(+/-)-(6aα,6bα,10aα,10bα)-6a-(Acetyloxy)-6a,6b,7,8,9,10,10a,10b-octahydrobenzo<3,4>cyclobuta<1,2-c>quinolin-6(5H)-one | 137793-02-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: (+/-)-(6aα,6bα,10aα,10bα)-6a-(Acetyloxy)-6a,6b,7,8,9,10,10a,10b-octahydrobenzo<3,4>cyclobuta<1,2-c>quinolin-6(5H)-one
• 英文别名: [(1R,10S,11R,16S)-9-oxo-8-azatetracyclo[8.6.0.02,7.011,16]hexadeca-2,4,6-trien-10-yl] acetate
• CAS: 137793-02-3
• 化学式: C₁₇H₁₉NO₃
• 分子量: 285.343
• InChiKey: YIHJCMCVWXRJCX-IYDIDCQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-(6aα,6bα,10aα,10bα)-6a-(Acetyloxy)-6a,6b,7,8,9,10,10a,10b-octahydrobenzo<3,4>cyclobuta<1,2-c>quinolin-6(5H)-one 在 水 、 碘 、 sodium hydride 、 potassium carbonate 、 mercury(II) oxide 作用下， 以 甲醇 、 苯 为溶剂， 反应 21.5h， 生成 5,7-Dihydro-5-methylcyclohexa<1>benzazocine-6,7-dione
  参考文献：
  名称：

  Photoinduced molecular transformations. 128. Regioselective [2 + 2] photocycloaddition of 3-acetoxyquinolin-2(1H)-one with alkenes and formation of furo[2,3-c]quinolin-4(5H)-ones, 1-benzazocine-2,3-diones, and cyclopropa[d]benz[1]azepine-2,3-diones via a .beta.-scission of cyclobutanoxyl radicals generated from the resulting [2 + 2] photoadducts

  摘要：

  We have found that [2 + 2]pi photoadducts can be obtained by the photoaddition of 3-acetoxyquinolin-2(1H)-one with acyclic and cyclic alkenes. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with 2-methylpropene, 2,3-dimethyl-2-butene, and 2-methoxypropene thus afforded regioselective head-to-tail adducts in 59-97% yields. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with cyclopentene and cyclohexene resulted in the formation of sterically disfavored cis-cisoid-cis photoadducts as the major products, with the accompanying formation of cis-transoid-cis photoadducts as the minor products in combined yields of 87 and 66%, respectively. The photolysis of the hypoiodites generated in situ from cyclobutanols derived from all of the photoadducts induced beta-scissions at the outer bonds of the corresponding cyclobutanoxyl radicals to give furo[2,3-c]quinolin-4(5H)-ones in 15-50% yields with an accompanying formation of 7- and 8-membered lactams arising from beta-scissions at the catacondensed bonds of the cyclobutanoxyl radicals in 2-62% yields. The molecular structure of one of the novel 7-membered lactams that successively fused with cyclopropane and cyclopentane rings was established to be trans-5,8,9,10,10a,10b-hexahydro-5-methylcyclopenta[3,4]cyclopropa[1,2-d]benzazepine-6,7-dione by X-ray crystallographic analysis. The pathways leading to the formation of all of these products arising from beta-scissions are discussed.

  DOI：

  10.1021/jo00028a037
• 作为产物：
  描述：

  3-羟基喹啉-2-酮 在 吡啶 作用下， 以 甲醇 为溶剂， 反应 35.0h， 生成 (+/-)-(6aα,6bα,10aα,10bα)-6a-(Acetyloxy)-6a,6b,7,8,9,10,10a,10b-octahydrobenzo<3,4>cyclobuta<1,2-c>quinolin-6(5H)-one
  参考文献：
  名称：

  Photoinduced molecular transformations. 128. Regioselective [2 + 2] photocycloaddition of 3-acetoxyquinolin-2(1H)-one with alkenes and formation of furo[2,3-c]quinolin-4(5H)-ones, 1-benzazocine-2,3-diones, and cyclopropa[d]benz[1]azepine-2,3-diones via a .beta.-scission of cyclobutanoxyl radicals generated from the resulting [2 + 2] photoadducts

  摘要：

  We have found that [2 + 2]pi photoadducts can be obtained by the photoaddition of 3-acetoxyquinolin-2(1H)-one with acyclic and cyclic alkenes. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with 2-methylpropene, 2,3-dimethyl-2-butene, and 2-methoxypropene thus afforded regioselective head-to-tail adducts in 59-97% yields. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with cyclopentene and cyclohexene resulted in the formation of sterically disfavored cis-cisoid-cis photoadducts as the major products, with the accompanying formation of cis-transoid-cis photoadducts as the minor products in combined yields of 87 and 66%, respectively. The photolysis of the hypoiodites generated in situ from cyclobutanols derived from all of the photoadducts induced beta-scissions at the outer bonds of the corresponding cyclobutanoxyl radicals to give furo[2,3-c]quinolin-4(5H)-ones in 15-50% yields with an accompanying formation of 7- and 8-membered lactams arising from beta-scissions at the catacondensed bonds of the cyclobutanoxyl radicals in 2-62% yields. The molecular structure of one of the novel 7-membered lactams that successively fused with cyclopropane and cyclopentane rings was established to be trans-5,8,9,10,10a,10b-hexahydro-5-methylcyclopenta[3,4]cyclopropa[1,2-d]benzazepine-6,7-dione by X-ray crystallographic analysis. The pathways leading to the formation of all of these products arising from beta-scissions are discussed.

  DOI：

  10.1021/jo00028a037

文献信息

• Photoinduced molecular transformations. 128. Regioselective [2 + 2] photocycloaddition of 3-acetoxyquinolin-2(1H)-one with alkenes and formation of furo[2,3-c]quinolin-4(5H)-ones, 1-benzazocine-2,3-diones, and cyclopropa[d]benz[1]azepine-2,3-diones via a .beta.-scission of cyclobutanoxyl radicals generated from the resulting [2 + 2] photoadducts
  作者：Kazuhiro Kobayashi、Masayoshi Suzuki、Hiroshi Suginome

  DOI：10.1021/jo00028a037

  日期：1992.1

  We have found that [2 + 2]pi photoadducts can be obtained by the photoaddition of 3-acetoxyquinolin-2(1H)-one with acyclic and cyclic alkenes. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with 2-methylpropene, 2,3-dimethyl-2-butene, and 2-methoxypropene thus afforded regioselective head-to-tail adducts in 59-97% yields. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with cyclopentene and cyclohexene resulted in the formation of sterically disfavored cis-cisoid-cis photoadducts as the major products, with the accompanying formation of cis-transoid-cis photoadducts as the minor products in combined yields of 87 and 66%, respectively. The photolysis of the hypoiodites generated in situ from cyclobutanols derived from all of the photoadducts induced beta-scissions at the outer bonds of the corresponding cyclobutanoxyl radicals to give furo[2,3-c]quinolin-4(5H)-ones in 15-50% yields with an accompanying formation of 7- and 8-membered lactams arising from beta-scissions at the catacondensed bonds of the cyclobutanoxyl radicals in 2-62% yields. The molecular structure of one of the novel 7-membered lactams that successively fused with cyclopropane and cyclopentane rings was established to be trans-5,8,9,10,10a,10b-hexahydro-5-methylcyclopenta[3,4]cyclopropa[1,2-d]benzazepine-6,7-dione by X-ray crystallographic analysis. The pathways leading to the formation of all of these products arising from beta-scissions are discussed.