1,2,2-triphenyl-1-ethenethiol | 89703-81-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1,2,2-triphenyl-1-ethenethiol
• 英文别名: triphenylethenethiol；triphenyl-ethenethiol；Triphenyl-aethenthiol；Triphenylvinylthiol；Triphenylvinyl sulfurane；1,2,2-triphenylethenethiol
• CAS: 89703-81-1
• 化学式: C₂₀H₁₆S
• 分子量: 288.413
• InChiKey: JPTSAZQFCMCNRE-UHFFFAOYSA-N

物化性质

• 熔点：
  110-111 °C
• 沸点：
  407.5±45.0 °C(Predicted)
• 密度：
  1.124±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,2,2-triphenyl-1-ethenethiol 在 nickel dichloride 作用下， 以 二甲基亚砜 为溶剂， 反应 1.5h， 以14%的产率得到bis-triphenylvinyl disulfide
  参考文献：
  名称：

  钯催化从硫烯酚直接合成苯并[b]噻吩。

  摘要：

  通过使用简单的钯催化剂（例如PdCl（2）或PdCl（2）（cod）），将单烯醇单锅转化为苯并[b]噻吩。

  DOI：

  10.1039/b811362a
• 作为产物：
  描述：

  1,2,2-三苯乙酮 在 劳森试剂 作用下， 以 甲苯 为溶剂， 反应 50.0h， 以46%的产率得到1,2,2-triphenyl-1-ethenethiol
  参考文献：
  名称：

  Triphenylethenethiol. Structure, Equilibria with the Thioketone, Solvation, and Association with DMSO

  摘要：

  The simple thioenols, triphenylethenethiol (12) and 2,2-diphenyl-1-anisylethenethiol (13) were prepared. Both are the only observed constituent of the thioenol reversible arrow thioketone equilibria and comparison and estimation suggested that the thiocarbonyl reversible arrow thioenol equilibrium constant K-enol for 12 and other simple thioenols is greater than or equal to 10(6) higher than for the corresponding carbonyl reversible arrow enol equilibria. The X-ray diffraction of 12, which is the first measured for a simple thioenol, shows a propeller arrangment of the three rings. The delta(SH) in the H-1 NMR spectrum increases with the increase in the hydrogen bonding accepting parameter beta of the solvent. The association constant K-assoc of 12 with DMSO is 0.087, much lower than values of triarylethenols with DMSO. Reaction of diphenylacetaldehyde with Lawesson's reagent did not give the thioenol, but gave bis(2,2-diphenylvinyl) sulfide (16) and a substance (17) having a trithiaphosphorinane system.

  DOI：

  10.1021/jo9604651

文献信息

• A Search for Unambiguous Vinylic SRN1 Reactions
  作者：Alfonso Annunziata、Carlo Galli、Patrizia Gentili、Alessandra Guarnieri、Michal Beit-Yannai、Zvi Rappoport

  DOI：10.1002/1099-0690(200207)2002:13<2136::aid-ejoc2136>3.0.co;2-8

  日期：2002.7

  unambiguous examples of the vinylic SRN1 route, vinyl bromides Ph(CH3)C=CHBr (10), Ph2C=CHBr (15), An2C=C(Br)An (18) and An2C=CBr2 (20) were treated with Me3CCOCH2− under photostimulation conditions in Me2SO, whereas substrates PhCH=CHBr (2), Ph2C=C(Br)Ph (3), 10 and 15 were similarly allowed to react with PhS− and PhCH2S−. With the strongly basic enolate ion, the prevailing reactions were elimination/addition

