2',3'-Dihydrospiro<2,5-cyclohexadiene-1,1'(4'H)-naphthalene>-4,4'-dione | 143591-50-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 2',3'-Dihydrospiro<2,5-cyclohexadiene-1,1'(4'H)-naphthalene>-4,4'-dione
• 英文别名: Spiro[2,3-dihydronaphthalene-4,4'-cyclohexa-2,5-diene]-1,1'-dione
• CAS: 143591-50-8
• 化学式: C₁₅H₁₂O₂
• 分子量: 224.259
• InChiKey: BNINCSHTHYFHRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  Dispiro<2,5-cyclohexadiene-1,1'-phthalane-3',1''cyclopropan>-4-one 以 苯 为溶剂， 反应 17.0h， 以55%的产率得到2',3'-Dihydrospiro<2,5-cyclohexadiene-1,1'(4'H)-naphthalene>-4,4'-dione
  参考文献：
  名称：

  Thermal and photochemical rearrangements of cyclopropyl ethers of p-quinols. Competing reaction pathways leading to five- and six-membered ring spirocyclic ketones

  摘要：

  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.

  DOI：

  10.1021/jo00047a006

文献信息

• 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：——
• 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.