Di(1-phenyl-ethinyl)-Sulfan | 68634-32-2

• 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: Di(1-phenyl-ethinyl)-Sulfan
• 英文别名: bis(phenylethynyl) sulfide；bis-(phenylethynyl)sulfane；Bis(phenylethynyl)sulfane；bis(phenylethynyl)sulfide；2-(2-Phenylethynylsulfanyl)ethynylbenzene
• CAS: 68634-32-2
• 化学式: C₁₆H₁₀S
• 分子量: 234.321
• InChiKey: PKXXICCARSADNL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Di(1-phenyl-ethinyl)-Sulfan 在 正丁基锂 、 1,4-环己二烯 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 2.0h， 生成 phenyl-thioacetic acid O-ethyl ester
  参考文献：
  名称：

  二乙炔基硫化物的光化学：形成五元环的环芳香化。

  摘要：

  已经证明了第一个五元环芳环化反应。通过假定的2，5-二氢二噻吩中间物，在己烷/ 1,4-环己二烯中对双（苯基乙炔基）硫化物进行光辐照可生成3,4-二苯基噻吩。另外，在该反应中产生苯基乙炔，这与竞争性的直接碳硫裂解一致。对于在乙醇或2-丙醇中的反应，噻吩的生产伴随有苯乙炔和相应醇的硫代酸酯的形成。噻吩产物还源于其他二乙炔硫醚的辐射。[反应：看文字]

  DOI：

  10.1021/ol034266x
• 作为产物：
  描述：

  硫化双(苯甲酰甲基) 在 lithium hexamethyldisilazane 、 氯磷酸二乙酯 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以77%的产率得到Di(1-phenyl-ethinyl)-Sulfan
  参考文献：
  名称：

  Thiophene synthesis via 1,1-carboboration

  摘要：

  在室温下，叔丁基乙炔硫与硼Lewis酸试剂X–B(C6F5)2（X = CH3，Cl，C6F5）在戊烷中反应，得到相应的硼化噻吩，这是一系列1,1-碳硼化反应的过程。

  DOI：

  10.1039/c5cc01806d

文献信息

• Fast and Highly Chemoselective Alkynylation of Thiols with Hypervalent Iodine Reagents Enabled through a Low Energy Barrier Concerted Mechanism
  作者：Reto Frei、Matthew D. Wodrich、Durga Prasad Hari、Pierre-Antoine Borin、Clément Chauvier、Jérôme Waser

  DOI：10.1021/ja5083014

  日期：2014.11.26

  Nevertheless, general methods to access these compounds are lacking. In this article, we describe the mechanism and full scope of the alkynylation of thiols using ethynyl benziodoxolone (EBX) hypervalent iodine reagents. Computations led to the discovery of a new, three-atom concerted transition state with a very low energy barrier, which rationalizes the high reaction rate. On the basis of this result

  在所有官能团中，炔烃在合成化学和药物化学、化学生物学和材料科学中占据着特殊的地位。硫代炔尤其非常有用，因为它们将三键的增强反应性与生物活性化合物和材料中经常遇到的硫原子结合起来。然而，缺乏获取这些化合物的通用方法。在本文中，我们描述了使用乙炔基苯并氧酮 (EBX) 高价碘试剂对硫醇进行炔基化的机制和完整范围。计算发现了一种新的三原子协同过渡态，其能垒非常低，这使得高反应速率合理化。在此结果的基础上，反应范围扩展到合成含有多种官能团的芳基和烷基取代的炔烃。新的硫亲核试剂如硫代糖苷、硫代酸和硫化氢钠也被成功地炔基化，形成了迄今为止报道的最通用和实用的硫代炔烃合成方法。
• One-Pot Preparation of Arylethynyl Sulfides and Bis(arylethynyl) Sulfides
  作者：Qiong Su、Zi-Jian Zhao、Feng Xu、Peng-Cai Lou、Kai Zhang、De-Xun Xie、Lei Shi、Qing-Yun Cai、Zhi-Hong Peng、De-Lie An

  DOI：10.1002/ejoc.201201422

  日期：2013.3

  An efficient preparation for arylethynyl sulfides 1 and bis(arylethynyl) sulfides 2 has been accomplished through a one-pot, three-step strategy that starts from arylethanonyl sulfides and bis(arylethanonyl) sulfides, respectively, without the use of various terminal arylacetylenes as substrates. When lithium hexamethyldisilazane (LHMDS), ClP(O)(OEt)2, and LHMDS were sequentially added to a tetrahydrofuran

  芳基乙炔基硫化物 1 和双（芳基乙炔基）硫化物 2 的有效制备已通过一锅三步策略完成，该策略分别从芳基乙炔基硫化物和双（芳基乙炔基）硫化物开始，无需使用各种末端芳基乙炔作为底物. 当将六甲基二硅氮烷锂 (LHMDS)、ClP(O)(OEt)2 和 LHMDS 依次加入不同底物 [芳基乙酮硫化物或双（芳基乙炔基）硫化物] 的四氢呋喃溶液中时，以中等至良好的收率获得 1 或 2。反应过程包括烯醇磷酸酯的形成和随后的碱诱导消除。
• Reactivity of the [η ² ‐Bis( <i>tert</i> ‐butylsulfonyl)acetylene](carbonyl)(η ⁵ ‐cyclopentadienyl)cobalt Complex Towards Electron‐Rich and ‐Poor Acetylenes
  作者：Avijit Goswami、Tobias H. Staeb、Frank Rominger、Rolf Gleiter、Walter Siebert

