3-(prop-2-ynylsulfanyl)cycloheptene | 208759-63-1

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: 3-(prop-2-ynylsulfanyl)cycloheptene
• 英文别名: 3-Prop-2-ynylsulfanylcycloheptene
• CAS: 208759-63-1
• 化学式: C₁₀H₁₄S
• 分子量: 166.287
• InChiKey: HGAZFKQHXJBDJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  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：
  0.6
• 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：

  3-(prop-2-ynylsulfanyl)cycloheptene 在 copper(l) iodide 、 N-甲基吲哚酮 、 镍 、 potassium carbonate 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 27.67h， 生成 (3RS,3aRS,8aRS)-3-methyl-3-phenyl-octahydro-azulen-1-one
  参考文献：
  名称：

  Ready Access to Bicyclo[5.3.0]decan-1-ones and to Bicyclo[6.3.0]undecan-1-ones by Intramolecular Pauson−Khand Reactions Using a Temporary Sulfur Bridge

  摘要：

  An intramolecular Pauson-Khand-based route to octahydroazulenones and decahydrocyclopentacyclooctenones is described. The amine oxide-induced cycloaddition of the dicobalt hexacarbonyl complexes of the sulfur-bridged enynes 1 and 2 leads to the exclusive formation of the tricyclic cyclopentenones 3 and 4, respectively. This stereochemical outcome, which implies that the olefin moieties in both 1 and 2 react by the less substituted alpha-face, is rationalized on the basis of the steric requirements of the putative cobaltacyclic intermediates of the Pauson-Khand reaction. The totally stereoselective conjugate addition of methyl or phenyl groups to enones 3 and 4, effected by the corresponding lithium diorganocuprates, and the subsequent reductive desulfurization with Raney nickel in refluxing ethanol, lead to the cis-bicyclo[5.3.0]decan-2-ones 5a,b and to the cis-bicyclo[6.3.0]undecan-2-one 6, respectively, in good overall yields. The stereochemistry of intermediates 3, 4, 7b, 8, and 9 has been firmly established with the aid of both NOESY experiments and AM1 MO semiempirical MO calculations.

  DOI：

  10.1021/jo9722257
• 作为产物：
  描述：

  3-溴环庚烯 在 caesium carbonate 、 四乙烯五胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 3-(prop-2-ynylsulfanyl)cycloheptene
  参考文献：
  名称：

  闪真空热解——不稳定环烯硫酮的合成和表征

  摘要：

  环烯基烯丙基（或炔丙基）硫化物 8、9、12 和 13 的快速真空热解 (FVT) 作为主要热途径导致共轭环烯硫酮 1、3 和 5，由逆烯反应产生。这些反应性硫酮，因此在大约。70% 的产率已通过质谱在气相中进行表征，并在低温下通过 IR、UV/Vis 和 NMR 光谱进行表征。加热后 1、3 和 5 的聚合通常比其他尝试的反应更快，并且只有与重氮甲烷的 [2 + 3] 偶极环加成以低产率导致，除了聚合材料外，从环戊烯硫酮 1. 硫化物 10 和 11 的 FVT 中预期的非共轭环烯硫酮 2 和 4 的获得仅通过 –196 °C 下的 UV/Vis 光谱证实，由于它们的快速烯硫醇化。在大环硫化物 14 的情况下，双键的 (E) 几何结构有利于竞争性逆烯反应，生成环十二烯和丙炔；另一方面，三环偕二硫醇 15（环丁烯硫酮 (7) 的可能前体）的 FVT 导致通过 7 的热开环获得乙烯基硫酮 (18)。

  DOI：

  10.1002/(sici)1099-0690(199904)1999:4<869::aid-ejoc869>3.0.co;2-o

文献信息

• Access to New Reactive Unsaturated Cycloalkenethiones by Flash Vacuum Thermolysis
  作者：Emmanuelle Briard、Jocelyne Levillain、Jean-Louis Ripoll

