(E)-5-(benzylthio)-1-phenyl-1-pentene | 148470-51-3

• 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: (E)-5-(benzylthio)-1-phenyl-1-pentene
• CAS: 148470-51-3
• 化学式: C₁₈H₂₀S
• 分子量: 268.423
• InChiKey: YONMNGOOMACUPA-XYOKQWHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.41
• 重原子数：
  19.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (E)-5-(benzylthio)-1-phenyl-1-pentene 在 [MoO(O₂)2(O-pyridine)(H₂O)] coated on SiO₂ 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 9.0h， 以94%的产率得到5-phenyl-4-pentenyl benzyl sulfoxide
  参考文献：
  名称：

  吸附在硅胶上的二氧杂过氧钼络合物将硫化物选择性和温和地氧化为亚砜

  摘要：

  使用涂在硅胶上（孔径为150Å）的钼的氧代二氧杂配合物，脂肪族和芳香族硫化物，酮硫醚，亚磺酸基酸和酯以及烯属硫化物被氧化为亚砜。观察到所有功能性硫化物的氧化具有完全的化学选择性。然而，当配合物未涂覆在硅胶上时，砜是反应的主要产物。还研究了硅胶作为这些反应支持物的影响，并证明了它改变了配合物的反应性，但对配合物的优异的化学选择性不负责任。络合物[MoO（O 2）2（吡唑）（H 2 O）]被证明比[MoO（O 2）具有更高的反应性2（Opyr）（H 2 O）]。

  DOI：

  10.1016/s0040-4020(01)00969-3
• 作为产物：
  描述：

  (E)-5-phenylpent-4-en-1-yl 4-methylbenzenesulfonate 在 sodium hydroxide 、 sodium iodide 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 24.0h， 生成 (E)-5-(benzylthio)-1-phenyl-1-pentene
  参考文献：
  名称：

  Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides

  摘要：

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.

  DOI：

  10.1021/jo00125a038

文献信息

• Regiochemical studies on halocyclization reactions of unsaturated sulfides
  作者：Ren Xiao-Feng、Edward Turos

  DOI：10.1016/0040-4039(93)85010-t

  日期：1993.3
• Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides
  作者：Xiao-Feng Ren、Edward Turos、Charles H. Lake、Melvyn Rowen Churchill

  DOI：10.1021/jo00125a038

  日期：1995.10

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.
• Selective and mild oxidation of sulfides to sulfoxides by oxodiperoxo molybdenum complexes adsorbed onto silica gel
  作者：Fabiana Batigalhia、Marcelo Zaldini-Hernandes、Antônio G Ferreira、Ivani Malvestiti、Quezia B Cass

  DOI：10.1016/s0040-4020(01)00969-3

  日期：2001.11

  Aliphatic and aromatic sulfides, ketosulfides, sulfinyl acids and esters, and olefinic sulfides were oxidized to sulfoxides using oxodiperoxo complexes of molybdenum coated on silica gel (150 Å pore size) in very high yields. Complete chemoselectivity was observed for the oxidation of all functional sulfides. Sulfones were, however, the main products of the reaction when the complexes were not coated

  使用涂在硅胶上（孔径为150Å）的钼的氧代二氧杂配合物，脂肪族和芳香族硫化物，酮硫醚，亚磺酸基酸和酯以及烯属硫化物被氧化为亚砜。观察到所有功能性硫化物的氧化具有完全的化学选择性。然而，当配合物未涂覆在硅胶上时，砜是反应的主要产物。还研究了硅胶作为这些反应支持物的影响，并证明了它改变了配合物的反应性，但对配合物的优异的化学选择性不负责任。络合物[MoO（O 2）2（吡唑）（H 2 O）]被证明比[MoO（O 2）具有更高的反应性2（Opyr）（H 2 O）]。