  DOI：10.1002/ejic.200500308

  日期：2005.10

  react smoothly with [η2-bis(tert-butylsulfonyl)acetylene](carbonyl)(η5-cyclopentadienyl)co-balt (1) to form the donor–acceptor stabilized (η4-cyclobutadiene)cobalt complexes 3a–c in good yields. However, treatment of the electron-poor borylacetylenes 2d–f with the cobalt complex 1 does not lead to the expected (η4-cyclobutadiene)cobalt complexes. Analogously, the reaction of bis(1-phenylethynyl)sulfide

  富电子氨基乙炔 Et2NC2R（分别为 2a–c，R = SPh、PPh2 和 Ph）与 [η2-双（叔丁基磺酰基）乙炔]（羰基）（η5-环戊二烯基）钴 (1)以良好的收率形成供体-受体稳定的（η4-环丁二烯）钴配合物3a-c。然而，用钴配合物 1 处理缺电子硼炔乙炔 2d-f 不会产生预期的（η4-环丁二烯）钴配合物。类似地，双(1-苯基乙炔基)硫化物(2g)与两个当量的1的反应产生硫桥连的双[η4-(环丁二烯)钴]配合物3g。新的钴配合物通过 NMR 光谱、质谱和 X 射线结构分析对 3a 进行了表征，这表明环丁二烯环内的 C-C 键长度几乎相等。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
• Synthesis of [Fe2(CO)6(μ-SC2H5)(μ-CCR)] (R = CH3 or C6H5) and reactivity with electron-rich molecules, triphenylphosphine, diphenylacetylene, ethylthio(phenyl) ethyne and (diethylamino) propyne. Preparation of [Fe2(CO)6(μ-SCCC6H5)(μ-CCC6H5)] and formation of [Fe4(CO)12(μ4-S)(μ-CCC6H5)2]
  作者：Céline Rosenberger、Nathalie Steunou、Suzanne Jeannin、Yves Jeannin

  DOI：10.1016/0022-328x(94)05298-p

  日期：1995.5

  Compounds [Fe-2(CO)(6)(mu-SC2H5)(mu-CCR)] with R = CH3 or C6H5, were prepared and allowed to react with triphenylphosphine, diphenylacetylene, (ethylthio)phenylethyne, 1-(diethylamino)prop-1-yne. These four reactants are electron-rich molecules able to attack at the acetylide carbon atoms C-alpha=C(beta)R. The structures of nine complexes were determined by X-ray diffraction.For R = CH3 or P(C6H5)(3) reaction occurred at C-beta leading to [Fe-2(CO)6(mu-SC2H5)mu-C=C[P(C6H5)(3)](CH3)}]. In the case of R = C6H5, a monosubstituted complex [Fe-2(CO)(5)P(C6H5)(3)}(mu-SC2H5)(mu-CCC6H5)] and a disubstituted complex [Fe-2(CO)(4)P(C6H5)(3)}(2)(mu SC2H5)(mu-CCC6H5)] were obtained. With C6H5C=CC6H5, [Fe-2(CO)(5)mu-S(C2H5)C(R)CC(C6H5)C(C6H5)C(O)}] was obtained (R = CH3 or C6H5). The opening of the triple bond of the incoming alkyne led to two C-C bonds, one with acetylide C-alpha, one with a carbonyl group. The SC2H5 moved around an iron atom from a bridging position to be linked to C-beta. In addition, for R = C6H5 an isomer was obtained the structure of which is based on a nido Fe2C3 framework. It readily transformed into [Fe-2(CO)(5)mu-S(C2H5)C(C6H5)CC(C6H5)C(C6H5)C(O)}]. With C6H5C=CSC2H5 two complexes, [Fe-2(CO)(5)mu-S(C2H5)C(C6H5)CC(C6H5)C(SC2H5)C(O)}] (80%) and [Fe-2(CO)(5)mu-S(C2H5)C(C6H5)CC(SC2H5)C(C6H5)C(O)}] (20%), were obtained. They are of the same structural type as above. The major product resulted from the coupling of thioalkyne C-beta with acetylide C-alpha.With CH3C-CN(C2H5)(2) the complex obtained, [Fe-2(CO)(6)C[C(O)SC2H5]C(C6H5)C(CH3)C[N(C2H5)(2)]}], has a structure based on a ferracyclopentadienyl fragment ligated to a second iron atom by a Fe-Fe bond and by an allylic fragment. An unprecedented CO insertion occured in a side chain, yielding an ethylthiocarboxy radical. Both CS bonds were eventually cleaved using S(C=CC6H5)(2) as a starting alkyne. First, [Fe-2(CO)(6)(mu-SC=CC6H5)(mu-C=CC6H5)] was prepared. Second, an excess of iron carbonyl yielded [Fe-4(CO)(12)(mu(4)-S)(mu-C=CC6H5)(2)]. The four iron atoms belong to two dinuclear entities and form a tetrahedron around sulfur.
• Voets, Marieke; Smet, Mario; Dehaen, Wim, Journal of the Chemical Society. Perkin transactions I, 1999, # 11, p. 1473 - 1475
  作者：Voets, Marieke、Smet, Mario、Dehaen, Wim

  DOI：——

  日期：——