5-(Dideuteriomethylene)spiro<3.4>octane | 132591-72-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 5-(Dideuteriomethylene)spiro<3.4>octane
• 英文别名: 8-(Dideuteriomethylidene)spiro[3.4]octane；8-(dideuteriomethylidene)spiro[3.4]octane
• CAS: 132591-72-1
• 化学式: C₉H₁₄
• 分子量: 124.194
• InChiKey: YRPULDYFWXJQQE-DICFDUPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  9
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5-(Dideuteriomethylene)spiro<3.4>octane 生成 1-(Dideuteriomethylidene)-2-methylidenecyclopentane 、 5-(Dideuteriomethylidene)-1-propylcyclopentene 、
  参考文献：
  名称：

  Cleavage vs. rearrangement ratios and secondary deuterium kinetic isotope effects in the thermolysis of conformationally fixed cisoid vinylcyclobutanes

  摘要：

  The first-order rate constants for the thermally induced retro 2 + 2 cleavage and rearrangement of 5-methylenespiro[3.5]nonane occur in a 1:2 ratio. In contrast, a 2:1 ratio of these rate constants is usual from conformationally unbiased vinylcyclobutanes. Comparison of the activation parameters suggests that the rearrangement in unbiased systems results from an unfavorable entropy of activation which suggests that the rearrangement is concerted. For the rearrangement of 5-methylenespiro[3.4]octane, the secondary deuterium kinetic isotope effect at the exo-methylene carbon (k(H)/k(D)2) is 1.086 +/- 0.023. This is also consistent with concert in the rearrangement where exo-methylene rotation contributes to the reaction coordinate. The secondary KIE for cleavage of 5-methylenespiro[3.4]octane is 1.025 +/- 0.027.

  DOI：

  10.1021/jo00006a006
• 作为产物：
  描述：

  2-亚乙二氧基环戊环羧酸乙酯 在 sodium tetrahydroborate 、 lithium aluminium deuteride 、 三氟化硼乙醚 、 potassium carbonate 、 对甲苯磺酸 、 一水合肼 、 二乙胺 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 乙醚 、 乙醇 、 丙酮 、 二乙二醇 为溶剂， 生成 5-(Dideuteriomethylene)spiro<3.4>octane
  参考文献：
  名称：

  Cleavage vs. rearrangement ratios and secondary deuterium kinetic isotope effects in the thermolysis of conformationally fixed cisoid vinylcyclobutanes

  摘要：

  The first-order rate constants for the thermally induced retro 2 + 2 cleavage and rearrangement of 5-methylenespiro[3.5]nonane occur in a 1:2 ratio. In contrast, a 2:1 ratio of these rate constants is usual from conformationally unbiased vinylcyclobutanes. Comparison of the activation parameters suggests that the rearrangement in unbiased systems results from an unfavorable entropy of activation which suggests that the rearrangement is concerted. For the rearrangement of 5-methylenespiro[3.4]octane, the secondary deuterium kinetic isotope effect at the exo-methylene carbon (k(H)/k(D)2) is 1.086 +/- 0.023. This is also consistent with concert in the rearrangement where exo-methylene rotation contributes to the reaction coordinate. The secondary KIE for cleavage of 5-methylenespiro[3.4]octane is 1.025 +/- 0.027.

  DOI：

  10.1021/jo00006a006

文献信息

• Cleavage vs. rearrangement ratios and secondary deuterium kinetic isotope effects in the thermolysis of conformationally fixed cisoid vinylcyclobutanes
  作者：J. J. Gajewski、G. C. Paul

  DOI：10.1021/jo00006a006

  日期：1991.3

  The first-order rate constants for the thermally induced retro 2 + 2 cleavage and rearrangement of 5-methylenespiro[3.5]nonane occur in a 1:2 ratio. In contrast, a 2:1 ratio of these rate constants is usual from conformationally unbiased vinylcyclobutanes. Comparison of the activation parameters suggests that the rearrangement in unbiased systems results from an unfavorable entropy of activation which suggests that the rearrangement is concerted. For the rearrangement of 5-methylenespiro[3.4]octane, the secondary deuterium kinetic isotope effect at the exo-methylene carbon (k(H)/k(D)2) is 1.086 +/- 0.023. This is also consistent with concert in the rearrangement where exo-methylene rotation contributes to the reaction coordinate. The secondary KIE for cleavage of 5-methylenespiro[3.4]octane is 1.025 +/- 0.027.