(E/Z)-1,1-dimethoxy-3-methyl-4-(phenylthio)but-2-ene | 151158-69-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (E/Z)-1,1-dimethoxy-3-methyl-4-(phenylthio)but-2-ene
• 英文别名: 3-methyl-4-(phenylthio)-but-2-enal methyl acetal；(4,4-dimethoxy-2-methylbut-2-enyl)sulfanylbenzene
• CAS: 151158-69-9
• 化学式: C₁₃H₁₈O₂S
• 分子量: 238.351
• InChiKey: GTJRJXYFHSYXCQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  16.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (E/Z)-1,1-dimethoxy-3-methyl-4-(phenylthio)but-2-ene 在 叔丁基锂 、 对甲苯磺酸 、 原苯甲酸三甲酯 作用下， 以 乙醚 、 正戊烷 为溶剂， 反应 4.58h， 生成
  参考文献：
  名称：

  Synthesis and Cycloaddition Reactions of 1-(Arylthio)-1,3-dienes. A Combined Experimental and Theoretical Study of Bicyclic Adducts Structures

  摘要：

  A method giving simple access to various 1-(phenylthio)-4-substituted-1,3-dienes (5-10) is described. The influence of the different functionalizations introduced on the dienic systems has been tested in a set of classical [4 + 2] cycloaddition reactions. Both the endo/exo and regio selectivities have been investigated. While the endo compound is, as expected, the only or major isomer in all cases, the regio competition between sulfur and oxygen is in favor of the oxygen substituent in the case studied here, in contrast to related works. For one type of adduct, X-ray crystallographic analysis and NMR spectroscopy have been used in conjunction with ab initio and semiempirical AM1 calculations to determine the structure and conformations of products as well as the energetic pathway from the primary concave endo cycloadduct (28) to a rearranged bicyclic structure (39), The theoretical results fully support the occurrence of a photochemical [1,3] sigmatropic shift of the thiophenyl group.

  DOI：

  10.1021/jo9519120
• 作为产物：
  描述：

  3-甲基-2-丁烯醛 在 溴 、 三乙胺 、 zinc(II) chloride 作用下， 以 乙醚 为溶剂， 反应 34.47h， 生成 (E/Z)-1,1-dimethoxy-3-methyl-4-(phenylthio)but-2-ene
  参考文献：
  名称：

  Unexpected behavior of dienol thio ethers gives versatile access to a large set of functionalized dienes

  摘要：

  DOI：

  10.1021/jo00012a045

文献信息

• Conjugate-elimination on unsaturated acetals: A one-step route to functionalized 1,3-dienes.
  作者：Jacques Maddaluno、Odile Gaonac'h、Yann Le Gallic、Lucette Duhamel

  DOI：10.1016/0040-4039(95)01832-3

  日期：1995.11

  γ-Functionalized α,β-unsaturated dimethyl acelals undergo a methanol δ-elimination upon basic treatment, leading to 1,4-disubstituted 1,3-dienes in good yields and, in several cases, with high stereocontrol of the newly formed double bonds.

  γ-官能化的α，β-不饱和二甲基硬脂酸酯经过碱性处理后会被甲醇δ消除，从而以良好的收率得到1,4-二取代的1,3-二烯，在某些情况下，对新形成的双键具有高度的立体控制。
• 1-(Phenylthio)- and 1-(phenylsulfoxide)-4-alkoxy-butadienes, a new class of chiral dienes.
  作者：Odile Gaonac'h、Jacques Maddaluno、Gérard Plé、Lucette Duhamel

  DOI：10.1016/s0040-4039(00)92218-4

  日期：1992.4

  Trans-acetalization of the methyl acetal of 3-methyl-4-(phenylthio)-but-2-enal in acidic medium leads to the expected trans-acetals or their γ-elimination products (i.e. 4-alkoxy-2-methyl-1-(phenylthio)buta-1,3-dienes ), depending on the nature of the selected alcohol. Both types of compounds may be easily oxidized into the expected sulfoxides . The menthyloxy and phenyl-8-menthyloxy sulfides and sulfoxides

  3-甲基-4-（苯硫基）-丁-2-烯醛的甲基缩醛在酸性介质中的反缩醛化反应可产生预期的反缩醛或它们的γ消除产物（即4-烷氧基-2-甲基-1 -（苯硫基）丁1,3-二烯），具体取决于所选醇的性质。两种化合物都容易被氧化成预期的亚砜。已经制备了薄荷氧基和苯基-8-薄荷氧基硫化物和亚砜。
• A mild and direct oxidation of dienol thioethers into ketene dithioacetals.
  作者：Frank Freidanck、Jacques F. Maddaluno、Odile Gaonac'h、Lucette Duhamel

  DOI：10.1016/s0040-4039(00)79250-1

  日期：1993.6

  Functionalized dienol thioethers reacts with 3 eq. of thiophenol at room temperature in presence of dioxygen to give directly corresponding ketene dithioacetals in high yields.