2-亚甲基-1-氧杂螺[4.5]癸-6,9-二烯-8-酮 | 135614-74-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢呋喃
• 中文名称: 2-亚甲基-1-氧杂螺[4.5]癸-6,9-二烯-8-酮
• 英文名称: 2-methylene-1-oxaspiro<4.5>deca-6,9-dien-8-one
• 英文别名: 2-Methylidene-1-oxaspiro[4.5]deca-6,9-dien-8-one
• CAS: 135614-74-3
• 化学式: C₁₀H₁₀O₂
• 分子量: 162.188
• InChiKey: RUWXBCQAKIHPDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-亚甲基-1-氧杂螺[4.5]癸-6,9-二烯-8-酮 以 苯 为溶剂， 反应 0.33h， 以75%的产率得到spiro<4.5>deca-6,9-diene-2,8-dione
  参考文献：
  名称：

  Efficient synthesis of vinyl ethers of spiroquinol ketals and their high-yield photochemical oxygen-to-carbon [1,3]-shift to spiro-fused 2,5-cyclohexadienones

  摘要：

  An efficient route to spiroquinol vinyl ethers involves addition of a 1-lithio-2-(trimethylsilyl)acetylene-substituted benzene to the monoethylene ketal of benzoquinone followed by desilylation/cyclization of the resulting product to give vinyl ethers of spiroquinol ketals. A high-yield photochemical conversion of these vinyl ethers of spiroquinol ketals to ketals of spiro-fused 2,5-cyclohexadienones has been developed. A complication in some of these photochemical reactions is formation of secondary products from light absorbed by the product, spiro dienone ketals. This has been solved by conducting the reaction in the presence of piperylene, which quenches the triplet-state chemistry of the product spiro dienone ketal without altering the singlet excited-state chemistry of the quinol ketal vinyl ether. The quantum yield for the photochemical [1,3]-shift reaction in a methyl-substituted vinyl ether is 0.4. Finally, irradiation of quinol spiro vinyl ethers was also observed to give spiro dienones in good yields. Although the spiro dienone is absorbing light in competition with starting quinol vinyl ether in this system, a high yield of product was obtained. The unexpected photochemical stability of these spiro dienones is discussed. The chemistry reported herein establishes an efficient high-yield route to spiro-fused 2,5-cyclohexadienones and their ketals under very mild conditions.

  DOI：

  10.1021/jo00027a017
• 作为产物：
  描述：

  4-(3-butynyl)-4-hydroxycyclohexa-2,5-dienone 在 丁二酰亚胺 、 三乙胺 、 mercury dichloride 作用下， 以 苯 为溶剂， 反应 0.08h， 以65%的产率得到2-亚甲基-1-氧杂螺[4.5]癸-6,9-二烯-8-酮
  参考文献：
  名称：

  Spiro-fused 2,5-cyclohexadienones from thermal 1,3-shifts in quinol vinyl ethers. Reactions in nonbenzenoid systems and limitations of the chemistry

  摘要：

  Addition of functionalized organolithium compounds to quinone monoketals furnished 4-hydroxy-2,5-cyclo-hexadienone derivatives. The 4-hydroxyl group of these molecules was then transformed into a vinyl ether, and the thermal [1,3]-shift chemistry of these functionalized vinyl ethers was studied. In dienone derivatives wherein a [3,3]-sigmatropic shift was not stereoelectronically possible, these molecules underwent thermal and photochemical [1,3]-oxygen-to-carbon migration, affording spiro-2,5-cyclohexadienones in good yield. However, for compounds in which the [3,3]-shift involving the vinyl ether was possible, this reaction occurred at or below room temperature. 1,5-Cyclooctadienebis(methyldiphenylphosphine)iridium hexafluorophosphate was found to be an especially efficient catalyst for the allyl-to-vinyl ether isomerization in these systems.

  DOI：

  10.1021/jo00021a037

文献信息

• Spiro-fused 2,5-cyclohexadienones from thermal 1,3-shifts in quinol vinyl ethers. Reactions in nonbenzenoid systems and limitations of the chemistry
  作者：John S. Swenton、David Bradin、Bradley D. Gates

  DOI：10.1021/jo00021a037

  日期：1991.10

  Addition of functionalized organolithium compounds to quinone monoketals furnished 4-hydroxy-2,5-cyclo-hexadienone derivatives. The 4-hydroxyl group of these molecules was then transformed into a vinyl ether, and the thermal [1,3]-shift chemistry of these functionalized vinyl ethers was studied. In dienone derivatives wherein a [3,3]-sigmatropic shift was not stereoelectronically possible, these molecules underwent thermal and photochemical [1,3]-oxygen-to-carbon migration, affording spiro-2,5-cyclohexadienones in good yield. However, for compounds in which the [3,3]-shift involving the vinyl ether was possible, this reaction occurred at or below room temperature. 1,5-Cyclooctadienebis(methyldiphenylphosphine)iridium hexafluorophosphate was found to be an especially efficient catalyst for the allyl-to-vinyl ether isomerization in these systems.
• Efficient synthesis of vinyl ethers of spiroquinol ketals and their high-yield photochemical oxygen-to-carbon [1,3]-shift to spiro-fused 2,5-cyclohexadienones
  作者：John S. Swenton、Andrew Callinan、Shaopeng Wang

  DOI：10.1021/jo00027a017

  日期：1992.1

  An efficient route to spiroquinol vinyl ethers involves addition of a 1-lithio-2-(trimethylsilyl)acetylene-substituted benzene to the monoethylene ketal of benzoquinone followed by desilylation/cyclization of the resulting product to give vinyl ethers of spiroquinol ketals. A high-yield photochemical conversion of these vinyl ethers of spiroquinol ketals to ketals of spiro-fused 2,5-cyclohexadienones has been developed. A complication in some of these photochemical reactions is formation of secondary products from light absorbed by the product, spiro dienone ketals. This has been solved by conducting the reaction in the presence of piperylene, which quenches the triplet-state chemistry of the product spiro dienone ketal without altering the singlet excited-state chemistry of the quinol ketal vinyl ether. The quantum yield for the photochemical [1,3]-shift reaction in a methyl-substituted vinyl ether is 0.4. Finally, irradiation of quinol spiro vinyl ethers was also observed to give spiro dienones in good yields. Although the spiro dienone is absorbing light in competition with starting quinol vinyl ether in this system, a high yield of product was obtained. The unexpected photochemical stability of these spiro dienones is discussed. The chemistry reported herein establishes an efficient high-yield route to spiro-fused 2,5-cyclohexadienones and their ketals under very mild conditions.