5-fluoroadamantane-2-thione | 117371-13-8

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: 5-fluoroadamantane-2-thione
• 英文别名: 5-Fluoro-2-adamantanethione
• CAS: 117371-13-8
• 化学式: C₁₀H₁₃FS
• 分子量: 184.278
• InChiKey: UFOBTUFWORLQEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-fluoroadamantane-2-thione 、 benzohydroximoyl chloride 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 、
  参考文献：
  名称：

  Face Selectivity in the 1,3-Dipolar Cycloaddition Reactions of Benzonitrile Oxide with 5-Substituted Adamantane-2-thiones and 2-Methyleneadamantanes

  摘要：

  The 1,3-dipolar cycloaddition reactions of benzonitrile oxide with 5-substituted adamantane-2-thiones (2-X) and 2-methyleneadamantanes (3-X) produced two geometrically isomeric Delta(2)-1,4,2-oxathiazolines (5-Xs) and two Delta(2)-isoxazolines (6-Xs), respectively. The substituent was varied from fluoro, chloro, bromo, to phenyl. X-ray single-crystal analysis confirmed the configuration of (Z)-5-F. The produce formation bias resulting from the favored attack of nitrile oxide on the zu-face is discussed in terms of transition-state hyperconjugation and frontier molecular orbital theory.

  DOI：

  10.1021/jo9703717
• 作为产物：
  描述：

  5-氟-2-金刚烷酮 在 tetraphosphorus decasulfide 作用下， 以 吡啶 为溶剂， 反应 11.0h， 以93%的产率得到5-fluoroadamantane-2-thione
  参考文献：
  名称：

  Face selection in thermal cycloaddition and -reversion

  摘要：

  The isomer distribution has been determined in several cycloaddition reactions involving 5-fluoro- and 5-phenyladamantane derivatives in which C2 serves as one of the trigonal termini. The reactions include a [2 + 2] cycloaddition with dichloroketene, a nucleophilic addition followed by cyclization, a [2 + 2] cycloreversion of a beta-lactone, and two Diels-Alder reactions; in the latter case, the adamantane moiety was incorporated in the diene in one instance and in the dienophile in the other. In all these reactions, the reagent attacking the adamantane substrate was found to do so preferentially at the zu face, by modest but clear margins. This observation is in accord with the concept of transition-state hyperconjugation. This explanation is extended to several literature examples involving substrates with faces that are not isosteric because the polarizing group is placed closer to the site of attack; the ratios are substantial and in favor of the more hindered product in many of these examples.

  DOI：

  10.1021/jo00020a041

文献信息

• Hyperconjugation as a factor in face selectivity during cycloaddition
  作者：Wen Sheng. Chung、N. J. Turro、Sushil. Srivastava、Haifang. Li、W. J. Le Noble

  DOI：10.1021/ja00231a052

  日期：1988.11

  oxidizer20) to be endothermic.26 It is likely that the endothermic oxidations of many azoalkanes are driven to nitrogen evolution by the instability of R-N=N-R'+.7 These cation radicals become less stable when the hydrocarbon cation radicals formed by deazatation are more heavily substituted. In the bridgehead dimethyl derivative of DBO, for example, we find that reaction with 2 equiv of TBPA" causes

  氧化剂 20) 是吸热的。26 许多偶氮烷的吸热氧化很可能是由于 RN=N-R'+ 的不稳定性而导致氮析出。7 当脱氮作用形成的烃阳离子自由基为更大量地取代。例如，在 DBO 的桥头二甲基衍生物中，我们发现与 2 当量的 TBPA" 反应导致定量的氮析出并且没有形成红色物质。从这项研究和其他研究中开始出现的偶氮烷烃的行为模式可能，也许，符合 Parker 推广的亲核试剂/阳离子自由基反应的一般概念。 20 如果偶氮烷烃和阳离子自由基之间的初始相遇导致复合物，可以想象，这种配合物要么分解产生偶氮烷阳离子自由基，要么被反应物阳离子自由基进一步氧化。在 DBO 的情况下，进一步氧化将以共价键结束，如产品 1 和 2 中所示。 总之，我们发现 DBO 氧化形成具有稳定阳离子自由基盐的加合物，这与先前研究的偶氮烷烃进行氧化脱氮形成对比.