spiro[2H-indene-3,4'-cyclohexa-2,5-diene]-1,1'-dione | 120254-82-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: spiro[2H-indene-3,4'-cyclohexa-2,5-diene]-1,1'-dione
• CAS: 120254-82-2
• 化学式: C₁₄H₁₀O₂
• 分子量: 210.232
• InChiKey: QUCQSKXVOYKMJZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  4-(2-acetylphenyl)phenol 在 lithium perchlorate 、 四氯化钛 、 三乙胺 作用下， 以 甲醇 、 溶剂黄146 、 乙腈 为溶剂， 反应 1.5h， 生成 spiro[2H-indene-3,4'-cyclohexa-2,5-diene]-1,1'-dione
  参考文献：
  名称：

  Intramolecular Anodic Carbon−Carbon Bond Formation from Oxidized Phenol Intermediates. Effect of Oxygenated Substituents on the Yields of Spiro Dienones in Electrochemical and Iodobenzene Diacetate Oxidations

  摘要：

  The single-cell, constant-current anodic oxidation of a series of 4-(2-alkenylaryl)phenols was studied in which the aryl substituents were 2-vinyl-4,5-dimethoxy, 6a; 2-propenyl-4,5-dimethoxy, 9a; 2-vinyl-4,5-methylenedioxy, 6b; 2-propenyl-4,5-methylenedioxy, 9b; 2-vinyl-4-methoxy, 6c; 2-propenyl-4-methoxy, 9c; 2-vinyl-5-methoxy, 6d; and 2-propenyl-5-methoxy, 9d. Two compounds having methoxyl groups on the phenolic ring were also studied: 4-(2'-propenylphenyl)-2-methoxyphenol, 9e, and 4-(2'-propenylphenyl)-3-methoxyphenol, 9f. A novel synthetic route to the methoxy compounds 6c, 9c, 6d, and 9d was developed. This involved as a key step the MAD, bis(2,6-ditert-butyl-4-methylphenoxide)methylaluminum, mediated addition of organolithium and Grignard reagents to functionalize quinol ether derivatives. Anodic oxidation of compounds 6a, 9a, 9b, 6c, 9c, and 9d gave good yields of spiro dienones arising from trapping of the phenoxonium ion by the alkenyl side chain followed by reaction of the resulting cation with methanol. The products from the electrochemical oxidation of these 4-(2'-alkenylaryl)phenols were compared with those obtained from the iodobenzene diacetate oxidations. In general, the compounds that gave good yields of spiro dienones from electrochemical oxidation gave good yields from iodobenzene diacetate oxidations. However, there were two cases in which the results of the two oxidations did not parallel each other. Whereas anodic oxidation of 9f gave a low yield of spiro dienone, the iodobenzene diacetate route gave a 74% yield of this product. In the case of 9d, the opposite effect was noted: the electrochemical route gave a higher yield than did the iodobenzene diacetate oxidation.

  DOI：

  10.1021/jo951799d

文献信息

• Spirodienones via a thermal uncatalyzed [1,3]-oxygen-to-carbon migration
  作者：Gary W Morrow、Shaopeng Wang、John S Swenton

  DOI：10.1016/0040-4039(88)85184-0

  日期：1988.1

  Exocyclic vinyl ethers derived from -quinols, readily available from aryllithium addition to quinone monoketals, undergo high-yield thermal [1,3]-oxygen-to-carbon migration, yielding spirodienones.

  衍生自-喹诺醇的环外乙烯基醚（可从芳基锂加成醌单缩酮）容易地进行高产率的热[1,3]-氧-碳迁移，从而生成螺二烯酮。
• Spiro-fused 2,5-cyclohexadienones from the thermal 1,3-alkyl migrations of quinol vinyl ethers. A strategy for conversion of a carbonyl carbon to a quaternary carbon
  作者：Shaopeng Wang、Gary W. Morrow、John S. Swenton

  DOI：10.1021/jo00283a035

  日期：1989.10
• 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.
• 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.
• MORROW, GARY W.;WANG, SHAOPENG;SWENTON, JOHN S., TETRAHEDRON LETT., 29,(1988) N 28, C. 3441-3444
  作者：MORROW, GARY W.、WANG, SHAOPENG、SWENTON, JOHN S.

  DOI：——

  日期：——