α-chloropropargyl phenyl sulfide | 13865-10-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: α-chloropropargyl phenyl sulfide
• 英文别名: Benzene, [(1-chloro-2-propynyl)thio]-；1-chloroprop-2-ynylsulfanylbenzene
• CAS: 13865-10-6
• 化学式: C₉H₇ClS
• 分子量: 182.674
• InChiKey: SYURRAFSUAPREJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  α-chloropropargyl phenyl sulfide 在 tetramethylguanidinum azide 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以95%的产率得到(1-azidoprop-2-ynylsulfanyl)benzene
  参考文献：
  名称：

  带有强受体取代基的第一炔丙基叠氮化物及其有效转化为烯丙基叠氮化物：取代基电子效应对炔丙基叠氮化物反应性的影响

  摘要：

  我们已成功合成含有 1- 或 3- 苯硫基官能团的炔丙基叠氮化物。将它们的硫原子选择性氧化为亚砜和砜，可以获得第一个带有受体取代基的炔丙基叠氮化物。有趣的是，后者炔丙基叠氮化物的质子重排导致形成具有相对高稳定性和中等至良好产率的烯基叠氮化物。含有苯硫基官能团的炔丙基叠氮化物在亲核试剂存在下反应，通过短寿命的烯基叠氮化物提供预期的 N-未取代的 1,2,3-三唑。这些结果与相应的亚砜和砜的结果完全不同，它们在类似条件下反应生成相应的双（三唑并）吡嗪衍生物或生成新取代的乙烯基叠氮化物。后一种化合物可以成功地用作原料，提供获得氮丙啶的途径。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  DOI：

  10.1002/ejoc.200500135
• 作为产物：
  描述：

  苯基丙炔基硫醚 在 N-氯代丁二酰亚胺 作用下， 以 四氯化碳 为溶剂， 反应 16.0h， 生成 α-chloropropargyl phenyl sulfide
  参考文献：
  名称：

  Arnecke, Ralf; Groth, Ulrich; Koehler, Thomas, Liebigs Annalen der Chemie, 1994, # 9, p. 891 - 894

  摘要：

  DOI：

文献信息

• Control of Skeletal Connectivity in Indium Promoted Reactions:  1,2-Additions and Cope Rearrangements En Route to Lactol Formation
  作者：Thomas Mitzel、Joe Wzorek、Annie Troutman、Kristen Allegue

  DOI：10.1021/jo070020k

  日期：2007.4.1

  Indium promoted coupling reactions between propargyl aldehydes (3) and allyl halides under aqueous and organic conditions are reported. Coupling reactions under aqueous conditions occur via 1,2-addition with excellent yields to afford 4-hydroxy-1-ene-5-ynes (8). Coupling reactions under organic conditions also add in a 1,2-fashion, but the initial products can be induced to undergo oxy-Cope rearrangements giving 2,5-hexadienals (9). Oxy-Cope rearrangement of 8 followed by a secondary addition step under highly basic conditions leads to lactol formation (10) in good to excellent yields. This paper reveals the versatility and control of product formation which may be attained when working with propargyl aldehyde (3) and allyl halide systems under indium promoted coupling conditions.
• Use of α-chlorosulfides in indium promoted CC couplings: easy entry into the stereoselective formation of epoxy alkynes
  作者：Gregory Engstrom、Meisha Morelli、Carolyn Palomo、Thomas Mitzel

  DOI：10.1016/s0040-4039(99)01152-1

  日期：1999.8

  The use of alpha-chlorosulfide compounds to control stereoselectivity in indium promoted C-C couplings occurs smoothly at room temperature under aqueous and mixed aqueous/organic conditions. Use of the halide to control syn/anti ratios simplifies the indium promoted coupling with respect to earlier studies and is used to gain entry into stereocontrolled epoxy alkynes in good yields. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Use of<i>N</i>-Methylformamide as a Solvent in Indium-Promoted Barbier Reactions en Route to Enediyne and Epoxy Diyne Formation: Comparison of Rate and Stereoselectivity in C−C Bond-Forming Reactions with Water
  作者：Kwame Frimpong、Joseph Wzorek、Claire Lawlor、Katharine Spencer、Thomas Mitzel

  DOI：10.1021/jo900763u

  日期：2009.8.21

  Indium-promoted coupling reactions between propargyl aldehydes (1) and alpha-chloropropargylphenyl sulfide are reported. Although water has been shown to accelerate indium metal promoted reactions, the reverse pattern was observed in this series. Use of N-methylformamide (NMF), which has riot previously been a solvent known for use in indium-promoted reactions, afforded ail acceleration or these Barbier-style reactions compared to water. Indium-promoted reactions in this study also showed excellent regiocontrol and good stereocontrol, allowing for easy entry into the formation of epoxydiyne and enediyne skeletal structures, This paper also describes use of the Barbier Coupled product (2) as a new, and easy, entry into the formation of enediyne and epoxydiyne skeletal structures.
• The Versatility of α-Chloropropargyl Phenyl Sulfide Affords High Stereo- and Regioselectivities in Indium-Promoted Coupling Reactions under Mild Conditions
  作者：Thomas M. Mitzel、Carolyn Palomo、Keith Jendza

  DOI：10.1021/jo015992l

  日期：2002.1.1

  Coupling reactions between alpha-chloropropargyl phenyl sulfide (11) and a series of aldehydes under aqueous conditions are reported. Not only is good stereoselectivity observed between syn and anti isomeric products, but excellent regioselectivity is also witnessed. In reactions using indium. metal as a promoter, the propargyl functionality (12) is retained, unlike the use of more traditional metals that result in formation of products containing a mixture of both propargyl (12) and allene (13) moieties. The reaction is postulated to proceed via either a chelated or nonchelated route, controlled by the presence or absence of indium (III) chloride, and may be used to create synthetically useful building blocks. The formation of epoxyalkyne (14) molecules, which are found in many natural products and have wide use as synthetic templates, is presented as one example.
• US4133964A
  申请人：——

  公开号：US4133964A

  公开（公告）日：1979-01-09