6'-methylidenespiro[cyclohexa-2,5-diene-4,7'-cyclopenta[f][1,3]benzodioxole]-1,5'-dione | 137256-64-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 6'-methylidenespiro[cyclohexa-2,5-diene-4,7'-cyclopenta[f][1,3]benzodioxole]-1,5'-dione
• CAS: 137256-64-5
• 化学式: C₁₆H₁₀O₄
• 分子量: 266.253
• InChiKey: HISJBFKOSPDTPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  6'-methylidenespiro[cyclohexa-2,5-diene-4,7'-cyclopenta[f][1,3]benzodioxole]-1,5'-dione 在 sodium acetate 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 为溶剂， 反应 0.25h， 生成 4a,5,6,6a-tetrahydro-5-methyl-3H-<1,3>dioxolo<5,6>indeno<2,1-c>indole-3,7(4H)-dione 3-dimethyl acetal
  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：

  6''-methylenedispiro<1,3-dioxolane-2,1'-<2,5>cyclohexadiene-4',5''-<5H>indeno<5,6-d><1,3>dioxol>-7''(6''H)-one 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 以93%的产率得到6'-methylidenespiro[cyclohexa-2,5-diene-4,7'-cyclopenta[f][1,3]benzodioxole]-1,5'-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