3α-Thiocyanatocholestan | 67664-73-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 3α-Thiocyanatocholestan
• CAS: 67664-73-7
• 化学式: C₂₈H₄₇NS
• 分子量: 429.754
• InChiKey: POSVXFDQEWXLGQ-IOIYRQMXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.69
• 重原子数：
  30.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  23.79
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  硫氰酸 、 粪甾烷-3-醇 在 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 苯 为溶剂， 生成 3α-Thiocyanatocholestan
  参考文献：
  名称：

  磷光体化学反应。XLI [1]。新合成系统Aspekte des Systems三苯膦-偶氮二碳酸酯-羟基邻苯二酚† ‡

  摘要：

  使用三苯基膦-二乙基-偶氮二羧酸酯-羟基化合物的新制备方法。

  DOI：

  10.1002/hlca.19760590622

文献信息

• Electrochemical Preparation and Some Reactions of Alkoxy Triphenylphosphonium Ions.
  作者：Hatsuo MAEDA、Takashi KOIDE、Toshihide MAKI、Hidenobu OHMORI

  DOI：10.1248/cpb.43.1076

  日期：——

  The formation of an alkoxy triphenylphosphonium ion by anodic oxidation of Ph3 P in the presence of an alcohol was reinvestigated. When a CH2CL2 solution of Ph3P, Ph3P+H·ClO-4, and an alcohol was subjected to constantcurrent electrolysis in an undivided cell equipped with a graphite anode and a Pt cathode, the 31P-NMR spectra of the resulting electrolyte showed that alkoxy triphenylphosphonium perchlorates (2) were formed in good to fair yields from primary and secondary aliphatic alcohols, while allylic and benzylic alcohols were transformed to the correspinding alkyl phosphonium ions, and in the case of tertiary aliphatic alcohols, no formation of the corresponding alkoxy or alkyl phosphonium ions was recognized at all. The isolation of 2 thus formed was achieved in good yields by a simple procedure. For the electrolysis, Ph3P+H·BF-4 could be utilized insted of the perchlorate salt, giving an alkoxy triphenylphosphonium tetrafluoroborate (3) from primary and secondary aliphatic alcohols. The reaction of the alkoxy phosphonium ions prepared from β- and α-cholestanol with various nucleophiles such as Bu4N+·X- (X=Br, Cl, F, N3, SCN), PhSH, and PhOH was examined. The results indicated that the reaction site of the phosphonium ions is dictated by the identity of the nucleophile. A soft nucleophile was apt to attack at the α-carbon, giving the corresponding SN2 reaction product in a good yield, while a hard one tended to react at the phosphorus of the phosphonium ion, leading to the regeneration of the cholestanol.

  重新研究了在醇存在下通过阳极氧化 Ph3 P 形成烷氧基三苯基鏻离子。当 Ph3P、Ph3P+H·ClO-4 和醇的 CH2CL2 溶液在配有石墨阳极和 Pt 阴极的整体电解槽中进行恒流电解时，所得电解液的 31P-NMR 谱表明烷氧基三苯基鏻高氯酸盐 (2) 由脂肪伯醇和仲脂肪醇以良好到中等的产率形成，而烯丙醇和苄醇转化为相应的烷基磷鎓离子，并且在脂肪族叔醇的情况下，没有形成相应的烷氧基或烷基磷鎓离子离子完全被识别。通过简单的程序以良好的产率实现了由此形成的2的分离。对于电解，可以使用Ph3P+H·BF-4代替高氯酸盐，由伯和仲脂肪醇得到烷氧基三苯基鏻四氟硼酸盐(3)。研究了由β-和α-胆甾烷醇制备的烷氧基鏻离子与Bu4N+·X-（X=Br、Cl、F、N3、SCN）、PhSH和PhOH等各种亲核试剂的反应。结果表明，鏻离子的反应位点由亲核试剂的特性决定。软亲核试剂易于攻击α-碳，以良好的产率生成相应的SN2反应产物，而硬亲核试剂则易于攻击磷鎓离子的磷，从而导致胆甾烷醇的再生。