trimethyl(9-methyl-9,10-dihydroanthracen-9-yl)silane
• 英文别名: 9-(trimethylsilyl)-9-methyl-9,10-dihydroanthracene；9-Trimethylsilyl-9-methyl-9,10-dihydroanthracen；trimethyl-(9-methyl-10H-anthracen-9-yl)silane
• CAS: 68573-95-5
• 化学式: C₁₈H₂₂Si
• 分子量: 266.458
• InChiKey: VVHGYXNDCBRJQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  trimethyl(9-methyl-9,10-dihydroanthracen-9-yl)silane 在 正丁基锂 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 生成 9-Benzyl-9,10-dimethyl-9,10-dihydroanthracene
  参考文献：
  名称：

  A convenient synthesis of 9,9-dialkyl-9,10-dihydroanthracenes and 10,10-dialkylanthrones: silicon-mediated regioselective dialkylation of 9,10-dihydroanthracene

  摘要：

  Described is a short and convenient approach to the synthesis of 9,9-dialkyl-9,10-dihydroanthracenes, 9,9,10-trialkyl-9,10-dihydroanthracenes, and 10,10-dialkylanthrones, some of which are otherwise unknown or inaccessible by conventional methods. Deprotonation of 9-(trimethylsilyl)-9,10-dihydroanthracene (2; 9-(trimethylsilyl)-9,10-DHA) followed by reaction with alkyl halides (RX) produces 9-alkyl-9-(trimethylsilyl)-9,10-DHAs 3-7 in 80-90% yields. Treatment of 3-7 with n-BuLi produces the 10-lithio derivatives that rearrange to 9-alkyl-9-lithio-10-(trimethylsilyl) intermediates; subsequent alkylation with RX generates 9,9-dialkyl-10-(trimethylsilyl)-9,10-DHAs 8-19. Formation of single stereoisomers 13-19 was suggested by NMR and confirmed in two cases, 15 and 16, by X-ray structure determination. The trimethylsilyl group is removed by tetra-butlyammonium fluoride (TBAF) to provide 9,9-dialkyl-9,10-DHAs 20-29 with impressive yields. Oxidation of either the 9,9-dialkyl-9,10-DHAs or 9,9-dialkyl-10-(trimethylsilyl)-9,10-DHAs with Cr(VI) oxidant furnished 10,10-dialkylanthrones 36-41 in 80-90% yields.

  DOI：

  10.1021/jo00036a029
• 作为产物：
  描述：

  9,10-二氢蒽 在 正丁基锂 作用下， 反应 1.5h， 生成 trimethyl(9-methyl-9,10-dihydroanthracen-9-yl)silane
  参考文献：
  名称：

  9,10-二氢蒽系统中的硅介导的烷基化：9,9-二烷基-9,10-二氢蒽的便捷合成。

  摘要：

  三甲基甲硅烷基（TMS）取代基用于控制提供9,9-二烷基-10-TMS-9,10-DHA的9,10-二氢蒽（9,10-DHA）中烷基化的区域化学。随后除去TMS基团，从而以高产率至优异产率首次方便地合成各种9,9-二烷基-9,10-DHA。

  DOI：

  10.1016/0040-4039(91)80602-3

文献信息

• Silylated Cyclohexadienes as New Radical Chain Reducing Reagents:  Preparative and Mechanistic Aspects
  作者：Armido Studer、Stephan Amrein、Florian Schleth、Tobias Schulte、John C. Walton

  DOI：10.1021/ja0341743

  日期：2003.5.1

  superior tin hydride substitutes for the conduction of various radical chain reductions. Debrominations, deiodinations, and deselenations can be performed using these environmentally benign reagents. Furthermore, Barton-McCombie-type deoxygenations using silylated cyclohexadienes are described. Radical cyclizations, ring expansions, and Giese-type addition reactions with the new tin hydride substitutes

