5-溴-1-[甲基(二苯基)甲硅烷基]戊-1-酮 | 144692-56-8

• 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
• 中文名称: 5-溴-1-[甲基(二苯基)甲硅烷基]戊-1-酮
• 英文名称: Silane, (5-bromo-1-oxopentyl)methyldiphenyl-
• 英文别名: 5-bromo-1-[methyl(diphenyl)silyl]pentan-1-one
• CAS: 144692-56-8
• 化学式: C₁₈H₂₁BrOSi
• 分子量: 361.354
• InChiKey: PWDWJCYKGUGXDA-UHFFFAOYSA-N

物化性质

• 沸点：
  410.6±37.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.55
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-溴-1-[甲基(二苯基)甲硅烷基]戊-1-酮 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 以81%的产率得到cyclopentyloxy(methyl)diphenylsilane
  参考文献：
  名称：

  Intramolecular free radical cyclizations using acylsilanes as radicalphiles

  摘要：

  Carbon radicals add intramolecularly to acylsilanes at the carbonyl carbon followed by radical Brook rearrangement to give silylated cyclopentanols or cyclohexanols in good yields.

  DOI：

  10.1016/0040-4039(91)80820-v
• 作为产物：
  描述：

  甲基二苯基氯硅烷 在 正丁基锂 、 Celite 、 三氟化硼乙醚 、 mercury(II) oxide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 5-溴-1-[甲基(二苯基)甲硅烷基]戊-1-酮
  参考文献：
  名称：

  The Scope and Limitations of Intramolecular Radical Cyclizations of Acylsilanes with Alkyl, Aryl, and Vinyl Radicals

  摘要：

  5-Exo cyclizations of primary and secondary radicals with acylsilanes successfully give cyclopentyl silyl ethers. The corresponding 6-exo cyclizations are sensitive to changes of the size of silyl groups. Secondary radicals undergo 6-exo cyclizations with acylsilanes more slowly. Reaction of aryl radical with acylsilane proceeds well for 5-exo cyclization but not for 6-exo cyclization. Vinyl radicals give best results in 5-exo cyclizations with acylsilanes but give low yields (similar to 30%) in 6-exo cyclizations. Intramolecular cyclizations of vinyl radicals with acylsilanes give enol silyl ethers regiospecifically.

  DOI：

  10.1021/jo9711302

文献信息

• The Application of Intramolecular Radical Cyclizations of Acylsilanes in the Regiospecific Formation of Cyclic Silyl Enol Ethers
  作者：Chih-Hao Huang、Sheng-Yueh Chang、Nung-Sen Wang、Yeun-Min Tsai

  DOI：10.1021/jo010883s

  日期：2001.12.1

  terminal alpha-stannyl bromide or xanthate functionalities are prepared. Alpha-stannyl radicals generated from these acylsilanes undergo intramolecular cyclizations to give cyclic silyl enol ethers regiospecifically. The radical processes involve radical cyclization, Brook rearrangement, and beta-fragmentation in sequence. A tributylstannyl group serves as the radical leaving group. The newly formed

  制备具有末端α-锡烷基溴或黄原酸酯官能团的酰基硅烷。由这些酰基硅烷产生的α-锡烷基自由基进行分子内环化，以区域特异性地产生环状甲硅烷基烯醇醚。自由基过程依次涉及自由基环化，布鲁克重排和β片段化。三丁基锡烷基用作自由基离去基团。新形成的sigma键和pi键位于相同的两个碳原子之间。这种方法仅限于五元环的形成。在另一种途径中，合成了ω-溴-α-苯基磺酰甲硅烷基硅烷。这些α-磺酰基甲硅烷基硅烷的自由基环化还产生环状甲硅烷基烯醇醚。苯磺酰基部分是该系统中的自由基离去基团。此外，新形成的sigma键和pi键位于共享一个碳原子的相邻位置。后一种方法对于五元和六元环形成均有效。
• α-Sulfenylation of acylsilanes and aldehydes with N-(phenylthio)succinimide
  作者：Chih-Hao Huang、Kang-Shyang Liao、Surya Kanta De、Yeun-Min Tsai

  DOI：10.1016/s0040-4039(00)00515-3

  日期：2000.5

  The reactions of acylsilanes with N-(phenylthio)succinimide in the presence of p-toluenesulfonic acid in acetonitrile give alpha-sulfenylated acylsilanes in good yields. Aldehydes with alpha-alkyl substituent afford moderate yields of alpha-sulfenylated products under the same conditions. (C) 2000 Elsevier Science Ltd. All rights reserved.
• The formation of oxygen-containing heterocycles via intramolecular cyclizations of halo-substituted acylsilanes and unsaturated acylsilanes
  作者：Yeun-Min Tsai、Chaur-Donp Cherng、Hong-Chang Nieh、Jiuen-Ahn Sieh

  DOI：10.1016/s0040-4020(99)00936-9

  日期：1999.12

  Halo-substituted acylsilanes undergo cyclizations easily when heated in a polar solvent such as NMP to afford 2-silyldihydrofurans and 2-silyldihydropyrans. Unsaturated acylsilanes undergo cyclizations through reactions with iodine, phenylselenenyl bromide, or chloride. Further reactions of the cyclized products with pyridinium perbromide, phenylselenenyl bromide, or chloride give highly functionalized dihydrofurans and dihydropyrans. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Cyclizations of functionalized acylsilanes to form 2-silyldihydropyrans and 2-silyldihydrofurans
  作者：Yeun Min Tsai、Hong Chang Nieh、Chaur Donp Cherng

  DOI：10.1021/jo00052a006

  日期：1992.12

  Cyclizations of (delta-haloacyl)- and (gamma-haloacyl)silanes in a polar aprotic solvent gave 2-silyldihydropyrans and 2-silyldihydrofurans in good yields. This new type of cyclization could also be initiated by a carbocation and an olefin.
• Intramolecular free radical cyclizations using acylsilanes as radicalphiles
  作者：Yeun-Min Tsai、Chaur-Donp Cherng

  DOI：10.1016/0040-4039(91)80820-v

  日期：1991.7

  Carbon radicals add intramolecularly to acylsilanes at the carbonyl carbon followed by radical Brook rearrangement to give silylated cyclopentanols or cyclohexanols in good yields.