3-phenyl-2-phenylthio-1-propene | 85894-91-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3-phenyl-2-phenylthio-1-propene
• 英文别名: 3-phenyl-2-(phenylthio)propene；3-Phenylprop-1-en-2-ylsulfanylbenzene
• CAS: 85894-91-3
• 化学式: C₁₅H₁₄S
• 分子量: 226.342
• InChiKey: KKGIKBLHWAGJGU-UHFFFAOYSA-N

物化性质

• 沸点：
  352.2±35.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  3-phenyl-2-phenylthio-1-propene 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 氯仿 为溶剂， 生成 (Z)-1-phenyl-2-(phenylthio)-3-bromoprop-1-ene 、 (E)-1-phenyl-2-(phenylthio)-3-bromoprop-1-ene
  参考文献：
  名称：

  Enol thioethers as enol substitutes. An alkylation sequence

  摘要：

  DOI：

  10.1021/ja00353a037
• 作为产物：
  描述：

  (2-phenylethane-1,1-diyl)bis(phenylsulfane) 在 正丁基锂 、 三丁基(碘甲基)锡烷 作用下， 生成 3-phenyl-2-phenylthio-1-propene
  参考文献：
  名称：

  Ochiai, Masahito; Ukita, Tatsuzo; Fujita, Eiichi, Chemical and pharmaceutical bulletin, 1984, vol. 32, # 5, p. 1829 - 1839

  摘要：

  DOI：

文献信息

• Rhodium-catalyzed hydrothiolation of alkynes with thiols for construction of sulfur-containing π-conjugated systems
  作者：Aya Yoshimura、Akihiro Nomoto、Akiya Ogawa

  DOI：10.1007/s11164-014-1639-0

  日期：2014.7

  To synthesize sulfur-containing π-conjugated polymers, reaction conditions for rhodium-catalyzed hydrothiolation of terminal alkynes with arenethiols are optimized in detail. Under the optimized conditions, rhodium-catalyzed hydrothiolation of terminal alkynes proceeds regio- and stereoselectively to afford the corresponding vinyl sulfides via an anti-Markovnikov and syn-addition process. Then, the rhodium-catalyzed hydrothiolation is applied to polymerization of 2,5-diethynylthiophene with benzene-1,4-dithiol, which successfully provides sulfur-containing π-conjugated polymers with excellent regio- and stereoselectivities.

  为了合成含硫π共轭聚合物，我们详细优化了铑催化末端炔烃与壬硫醇氢硫化反应的条件。在优化的条件下，铑催化的末端炔烃氢硫化反应可通过反马尔科夫尼科夫和同步加成过程进行区域和立体选择性反应，生成相应的乙烯基硫化物。然后，将铑催化的氢硫化反应应用于 2,5- 二乙炔基噻吩与苯-1,4-二硫醇的聚合反应，成功地制备出了具有优异的区域和立体选择性的含硫 π 共轭聚合物。
• Hydroxo–Rhodium–N-Heterocyclic Carbene Complexes as Efficient Catalyst Precursors for Alkyne Hydrothiolation
  作者：Laura Palacios、Maria Jose Artigas、Victor Polo、Fernando J. Lahoz、Ricardo Castarlenas、Jesús J. Pérez-Torrente、Luis A. Oro

  DOI：10.1021/cs400739y

  日期：2013.12.6

  The new Rh-hydroxo dinuclear complexes stabilized by an N-heterocyclic carbene (NHC) ligand of type [Rh(mu-OH)(NHC)(eta(2)-olefin)](2) (coe, IPr (3), IMes (4); ethylene, IPr (5)) are efficient catalyst precursors for alkyne hydrothiolation under mild conditions, presenting high selectivity toward alpha-vinyl sulfides for a varied set of substrates, which is enhanced by pyridine addition. The structure of complex 3 has been determined by X-ray diffraction analysis. Several intermediates relevant for the catalytic process have been identified, including Rh-I-thiolato species Rh(SCH2Ph)(IPr)(eta(2)-coe)(py) (6) and Rh(SCH2Ph)(IPr)(eta(2)-HC CCH2Ph)(py) (7), and the Rh-III-hydride-dithiolato derivative RhH(SCH2Ph)(2)(IPr)(py) (8) as the catalytically active species. Computational DFT studies reveal an operational mechanism consisting of sequential thiol deprotonation by the hydroxo ligand, subsequent S-H oxidative addition, alkyne insertion, and reductive elimination. The insertion step is rate-limiting with a 1,2 thiometalation of the alkyne as the more favorable pathway in accordance with the observed Markovnikov-type selectivity.
• Highly Regioselective Addition of Benzenethiol to Allenes Catalyzed by Palladium Acetate
  作者：Akiya Ogawa、Jun-ichi Kawakami、Noboru Sonoda、Toshikazu Hirao

  DOI：10.1021/jo9521357

  日期：1996.1.1
• Addition of benzenethiol to terminal alkynes catalyzed by hydrotris(3,5-dimethylpyrazolyl)borate–Rh(III) bis(thiolate) complex: Mechanistic studies with characterization of the key intermediate
  作者：Yoshiyuki Misumi、Hidetake Seino、Yasushi Mizobe

  DOI：10.1016/j.jorganchem.2006.03.005

  日期：2006.7

  The Rh(III)-thio late complex [Tp*Rh(SPh)(2)(MeCN)] (2; Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) readily undergoes substitution of MeCN by XyNC (Xy = 2,6-dimethylphenyl) to give the isocyanide complex [Tp*Rh(SPh)2(XyNC)l (3), 4 whereas reaction of 2 with terminal alkynes results in the formation of the rhodathiacyclobutene complex [Tp*Rh(SPh)eta(2)-CH = CR(SPh)}] (4; R = aryl, alkyl). Molecular structures of 3 and 4 (R = CH2Ph) have been determined by single crystal X-ray diffraction. Complex 2 as well as [Tp*Rh(cyclooctene)(MeCN)] have been found to catalyze regioselective addition of benzenethiol to terminal alkynes RC-CH at 50 degrees C to give R(PhS)C = CH2 in moderate to high yields. The above products are selectively formed when R = CH2Ph and n-C6H13, while cis-RCH = CHSPh and RC(SPh)(2)CH3 are also obtained as by-products when R = p-MeOC6H4. Catalytic cycle involving 2 and 4 is proposed based on the mechanistic studies using NMR measurement. (c) 2006 Elsevier B.V. All rights reserved.