(2-溴烯丙基)(苯基)硫烷 | 139930-06-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 中文名称: (2-溴烯丙基)(苯基)硫烷
• 英文名称: 2-bromo-3-phenylthiopropene
• 英文别名: 2-bromoallyl phenyl sulfide；(2-bromoallyl)(phenyl)sulfane；2-bromoprop-2-enylsulfanylbenzene
• CAS: 139930-06-6
• 化学式: C₉H₉BrS
• 分子量: 229.14
• InChiKey: AOYAIWVKWABBEE-UHFFFAOYSA-N

物化性质

• 沸点：
  256.9±33.0 °C(Predicted)
• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  11
• 可旋转键数：
  3
• 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：

  (2-溴烯丙基)(苯基)硫烷 在 samarium diiodide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 3.0h， 生成 苯硫酚
  参考文献：
  名称：

  Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals

  摘要：

  Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals. Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(pi-exo)exo, 6-(pi-endo)exo, and 6-(pi-exo)exo mode, respectively. Radical 7 undergoes competitive 1,5-hydrogen translocation. Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively. Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent beta-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation. Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization). Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group. Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. alpha-Oxy(and alpha-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.

  DOI：

  10.1021/jo00128a013
• 作为产物：
  描述：

  苯硫酚 、 2,3-二溴-1-丙烯 在 sodium methylate 作用下， 以 甲醇 为溶剂， 以81%的产率得到(2-溴烯丙基)(苯基)硫烷
  参考文献：
  名称：

  自由基烯丙基化的新试剂

  摘要：

  引入了三种用于自由基烯丙基化的试剂：3-苯硫基-2-溴丙烯，2,3-双（三甲基-锡烷基）丙烯和3-三（三甲基甲硅烷基）甲硅烷基硫丙烯。

  DOI：

  10.1016/s0040-4039(00)60898-5

文献信息

• Synthesis of Sulfimides and <i>N-</i>Allyl-<i>N-</i>(thio)amides by Ru(II)-Catalyzed Nitrene Transfer Reactions of <i>N-</i>Acyloxyamides
  作者：Xinyu Zhang、Bo Lin、Jianhui Chen、Jiajia Chen、Yanshu Luo、Yuanzhi Xia

  DOI：10.1021/acs.orglett.0c04043

  日期：2021.2.5

  precursors in reactions with thioethers under the catalysis of a commercially available Ru(II) complex, from which a variety of sulfimides were synthesized efficiently and mildly. If an allyl group is contained in the thioether precursor, the [2,3]-sigmatropic rearrangement of the sulfimide occurs simultaneously and the N-allyl-N-(thio)amides were obtained as the final products. Preliminary mechanistic studies

  所述N- acyloxyamides被用作有效N-市售的Ru（II）配合物，从该多种sulfimides被有效地和温和地合成的催化下酰基氮烯的前体在反应与硫醚。如果在硫醚前体中包含烯丙基，则硫酰亚胺的[2,3]-σ重排同时发生，最终获得N-烯丙基-N-（硫代）酰胺。初步的机理研究表明，钌-类胡萝卜素物质应该是转化的关键中间体。
• Highly chemoselective synthesis of aryl allylic sulfoxides through calcium hypobromite oxidation of aryl allylic sulfides
  作者：Vittorio Pace、Laura Castoldi、Wolfgang Holzer

  DOI：10.1016/j.tetlet.2011.12.046

  日期：2012.2

  A highly chemoselective oxidation of widely substituted aryl allylic sulfides, prepared by allylation of arylthioethers with KF-Celite, to the corresponding aryl allylic sulfoxide was achieved by employing calcium hypobromite. Neither over-oxidation to sulfones nor halogenation of the aromatic rings was observed. The protocol may be successfully applied for the oxidation of substituted allylic systems

  通过使用次溴酸钙将芳基硫醚与KF-Celite烯丙基化而制备的广泛取代的芳基烯丙基硫醚高度化学选择性氧化成相应的芳基烯丙基亚砜。既未观察到砜的过度氧化也未观察到芳环的卤化。该方案可以成功地用于本身可以与氧化剂相互作用的取代的烯丙基系统（即2-卤代烯丙基）的氧化。
• Silver-catalysed Doyle–Kirmse reaction of allyl and propargyl sulfides
  作者：Paul W. Davies、Sébastien J.-C. Albrecht、Giulio Assanelli

  DOI：10.1039/b822584b

  日期：——

  The silver-catalysed Doyle–Kirmse reaction of propargyl and allyl sulfides with diazo compounds is disclosed. The carbon–carbon bond forming process proceeds with a range of substituents and functionality under mild conditions.

  公开了炔丙基和烯丙基硫与重氮化合物的银催化的Doyle-Kirmse反应。碳-碳键的形成过程在温和条件下会进行一系列取代基和官能化反应。
• Neighbouring-group Influence on the Ring Opening of 2-Aryloxymethyl-1,1,2-tribromocyclopropanes under Phase-transfer Conditions.
  作者：Einar Bakstad、Are S. Olsen、Marcel Sandberg、Leiv K. Sydnes、Bengt Långström、Shi-Ping Yan、Geng-Lin Wang、Xin-Kan Yao、Hong-Gen Wang、J. -P. Tuchagues、Mattias Ögren

  DOI：10.3891/acta.chem.scand.53-0465

  日期：——

  When a number of 2-aryloxymethyl-1,1,2-tribromocyclopropa were treated with sodium hydroxide and ethanol under phase-transfer conditions, ring opening occurred to give mixtures of acetylenic diethyl acetals and ketals in better than 80% total isolated yield. The acetylenic diethyl ketals predominated significantly and were, in some cases, almost the exclusive product. It is argued that this ketal selectivity is in part caused by hydrogen bonding between ethanol and the aryloxy group.
• New reagents for radical allylations
  作者：Dennis P. Curran、Byungwoo Yoo

  DOI：10.1016/s0040-4039(00)60898-5

  日期：1992.11

  Three reagents are introduced for radical allylations: 3-phenylthio-2-bromopropene, 2,3-bis(trimethyl-stannyl)propene, and 3-tris(trimethylsilyl)silylthiopropene.

  引入了三种用于自由基烯丙基化的试剂：3-苯硫基-2-溴丙烯，2,3-双（三甲基-锡烷基）丙烯和3-三（三甲基甲硅烷基）甲硅烷基硫丙烯。