2-allyl 2-adamantanethiocarbaldehyde oxide | 99097-39-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代羰基化合物
• 英文名称: 2-allyl 2-adamantanethiocarbaldehyde oxide
• 英文别名: (Z)-2-allyl 2-adamantanethiocarbaldehyde oxide；(E)-2-allyl 2-adamantanethiocarbaldehyde oxide；2-Prop-2-enyl-2-(sulfinylmethyl)adamantane
• CAS: 99097-39-9
• 化学式: C₁₄H₂₀OS
• 分子量: 236.378
• InChiKey: CJOPUPLBFYIQIT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  18.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-allyl 2-adamantanethiocarbaldehyde oxide 在 三氟化硼乙醚 、 mercury(II) oxide 作用下， 以 四氢呋喃 、 水 为溶剂， 以77%的产率得到2-Allyladamantane-2-carboxaldehyde
  参考文献：
  名称：

  亚硫酸盐化学。12. 1-烯基 2-烯基亚砜的异常简便的硫代-克莱森重排：一种新的亚砜合成

  摘要：

  L'oxydation des allylvinylvinylsulfes en leurs sulfoxydes 通讯员管道 a une 加速 remarquable de la vitesse de processus sigmatrope [3+3], conduisant a des sulfines isolables pouvant etre converties en les composes carbonyles dans des conditions douces

  DOI：

  10.1021/ja00309a063
• 作为产物：
  描述：

  2-(Prop-2-ene-1-sulfinylmethylene)-adamantane 反应 2.0h， 生成 2-allyl 2-adamantanethiocarbaldehyde oxide
  参考文献：
  名称：

  Electronic control of face selection in the [3,3] sigmatropic rearrangement of allyl vinyl sulfoxides

  摘要：

  A study has been made of the thermal rearrangement of adamantylidenemethyl allyl sulfoxide 4 as well as of the racemic RR,SS and RS,SR 5-fluoro diastereomers 8 at 80-degrees-C. The parent compound 4 initially gives a mixture of the (E)- and (Z)-sulfines 5; the E product subsequently isomerizes, more slowly but completely, to the Z compound. Under the same conditions, mixtures of the diastereomers 8 produce mixtures of four mesoforms, two of which ((EE)- and (ZE)-9) subsequently rearrange further to the other two ((EZ)- and (ZZ)-9). The configurations of the starting materials and products were determined by NMR methods. A study of the rates of these various processes made it possible to define the compositions of the sulfine mixtures that form initially from sulfoxides 8. The conclusion is that both a steric and an electronic effect are operating simultaneously to influence the stereochemistry. The steric effect is a response to the need to avoid axial oxygen in the pseudo-chair transition state; the electronic effect favors the formation of a CC bond antiperiplanar to the more electron-rich vicinal bonds. As was the case in the oxy-Cope reaction studied earlier, the steric effect is the larger of the two by a small margin.

  DOI：

  10.1021/jo00037a031

文献信息

• BLOCK, E.;AHMAD, S., J. AMER. CHEM. SOC., 1985, 107, N 23, 6731-6732
  作者：BLOCK, E.、AHMAD, S.

  DOI：——

  日期：——
• Chemistry of sulfines. 12. Unusually facile thio-Claisen rearrangement of 1-alkenyl 2-alkenyl sulfoxides: a new sulfine synthesis
  作者：Eric Block、Saleem Ahmad

  DOI：10.1021/ja00309a063

  日期：1985.11

  L'oxydation des allyl vinyl sulfures en leurs sulfoxydes correspondants conduit a une acceleration remarquable de la vitesse de processus sigmatrope [3+3], conduisant a des sulfines isolables pouvant etre converties en les composes carbonyles dans des conditions douces

  L'oxydation des allylvinylvinylsulfes en leurs sulfoxydes 通讯员管道 a une 加速 remarquable de la vitesse de processus sigmatrope [3+3], conduisant a des sulfines isolables pouvant etre converties en les composes carbonyles dans des conditions douces
• Electronic control of face selection in the [3,3] sigmatropic rearrangement of allyl vinyl sulfoxides
  作者：Ashis Mukherjee、Edward M. Schulman、William J. Le Noble

  DOI：10.1021/jo00037a031

  日期：1992.5

  A study has been made of the thermal rearrangement of adamantylidenemethyl allyl sulfoxide 4 as well as of the racemic RR,SS and RS,SR 5-fluoro diastereomers 8 at 80-degrees-C. The parent compound 4 initially gives a mixture of the (E)- and (Z)-sulfines 5; the E product subsequently isomerizes, more slowly but completely, to the Z compound. Under the same conditions, mixtures of the diastereomers 8 produce mixtures of four mesoforms, two of which ((EE)- and (ZE)-9) subsequently rearrange further to the other two ((EZ)- and (ZZ)-9). The configurations of the starting materials and products were determined by NMR methods. A study of the rates of these various processes made it possible to define the compositions of the sulfine mixtures that form initially from sulfoxides 8. The conclusion is that both a steric and an electronic effect are operating simultaneously to influence the stereochemistry. The steric effect is a response to the need to avoid axial oxygen in the pseudo-chair transition state; the electronic effect favors the formation of a CC bond antiperiplanar to the more electron-rich vicinal bonds. As was the case in the oxy-Cope reaction studied earlier, the steric effect is the larger of the two by a small margin.