  在寻找乙烯基 SRN1 路线的明确例子时，乙烯基溴化物 Ph(CH3)C=CHBr (10)、Ph2C=CHBr (15)、An2C=C(Br)An (18) 和 An2C=CBr2 (20) 是在 Me2SO 中的光刺激条件下用 Me3CCOCH2- 处理，而底物 PhCH=CHBr (2)、Ph2C=C(Br)Ph (3)、10 和 15 类似地允许与 PhS- 和 PhCH2S- 反应。对于强碱性烯醇化物离子，主要的反应是消除/加成路线、α-去质子化，然后是 1,2-Ph 转移和溴离子消除，或嗜盐步骤。然而，对于 18，获得了 SRN1 路线。弱碱性但还原性的阴离子 PhS− 为 SRN1 路线提供了 2、3 和 15。PhCH2S− 阴离子的亲核特性代替了 15，而 3 则获得了多种行为。电化学确定的底物氧化还原电位支持机械解释。(© Wiley-VCH Verlag GmbH, 69451
• The acid dissociation constant of triphenylethenethiol, a simple thioenol, and that of its oxygen-enol analog
  作者：Yvonne Chiang、A Jerry Kresge、Norman P Schepp、Vladimir V Popik、Zvi Rappoport、Tzvia Selzer

  DOI：10.1139/v98-027

  日期：1998.6.1

  The acidity constant, pQ_a^E = 8.49, for the stable thioenol, triphenylethenethiol, was determined by spectrophotometric titration, and that, pQ_a^E = 11.37, for its unstable oxygen analog, triphenylethenol, was determined by analysis of its ketonization rate using enol generated flash photolytically from triphenylvinyl bromide. (These acidity constants are concentration quotients applicable at 0.10 M ionic strength in 50 vol.% aqueous methanol.) This appears to be the first determination of the acid strength of a simple thioenol. Triphenylethenethiol was unreactive in dilute acid or base, but in concentrated perchloric acid solutions it was slowly transformed into diphenylacetophenone and 2,3-diphenylbenzo[b]thiophene; the mechanisms of these reactions are believed to involve rapid equilibrium protonation of the enol on the beta -carbon followed by rate-determining capture of the cation so formed, either externally by solvent or internally by one of the beta -phenyl groups of the ion.Key words: enol ketonization, thioenol, flash photolysis, vinyl halide.

  稳定的硫醇三苯乙烯硫醇的酸度常数pQ_a^E为8.49，通过分光光度滴定确定；其不稳定的氧类似物三苯乙醇的酸度常数pQ_a^E为11.37，通过分析其从三苯基乙烯溴生成的烯醇光解速率来确定。（这些酸度常数是适用于50%甲醇水溶液中0.10M离子强度的浓度商。）这似乎是对简单硫醇酸强度的首次测定。三苯乙烯硫醇在稀酸或碱中不活泼，但在浓盐酸溶液中，它缓慢地转化为二苯乙酮和2,3-二苯基苯并[b]噻吩；这些反应的机制被认为涉及到β-碳上的烯醇的快速平衡质子化，随后是由所形成的阳离子的捕获，可以是外部的溶剂，也可以是其中一个β-苯基团.Key words: 烯醇酮化，硫醇，闪光光解，乙烯卤代物。
• Silylated thiiran-1-oxides: Structure, ring opening and conversion to a benzothiophene.
  作者：Bianca F. Bonini、Elisabetta Foresti、Rino Leardini、Gaetano Maccagnani、Germana Mazzanti

  DOI：10.1016/s0040-4039(00)99907-6

  日期：1984.1

  Silylated thiirans upon oxidation with peroxyacids do not give exclusively the corresponding S-oxides but, in addition some products derived from ring opening. The stereochemistry of the oxidation to thiiran-1-oxides is to the silyl group as demonstrated by X-ray analysis.

  用过氧酸氧化时，甲硅烷基化的噻喃并不仅能得到相应的S-氧化物，而且还会产生一些来自开环的产物。X射线分析表明，氧化成噻喃-1-氧化物的立体化学是甲硅烷基。
• El-Sayed, Ibrahim; Abdel-Megeed, Mohamed F.; Yassin, Salah M., Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 86, # 1.4, p. 239 - 258
  作者：El-Sayed, Ibrahim、Abdel-Megeed, Mohamed F.、Yassin, Salah M.、Senning, Alexander

  DOI：——

  日期：——
• El-Sayed Ibrahim, Abdel-Megeed Mohamed F., Yassin Salah M., Senning Alexa+, Phosph., Sulfur and Silicon and Relat. Elem, 86 (1994) N 1-4, S 239-257
  作者：El-Sayed Ibrahim, Abdel-Megeed Mohamed F., Yassin Salah M., Senning Alexa+

  DOI：——

  日期：——