  DOI：10.1080/10426509908546484

  日期：1999.1

  The reactive conjugated cycloalkenethiones (3, 4, 5) have been synthesized from the corresponding cycloalkenylsulfanyl compounds under flash vacuum thermolysis (FVT) conditions. The nonconjugated cycloalkenethiones (8, 9) were prepared in the same way, the tautomerisation into cycloalkadienethiols (10, 11) occurred at 77 K. As for the cyclobutenethione 13, only the ring opening products were observed

  反应性共轭环烯硫酮 (3, 4, 5) 在快速真空热解 (FVT) 条件下由相应的环烯基硫烷基化合物合成。非共轭环烯硫酮 (8, 9) 以相同的方式制备，互变异构化为环二烯硫醇 (10, 11) 发生在 77 K。至于环丁烯硫酮 13，仅在 77 K 下观察到开环产物。
• Ready Access to Bicyclo[5.3.0]decan-1-ones and to Bicyclo[6.3.0]undecan-1-ones by Intramolecular Pauson−Khand Reactions Using a Temporary Sulfur Bridge
  作者：Jaume Castro、Albert Moyano、Miquel A. Pericàs、Antoni Riera

  DOI：10.1021/jo9722257

  日期：1998.5.1

  An intramolecular Pauson-Khand-based route to octahydroazulenones and decahydrocyclopentacyclooctenones is described. The amine oxide-induced cycloaddition of the dicobalt hexacarbonyl complexes of the sulfur-bridged enynes 1 and 2 leads to the exclusive formation of the tricyclic cyclopentenones 3 and 4, respectively. This stereochemical outcome, which implies that the olefin moieties in both 1 and 2 react by the less substituted alpha-face, is rationalized on the basis of the steric requirements of the putative cobaltacyclic intermediates of the Pauson-Khand reaction. The totally stereoselective conjugate addition of methyl or phenyl groups to enones 3 and 4, effected by the corresponding lithium diorganocuprates, and the subsequent reductive desulfurization with Raney nickel in refluxing ethanol, lead to the cis-bicyclo[5.3.0]decan-2-ones 5a,b and to the cis-bicyclo[6.3.0]undecan-2-one 6, respectively, in good overall yields. The stereochemistry of intermediates 3, 4, 7b, 8, and 9 has been firmly established with the aid of both NOESY experiments and AM1 MO semiempirical MO calculations.
• Flash Vacuum Thermolysis – Synthesis and Characterization of Unstabilized Cycloalkenethiones
  作者：Emmanuelle Briard、Jocelyne Levillain、Jean-Louis Ripoll、Yves Dat、Albert Marcual、Catherine Lange

  DOI：10.1002/(sici)1099-0690(199904)1999:4<869::aid-ejoc869>3.0.co;2-o

  日期：1999.4

  The flash vacuum thermolysis (FVT) of cycloalkenyl allyl (or propargyl) sulfides 8, 9, 12, and 13 led, as the main thermal pathway, to the conjugated cycloalkenethiones 1, 3, and 5, resulting from a retro-ene reaction. These reactive thioketones, thus obtained in ca. 70% yield, have been characterized in the gas phase by mass spectrometry, and at low temperature by IR, UV/Vis and NMR spectroscopy.

  环烯基烯丙基（或炔丙基）硫化物 8、9、12 和 13 的快速真空热解 (FVT) 作为主要热途径导致共轭环烯硫酮 1、3 和 5，由逆烯反应产生。这些反应性硫酮，因此在大约。70% 的产率已通过质谱在气相中进行表征，并在低温下通过 IR、UV/Vis 和 NMR 光谱进行表征。加热后 1、3 和 5 的聚合通常比其他尝试的反应更快，并且只有与重氮甲烷的 [2 + 3] 偶极环加成以低产率导致，除了聚合材料外，从环戊烯硫酮 1. 硫化物 10 和 11 的 FVT 中预期的非共轭环烯硫酮 2 和 4 的获得仅通过 –196 °C 下的 UV/Vis 光谱证实，由于它们的快速烯硫醇化。在大环硫化物 14 的情况下，双键的 (E) 几何结构有利于竞争性逆烯反应，生成环十二烯和丙炔；另一方面，三环偕二硫醇 15（环丁烯硫酮 (7) 的可能前体）的 FVT 导致通过 7 的热开环获得乙烯基硫酮 (18)。