2-(diphenylhydroxymethyl)-1,3-dithiane | 5849-23-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(diphenylhydroxymethyl)-1,3-dithiane
• 英文别名: (1,3-dithian-2-yl)diphenylmethanol；[1,3]dithian-2-yl-diphenyl-methanol；1,3-Dithian-2-yl(diphenyl)methanol
• CAS: 5849-23-0
• 化学式: C₁₇H₁₈OS₂
• 分子量: 302.461
• InChiKey: YUPQKLKTSXXYFK-UHFFFAOYSA-N

物化性质

• 熔点：
  135 °C
• 沸点：
  484.8±40.0 °C(predicted)
• 密度：
  1.233±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  70.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(diphenylhydroxymethyl)-1,3-dithiane 在 盐酸 作用下， 以 水 、 乙腈 为溶剂， 反应 2.0h， 以64%的产率得到3-[(2,2-diphenylvinyl)sulfanyl]propane-1-thiol
  参考文献：
  名称：

  酸诱导的α-羟基-1,3-二噻烷的重排反应

  摘要：

  当用酸处理时，仲苄基或脂族α-羟基二硫杂环丁烷1a - c重新排列为α-硫酮。相关的叔醇1d - g消除了二硫代酮烯缩酮（例如2d），后者在某些情况下（1e，1f）对硫醇开环。烯丙基α-羟基二硫杂环丁烷1h和1i形成硫酯2h和2i（同位），叔醇1j和1k脱氧成2j和2k。 1,3-二噻烷-二硫缩醛-1,3-二噻-1-氧化物-重排-脱氧-同源

  DOI：

  10.1055/s-0029-1218658
• 作为产物：
  描述：

  1,3-二噻烷 、 二苯甲酮 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.17h， 以60%的产率得到2-(diphenylhydroxymethyl)-1,3-dithiane
  参考文献：
  名称：

  Photochemically amplified detection of molecular recognition events: an ultra-sensitive fluorescence turn-off binding assay

  摘要：

  基于双功能光敏剂-淬灭剂的大量自催化光解蔽，开发并采用了一种增强型荧光淬灭方法，用于分子识别事件的超灵敏光辅助检测。这种结合基于分子识别触发的光放大级联反应与伴随的荧光下降，通过生物素-抗生物素蛋白对的验证，实现了阿托摩尔级的检测。

  DOI：

  10.1039/c1ob05289f

文献信息

• Hydroltsis of Ketol Trimethylenedithioacetals. Attempted Synthesis of Yashabushiketol
  作者：Tse-Lok Ho、Raymond J. Hill、C. M. Wong

  DOI：10.3987/com-88-4584

  日期：——
• Watanabe, Yoshihiko; Ohno, Yohjiro; Ueno, Yoshio, Journal of the Chemical Society. Perkin transactions I, 1998, # 6, p. 1087 - 1093
  作者：Watanabe, Yoshihiko、Ohno, Yohjiro、Ueno, Yoshio、Toru, Takeshi

  DOI：——

  日期：——
• An Efficient Photo-SET-Induced Cleavage of Dithiane−Carbonyl Adducts and Its Relevance to the Development of Photoremovable Protecting Groups for Ketones and Aldehydes
  作者：William A. McHale、Andrei G. Kutateladze

  DOI：10.1021/jo981697y

  日期：1998.12.1

  Irradiation of dithiane-aldehyde/ketone adducts in the presence of benzophenone leads to C-C bond cleavage regenerating the carbonyl compounds. It is established that the mechanism of this reaction involves photochemically induced single electron transfer from the dithiane moiety to the excited molecule of ET-photosensitizer, accompanied by mesolytic C-C cleavage in the generated cation-radical, which is assisted by the anion-radical of benzophenone. This mechanism is confirmed by a Hammett plot study of the cleavage in the dithiane adducts of substituted aromatic aldehydes and a deuterium kinetic isotope effect study. Ab initio computations at UHF/6-31G* and MP2/6-31G* levels of theory in conjunction with self-consistent reaction field (self-consistent isodensity-polarized continuum model), to account for the solvent effect, also support the experimental findings. The reaction is most efficient for protection of aromatic aldehydes and ketones and aliphatic ketones, and is a novel method for protecting carbonyl functionalities with a photoremovable group.
• Externally sensitized mesolytic fragmentations in dithiane–ketone adducts
  作者：Tiffany P. Gustafson、Alexei N. Kurchan、Andrei G. Kutateladze

  DOI：10.1016/j.tet.2006.03.065

  日期：2006.7

  The apparent activation enthalpies, Delta H-not equal, for externally sensitized mesolytic fragmentations in benzophenone-dithiane adducts were obtained in variable temperature photolyses and compared with DFT activation barriers calculated for beta-scission in the corresponding oxygen-centered radicals. The results of these experimental and theoretical studies further support the mechanism in which deprotonation of the hydroxy-group, in the transient cation radical, is coupled with intramolecular electron transfer furnishing the O-centered radical, which subsequently fragments. The quantum yields of fragmentation increase for higher alkyl substituted dithiane adducts. (c) 2006 Elsevier Ltd. All rights reserved.
• HO, TNE-LOK;HUL, RAYMOND J.;WONG, C. M., HETEROCYCLES, 27,(1989) N, C. 1719-1725
  作者：HO, TNE-LOK、HUL, RAYMOND J.、WONG, C. M.

  DOI：——

  日期：——