9-Methylene-7-oxobicyclo<4.3.0>nonane | 82668-88-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 9-Methylene-7-oxobicyclo<4.3.0>nonane
• 英文别名: 9-methylene-7-oxabicyclo<4.3.0>nonane；3-Methyleneoctahydro-1-benzofuran；3-methylidene-3a,4,5,6,7,7a-hexahydro-1-benzofuran
• CAS: 82668-88-0
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: ZYYJKMVNOHIKQF-UHFFFAOYSA-N

物化性质

• 沸点：
  195.6±19.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  9-Methylene-7-oxobicyclo<4.3.0>nonane 在 吡啶 、 chromium(III) oxide 作用下， 以 二氯甲烷 为溶剂， 生成 cis-3-methylenehexahydrobenzofuran-2-one
  参考文献：
  名称：

  双(二甲基乙醛肟)(吡啶)钴(I)、钴肟(I)与2-(烯丙氧基)乙基卤化物的反应和所得有机钴肟的光解

  摘要：

  2-（烯丙氧基）乙基卤化物与钴肟（I）的反应通过从钴肟（I）到卤化物的电子转移产生（四氢-3-呋喃基）甲基钴肟以产生自由基阴离子。卤化物离子断裂产生有机自由基和闭环产生(四氢-3-呋喃基)甲基自由基，随后有机自由基与钴肟(II)之间的自由基偶联。有机钴肟的结构是通过在有氧或无氧条件下对光解产物的分析来确定的。

  DOI：

  10.1246/bcsj.55.1498
• 作为产物：
  描述：

  2-Bromoprop-2-enyl cyclohex-2-enyl ether 在 samarium diiodide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 3.0h， 以75%的产率得到9-Methylene-7-oxobicyclo<4.3.0>nonane
  参考文献：
  名称：

  Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals

  摘要：

  Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals. Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(pi-exo)exo, 6-(pi-endo)exo, and 6-(pi-exo)exo mode, respectively. Radical 7 undergoes competitive 1,5-hydrogen translocation. Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively. Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent beta-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation. Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization). Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group. Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. alpha-Oxy(and alpha-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.

  DOI：

  10.1021/jo00128a013

文献信息

• Electrooxidative initiation of tin hydride-promoted radical chain reactions
  作者：Hideo Tanaka、Hiroaki Suga、Hidenori Ogawa、A.K.M. Abdul Hai、Sigeru Torii、Anny Jutand、Christian Amatore

  DOI：10.1016/s0040-4039(00)79024-1

  日期：1992.10

  Electrooxidative initiation of tin hydride-promoted radical chain reactions at ambient temperature has been performed by passing 0.2–0.5 F/mol of electricity through a solution of triphenyltin hydride and substrates in THF containing Bu4NClO4.

  氢化锡促进的自由基链反应在环境温度下的电氧化引发反应是通过使0.2–0.5 F / mol的电流通过氢化三苯锡和底物在含有Bu 4 NClO 4的THF中的溶液进行的。
• A new synthetic route to 2,5-dihydrofurans
  作者：Jean-Pierre Dulcère、Nathalie Baret、Jean Rodriguez

  DOI：10.1039/c39940000303

  日期：——

  ButOK–dimethyl sulfoxide-catalysed selective isomerization of 3-methylene tetrahydrofurans 1 provides a new convenient route to 2,5-dihydrofuran 2 precursors of furan-2(3H)-ones 8 or furans 4 or 9.

  但是，3-亚甲基四氢呋喃1在二甲基亚砜催化下的选择性异构化反应为呋喃-2(3H)-酮8或呋喃4或9的前体2,5-二氢呋喃2提供了新的便捷合成途径。
• Electrogeneration of Triphenyltin Radical, Anion, and Cation. Electrochemical Initiation of Tin Hydride-Promoted Radical Chain Reactions
  作者：Hideo Tanaka、Hidenori Ogawa、Hiroaki Suga、Sigeru Torii、Anny Jutand、Said Aziz、Alejandra G. Suarez、Christian Amatore

  DOI：10.1021/jo960741b

  日期：1996.1.1

  In our research of precursors of tin radicals able to initiate radical chain reactions under mild conditions, a series of triphenyltin derivatives Ph(3)SnY (Y = H, I, Cl, OTf, OCHO, SnPh(3), SPh) is investigated by cyclic voltammetry. The results show that the tin radical Ph(3)Sn(.) is only produced from two compounds: by a one-electron oxidation of Ph(3)SnH or by a one-electron reduction of Ph(3)SnI. Therefore electrooxidation of Ph(3)SnH generates Ph(3)Sn(.) which is able to initiate cyclization of haloalkynes. Reduction or oxidation of the other derivatives affords respectively the anion Ph(3)Sn(-) or the cation Ph(3)Sn(+) because they are generated at potentials where the radical Ph(3)Sn(.) is either reduced or oxidized.
• OKABE, MASAMI;ABE, MASAYOSHI;TADA, MASARU, J. ORG. CHEM., 1982, 47, N 9, 1775-1777
  作者：OKABE, MASAMI、ABE, MASAYOSHI、TADA, MASARU

  DOI：——

  日期：——
• Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals
  作者：Laura Capella、Pier Carlo Montevecchi、Maria Luisa Navacchia

  DOI：10.1021/jo00128a013

  日期：1995.11

  Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals. Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(pi-exo)exo, 6-(pi-endo)exo, and 6-(pi-exo)exo mode, respectively. Radical 7 undergoes competitive 1,5-hydrogen translocation. Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively. Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent beta-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation. Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization). Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group. Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. alpha-Oxy(and alpha-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.