  各种甲硅烷基化的 1,4-环己二烯作为优良的氢化锡替代物，可用于各种自由基链还原的传导。可以使用这些环境友好的试剂进行脱溴、脱碘和脱硒。此外，还描述了使用甲硅烷基化环己二烯的 Barton-McCombie 型脱氧作用。介绍了与新的氢化锡替代物的自由基环化、扩环和 Giese 型加成反应。苯乙烯的聚合可以使用甲硅烷基化的环己二烯进行调节。测定了通过初级 C-自由基从两个 1-甲硅烷基-环己二烯中提取氢原子的速率常数。讨论了环己二烯取代基对反应结果的影响。最后，
• Silicon Mediated Alkylations in the 9,10-Dihydroanthracene System: a Convenient Synthesis of 9,9-Dialkyl-9,10- Dihydroanthracenes.
  作者：Peter W. Rabideau、R.K. Dhar、D.K. Clawson、Zhengyun Zhan

  DOI：10.1016/0040-4039(91)80602-3

  日期：1991.8

  A trimethylsilyl (TMS) substituent is used to control the regiochemistry of alkylation in 9,10-dihydroanthracene (9,10-DHA) furnishing 9,9-dialkyl-10-TMS-9,10-DHAs. The TMS group is subsequently removed resulting in the first convenient synthesis of a variety of 9,9-dialkyl-9,10-DHAs in good to excellent yields.

  三甲基甲硅烷基（TMS）取代基用于控制提供9,9-二烷基-10-TMS-9,10-DHA的9,10-二氢蒽（9,10-DHA）中烷基化的区域化学。随后除去TMS基团，从而以高产率至优异产率首次方便地合成各种9,9-二烷基-9,10-DHA。
• Reactivity of benzylic carbanions. 10. [1,4]-Rearrangement of the trimethylsilyl group in 9,9-bis(trimethylsilyl)- and 9-alkyl-9-(trimethylsilyl)-10-lithio-9,10-dihydroanthracenes
  作者：Michele Daney、Rene Lapouyade、Henri Bouas-Laurent

  DOI：10.1021/jo00173a052

  日期：1983.12
• DANEY, M.;LAPOUYADE, R.;BOUAS-LAURENT, H., J. ORG. CHEM., 1983, 48, N 25, 5055-5062
  作者：DANEY, M.、LAPOUYADE, R.、BOUAS-LAURENT, H.

  DOI：——

  日期：——
• A convenient synthesis of 9,9-dialkyl-9,10-dihydroanthracenes and 10,10-dialkylanthrones: silicon-mediated regioselective dialkylation of 9,10-dihydroanthracene
  作者：Raj K. Dhar、D. K. Clawson、Frank R. Fronczek、Peter W. Rabideau

  DOI：10.1021/jo00036a029

  日期：1992.5

  Described is a short and convenient approach to the synthesis of 9,9-dialkyl-9,10-dihydroanthracenes, 9,9,10-trialkyl-9,10-dihydroanthracenes, and 10,10-dialkylanthrones, some of which are otherwise unknown or inaccessible by conventional methods. Deprotonation of 9-(trimethylsilyl)-9,10-dihydroanthracene (2; 9-(trimethylsilyl)-9,10-DHA) followed by reaction with alkyl halides (RX) produces 9-alkyl-9-(trimethylsilyl)-9,10-DHAs 3-7 in 80-90% yields. Treatment of 3-7 with n-BuLi produces the 10-lithio derivatives that rearrange to 9-alkyl-9-lithio-10-(trimethylsilyl) intermediates; subsequent alkylation with RX generates 9,9-dialkyl-10-(trimethylsilyl)-9,10-DHAs 8-19. Formation of single stereoisomers 13-19 was suggested by NMR and confirmed in two cases, 15 and 16, by X-ray structure determination. The trimethylsilyl group is removed by tetra-butlyammonium fluoride (TBAF) to provide 9,9-dialkyl-9,10-DHAs 20-29 with impressive yields. Oxidation of either the 9,9-dialkyl-9,10-DHAs or 9,9-dialkyl-10-(trimethylsilyl)-9,10-DHAs with Cr(VI) oxidant furnished 10,10-dialkylanthrones 36-41 in 80-90% yields.