spiro<2,5-cyclohexadiene-1,1'-<1H>indene>-3'(2'H),4-dione 4-ethylene acetal | 126084-15-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: spiro<2,5-cyclohexadiene-1,1'-<1H>indene>-3'(2'H),4-dione 4-ethylene acetal
• 英文别名: spiro[2,5-cyclohexadiene-1,1'-[1H]indene]-3'(2'H),4-dione 4-ethylene acetal
• CAS: 126084-15-9
• 化学式: C₁₆H₁₄O₃
• 分子量: 254.285
• InChiKey: NUCQBAIWBXBEOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  spiro<2,5-cyclohexadiene-1,1'-<1H>indene>-3'(2'H),4-dione 4-ethylene acetal 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以100%的产率得到spiro[2H-indene-3,4'-cyclohexa-2,5-diene]-1,1'-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：

  邻碘溴苯 在 bis-triphenylphosphine-palladium(II) chloride 、 18-冠醚-6 potassium fluoride 、 copper(l) iodide 、 正丁基锂 、 间戊二烯 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 124.17h， 生成 spiro<2,5-cyclohexadiene-1,1'-<1H>indene>-3'(2'H),4-dione 4-ethylene 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

文献信息

• Thermal and photochemical rearrangements of cyclopropyl ethers of p-quinols. Competing reaction pathways leading to five- and six-membered ring spirocyclic ketones
  作者：Timothy N. Biggs、John S. Swenton

  DOI：10.1021/jo00047a006

  日期：1992.10

  Cyclopropyl ethers of p-quinols were prepared by reaction of 3"-methylenedispiro[1,3-dioxolone-2,1'-[2,5]-cyclohexadiene-4',1"(3"H)-isobenzofuran] and the associated ketone with ethyl diazoacetate/rhodium(II) acetate and diethylzinc/methylene iodide, respectively, and their thermal and photochemical rearrangements were studied. One major process at 180-200-degrees-C is cleavage of the carbon-oxygen bond at the spiro center of the quinol to give a phenoxy and cyclopropoxy radical pair. A cyclopropylcarbinyl-like opening of the latter radical followed by recombination of the ring-opened radical with the phenoxy radical resulted in formation of a six-membered ring spirocyclic ketone. The other major thermal process for the cyclopropyl ether is conveniently viewed as ring-opening of the cyclopropane ring without breakage of the quinol carbon-oxygen bond followed by a hydrogen shift to afford a functionalized vinyl ether. This compound reacts under the thermal conditions to afford as the final product the five-membered ring spirocyclic ketone. Interestingly, the importance of these two competing pathways is influenced by the stereochemistry of ester substituents on the cyclopropane ring. Two major processes have been established in the photochemistry of these cyclopropyl ethers of p-quinols. One is rearrangement to the same six-membered ring spirocyclic ketone as discussed above. The second process is photolysis to a styrene derivative and a carbene.
• WANG, SHAOPENG;CALLINAN, ANDREW;SWENTON, JOHN S., J. ORG. CHEM., 55,(1990) N, C. 2272-2274
  作者：WANG, SHAOPENG、CALLINAN, ANDREW、SWENTON, JOHN S.

  DOI：——

  日期：——
• Biggs Timothy N., Swenton John S., J. Org. Chem., 57 (1992) N 21, S 5568- 5573
  作者：Biggs Timothy N., Swenton John S.

  DOI：——

  日期：——
• Photochemical 1,3-oxygen-to-carbon migrations. An efficient, high-yield route to protected spirodienones
  作者：Shaopeng Wang、Andrew Callinan、John S. Swenton

  DOI：10.1021/jo00295a003

  日期：1990.4