6,7,8,9-tetrahydro-9-(2-propenyl)-5,9-methanobenzocyclooctene-10(5H)-one | 139606-57-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 6,7,8,9-tetrahydro-9-(2-propenyl)-5,9-methanobenzocyclooctene-10(5H)-one
• 英文别名: 9-Prop-2-enyltricyclo[7.3.1.02,7]trideca-2,4,6-trien-8-one
• CAS: 139606-57-8
• 化学式: C₁₆H₁₈O
• 分子量: 226.318
• InChiKey: PQXSSEYHDAPGJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-Allyl-1-phenyl-hept-6-en-1-one 在 ammonium cerium(IV) nitrate 、 碳酸氢钠 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 6.0h， 生成 6,7,8,9-tetrahydro-9-(2-propenyl)-5,9-methanobenzocyclooctene-10(5H)-one
  参考文献：
  名称：

  Oxidative cyclization of .delta.,.epsilon.- and .epsilon.,.zeta.-unsaturated enol silyl ethers and unsaturated siloxycyclopropanes

  摘要：

  Oxidative cyclization of delta,epsilon- and epsilon,zeta-unsaturated enol silyl ethers 4a and 4b with cupric triflate and cuprous oxide or ceric ammonium nitrate and sodium bicarbonate in acetonitrile provides the tricyclic ketones 5a and 5b stereoselectively. These cyclizations proceed by oxidation of 4 to the cation radical 24 followed by cyclization of 24 to cation radical 27. This cation radical undergoes a second cyclization to give cation radical 30, which loses the silyl group, undergoes a second oxidation, and loses a proton to give 5. The stereochemistry of the cycloadduct is controlled by the stereochemistry of the enol ether. The Z-enol methyl ether (Z)-65 leads mainly to 5a while the E-enol methyl ether (E)-65 leads mainly to 6a. The oxidative cyclizations of 7, 13, 21, and 43 are also described. Oxidation of alpha-allyl silyl enol ethers 34a and 34b leads mainly to oxidation without cyclization to give the alpha,beta-unsaturated ketones 36a and 36b. Oxidative cyclizations of alkynyl silyl enol ethers 56 and 60 lead to 15 and 64, respectively. Oxidation of siloxycyclopropane 74 with Cu(BF4)2 generates cation radical 75, which cyclizes to 76, which is oxidized to give 21% of cyclopentane 77. This suggests that cation radicals are intermediates in the oxidative dimerization of siloxycyclopropanes.

  DOI：

  10.1021/jo00034a038