2-Methyl-2-hepten-5-yn-4-one | 103576-51-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Methyl-2-hepten-5-yn-4-one
• 英文别名: 2-methyl-2-hepten-5-in-4-one；2-Methylhept-2-en-5-yn-4-one
• CAS: 103576-51-8
• 化学式: C₈H₁₀O
• 分子量: 122.167
• InChiKey: BAJLPFGJIFTAIY-UHFFFAOYSA-N

物化性质

• 沸点：
  175.5±23.0 °C(Predicted)
• 密度：
  0.908±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-Methyl-2-hepten-5-yn-4-one 在 collidine p-toluenesulfonate 作用下， 以76%的产率得到3,5-二甲基苯酚
  参考文献：
  名称：

  Enynones in organic synthesis. III. A novel synthesis of phenols

  摘要：

  DOI：

  10.1016/s0040-4039(00)88463-4
• 作为产物：
  描述：

  3,3-二甲基丙烯酸 在 N,N'-羰基二咪唑 作用下， 生成 2-Methyl-2-hepten-5-yn-4-one
  参考文献：
  名称：

  (±)-Bisabosqual A 的全合成

  摘要：

  新型角鲨烯合酶抑制剂 bisabosqual A 的合成是通过 14 个步骤（最长的线性序列）从市售起始材料完成的。双收敛路线采用串联5-exo、6-exo自由基环化作为关键步骤。该反应组装了完全功能化的四环核心并引入了三个立体中心。其他有效的转化是高级烯酮中间体的区域选择性脱氧以及在酯存在下将三甲基铝化学和非对映选择性加成到酮上。

  DOI：

  10.1021/ja3108577

文献信息

• Die Gasphasen-Flussthermolyse von 1-Isobutenyl- und 2-Methylphenyl-alkinyl-ketonen. Eine Synthese von Methylenomycin B
  作者：Manuel Koller、Martin Karpf、Andr� S. Dreiding

  DOI：10.1002/hlca.19860690306

  日期：1986.5.7

  The Gas-Flow Thermolysis of 1-Isobutenyl Alkynyl and 2-Methylphenyl Alkynyl Ketones. Synthesis of Methylenomycin B

  1-异丁烯基炔基和2-甲基苯基炔基酮的气流热解。甲基霉素B的合成
• The flow thermolyses of 1-isobutenyl alkynyl- and 2-methylphenyl alkynyl ketones. Synthesis of methylenomycin B
  作者：Manuel Roller、Martin Karpf、André S. Dreiding

  DOI：10.1016/s0040-4039(00)83928-3

  日期：1986.1

  lead to phenols and to cyclopentenones. The results are explained by a 5-ring carbene process (the known α-alkynone cyclization) and a 6-ring as well as a 5-ring addition process. The latter two (novel) processes are thought to be intramolecular “CH to CC additions” in two directions. The 5-ring addition process was used in a short (but low yield) synthesis of methylenomycin B.

  发现1-异丁烯基炔基和2-甲基苯基炔基酮的气流热解可导致苯酚和环戊烯酮。通过5-环卡宾法（已知的α-炔酮环化）和6-环以及5-环加成法解释了该结果。后两个（新的）过程被认为是两个方向上的分子内“CH至CC加成”。5环加成工艺用于甲基霉素（B）的短暂合成（但收率很低）。
• Enynones in Organic Synthesis. 6. Synthesis of Spirocyclic Methylenecyclopentenones and Analogs of the Methylenomycin Class of Antibiotics. Mechanism of Phenol Catalysis
  作者：Peter A. Jacobi、Lisa M. Armacost、Harry L. Brielmann、Reginald O. Cann、Joseph I. Kravitz、Michael J. Martinelli

  DOI：10.1021/jo00097a035

  日期：1994.9

  Spirocyclic methylenecyclopentenones of general structure 18 were prepared in a single step from bis-acetylenic alcohols 29 by a process involving initial oxy-Cope rearrangement to afford (Z)-enynones 30-Z followed by electrocyclic ring closure. Mechanistic studies indicate that the initial step leading from 30-Z to 18 is a thermal 1,5-prototropic shift to afford dienols which can cyclize by a symmetry-allowed (pi(4)s + sigma(2)s + pi(2)a) process. This last step is catalyzed by certain phenols having low oxidation potentials, most likely by a mechanism involving single electron transfer. Dramatic rate enhancements were also observed for the cyclization of simple enynones 37 to methylenecyclopentenones 39 upon catalysis with either a-tocopherol (vitamin E, 40) or tert-butylcatechol(41). Further enhancements in both rate and yield were obtained under conditions of photoassisted single electron transfer (PET), which afforded 39 in yields of 80-98%.
• Enynones in Organic Synthesis. 8. Synthesis of the Antimicrobial-Cytotoxic Agent Juncusol and Members of the Effusol Class of Phenols
  作者：Peter A. Jacobi、Joseph I. Kravitz、Wanjun Zheng

  DOI：10.1021/jo00107a017

  日期：1995.1

  Two new syntheses of phenols have been developed which have been utilized in an efficient preparation of the antimicrobial-cytotoxic agent juncusol (22) and several members of the effusol (23) class of phenols. These results complement our earlier studies with enynones of type 42 and provide for the highly efficient conversion of 42 to either methylenecyclopentenones 45 or phenols of type 47 or 54 with virtually 100% selectivity.
• Enynones in organic synthesis. II. An electron transfer mediated synthesis of methylenecyclopentenones
  作者：Peter A Jacobi、Lisa M Armacost、Joseph I Kravitz、Michael J Martinelli

  DOI：10.1016/s0040-4039(00)88462-2

  日期：1988.1