hex-1-yn-6-yl phenyl sulfide | 82276-25-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: hex-1-yn-6-yl phenyl sulfide
• 英文别名: Hex-5-ynylsulfanylbenzene
• CAS: 82276-25-3
• 化学式: C₁₂H₁₄S
• 分子量: 190.309
• InChiKey: JXHKEURWHBQVLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  hex-1-yn-6-yl phenyl sulfide 在 Oxone 作用下， 以 水 、 乙腈 为溶剂， 反应 0.5h， 生成 (hex-5-yne-1-sulfinyl)benzene
  参考文献：
  名称：

  金催化炔基芳基亚砜转化中的 [3,3]-Sigmatropic 重排与卡宾形成：机理研究和扩展反应范围

  摘要：

  以芳基亚磺酰基为束缚氧化剂的末端炔烃的金催化分子内氧化是金化学中具有重大影响的反应，因为它向该领域引入了通过炔氧化生成金卡宾的高度有价值的概念。然而，α-氧代金卡宾在这些反应中的中介作用从未得到证实。详细的实验研究表明，此类反应性中间体参与二氢苯并硫杂环己烷的形成的可能性极小。相反，初始环化中间体的[3,3]-σ重排提供了一条反应路径，可以很容易地解释高反应效率和缺乏锍形成。然而，对于内部炔烃底物，金卡宾物质的生成变得与[3,3]-σ重排竞争。然而，这种反应性中间体不会继续提供弗里德尔-克拉夫茨型环化产物。广泛的密度泛函理论研究支持了这样的机制结论：环化产物是通过分子内[3,3]-σ重排形成的，而不是之前提出的弗里德尔-克拉夫茨型环化。凭借新的机理见解，这种多功能形成的中型含硫环烯酮的产品范围已轻松扩展到各种二氢苯并硫辛酮、四氢苯并环壬酮，甚至那些没有稠合苯环的化合物。除了金之外，Hg(OTf)2

  DOI：

  10.1021/ja401343p
• 作为产物：
  描述：

  1-chloro-4-(phenylthio)butane 、 乙炔锂乙二胺配合物 以 乙醚 、 二甲基亚砜 为溶剂， 反应 17.0h， 以40%的产率得到hex-1-yn-6-yl phenyl sulfide
  参考文献：
  名称：

  SYNTHESIS AND IN VITRO EVALUATION OF NOVEL ANTI-VARICELLA-ZOSTER VIRUS (VZV) NUCLEOSIDES

  摘要：

  A series of alkyl-aryl, -phenoxy, and -thiophenoxy bicyclic furo pyrimidine nucleosides have been successfully synthesised by Pd-coupling of 5-iodo-2'-deoxyuridine (IDU) with terminal alkynes, followed by in situ copper-cyclisation. Synthesised compounds (4a-i) showed an anti-VZV activity at low muM concentration, comparable to that of current treatment acyclovir.

  DOI：

  10.1081/ncn-100002343

文献信息

• Expanding the versatility of Schwartz' reagent: Hydrozirconation of vinylic and acetylenic acyl silanes
  作者：Bruce H. Lipshutz、Craig Lindsley、Ashok Bhandari

  DOI：10.1016/s0040-4039(00)76937-1

  日期：1994.7

  By virtue of a triisopropylsilyl acyl silane contained within a substrate undergoing hydrozirconation, chemospecificity can be realized favoring addition across the alkene or alkyne, rather than competitive 1,2-addition of hydride to the carbonyl portion of the molecule.

  通过包含在经历氢锆化的底物中的三异丙基甲硅烷基酰基硅烷，可以实现化学特异性，这有利于跨烯烃或炔烃的加成，而不是氢化物向分子的羰基部分的竞争性1,2-加成。
• Tin Radical Addition to Alkynyl Sulfides: Reactivity of the Intermediate Thioalkyl-Substituted .beta.-(Tributylstannyl)vinyl Radicals
  作者：Laura Capella、Pier Carlo Montevecchi、Daniele Nanni

  DOI：10.1021/jo00091a025

  日期：1994.6

  Phenyl and benzyl alkynyl sulfides 1a-g and 3a, phenylalkynylamines 19a,b, ethers 22a,b, and selenide 31 reacted with tributyltin radicals to give intermediate beta-stannylvinyl radicals, whose fate depended on the nature of the side chain. 4-Phenylthio-substituted but-1-en-2-yl radicals underwent stereospecific 5-exo cyclization on the adjacent phenyl ring. The resulting spirocyclohexadienyl radicals gave thiophenes and thiopyrans by carbon-sulfur bond scission or ring expansion on the exocyclic double bond, respectively. Similar behavior was exhibited by the corresponding selenium-containnig radical, which afforded a selenophene almost exclusively. (Benzylthio) alkyl-substituted radicals gave products deriving from intramolecular S(H)2 substitution at the sulfur atom, whereas propargyl sulfides yielded a stannylallene via a beta-scission reaction. No 6(or more)-membered ring closure was observed with pentynyl and hexynyl phenyl sulfides 1b,c, which gave only the (E)-addition products of tin hydride; oxygen- and nitrogen-containing vinyl radicals also gave the (E)-adducts exclusively. An interaction between the unpaired electron orbital and the empty low-energy orbitals of the heteroatom might explain why sulfur and selenium can undergo 5-exo cyclization.
• Alkyne Carbonylation by Radicals: Tin‐Radical‐Catalyzed Synthesis of α‐Methylene Amides from 1‐Alkynes, Carbon Monoxide, and Amines
  作者：Yoshitaka Uenoyama、Takahide Fukuyama、Osamu Nobuta、Hiroshi Matsubara、Ilhyong Ryu

  DOI：10.1002/anie.200461954

  日期：2005.2.4
• Chromium(III) catalyzed synthesis of allenes from propargyl derivatives via a carbometalation–elimination sequence
  作者：Gary A. Molander、Erin M. Sommers

  DOI：10.1016/j.tetlet.2005.01.143

  日期：2005.3

  The syn-carbometalation/syn-elimination of propargyl substrates to form allenes has been achieved using cationic chromium(III) catalysts activated by alkylaluminums. The mechanism and scope of this transformation are presented. (c) 2005 Elsevier Ltd. All rights reserved.
• Carboalumination/transmetalation/conjugate addition: a new catalytic copper(I)-induced process for the 1,4-delivery of vinylic groups to enones
  作者：Bruce H. Lipshutz、Stuart H. Dimock

  DOI：10.1021/jo00020a012

  日期：1991.9

  Exposure of vinylalanes, derived from carbometalations of 1-alkynes, to catalytic amounts of CuCN.2LiCl in the presence of an alpha,beta-unsaturated carbonyl group affords products of vinylic ligand transfer in a 1,4-manner.