10-methylidenehexacyclo<10.2.1.0^2,11.0^4,9.0^4,14.0^9,13>pentadeca-5,7-dien-3-one | 132672-56-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 10-methylidenehexacyclo<10.2.1.0^2,11.0^4,9.0^4,14.0^9,13>pentadeca-5,7-dien-3-one
• 英文别名: 15-Methylidenehexacyclo[7.5.1.01,6.06,13.08,12.010,14]pentadeca-2,4-dien-7-one
• CAS: 132672-56-1
• 化学式: C₁₆H₁₄O
• 分子量: 222.287
• InChiKey: DNAJJUDPJGTEGM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  10-methylidenehexacyclo<10.2.1.0^2,11.0^4,9.0^4,14.0^9,13>pentadeca-5,7-dien-3-one 生成
  参考文献：
  名称：

  Facial differentiation in Diels-Alder reactions to dissymmetric cyclohexa-1,3-dienes

  摘要：

  Reactions of 2a-c with maleic anhydride (MA) and benzoquinone (BQ) show strong preference for addition to the ''carbonyl'' face of the diene. For dimethyl acetylenedicarboxylate (DMAD), attack from this face decreases with successive methylidene substitution while for N-phenyl-1,2,4-triazolinedione (PTAD) the reverse occurs. The consequence of orbital tilting and transition-state steric and torsional interactions cannot alone account for the facial selectivity for the reactions with DMAD and PTAD. Unfavorable orbital interaction of the closed shells of the carbonyl(s) and methylidene(s) syn to the incoming orthogonal pi orbital of DMAD is considered to be important.

  DOI：

  10.1021/jo00007a051
• 作为产物：
  描述：

  hexacyclo<10.2.1.0^2,11.0^4,9.0^4,14.0^9,13>pentadeca-5,7-diene-3,10-dione 、 methyl triphenylphosphonium bromide 在 sodium hydride 、 二甲基亚砜 作用下， 生成 3,10-dimethylidenehexacyclo<10.2.1.0^2,11.0^4,9.0^4,14.0^9,13>pentadeca-5,7-diene 、 10-methylidenehexacyclo<10.2.1.0^2,11.0^4,9.0^4,14.0^9,13>pentadeca-5,7-dien-3-one
  参考文献：
  名称：

  Facial differentiation in Diels-Alder reactions to dissymmetric cyclohexa-1,3-dienes

  摘要：

  Reactions of 2a-c with maleic anhydride (MA) and benzoquinone (BQ) show strong preference for addition to the ''carbonyl'' face of the diene. For dimethyl acetylenedicarboxylate (DMAD), attack from this face decreases with successive methylidene substitution while for N-phenyl-1,2,4-triazolinedione (PTAD) the reverse occurs. The consequence of orbital tilting and transition-state steric and torsional interactions cannot alone account for the facial selectivity for the reactions with DMAD and PTAD. Unfavorable orbital interaction of the closed shells of the carbonyl(s) and methylidene(s) syn to the incoming orthogonal pi orbital of DMAD is considered to be important.

  DOI：

  10.1021/jo00007a051

文献信息

• COXON, JAMES M.;MACLAGAN, ROBERT G. A. R.;MCDONALD, D. QUENTIN;STEEL, PET+, J. ORG. CHEM., 56,(1991) N, C. 2542-2549
  作者：COXON, JAMES M.、MACLAGAN, ROBERT G. A. R.、MCDONALD, D. QUENTIN、STEEL, PET+

  DOI：——

  日期：——
• Facial differentiation in Diels-Alder reactions to dissymmetric cyclohexa-1,3-dienes
  作者：James M. Coxon、Robert G. A. R. Maclagan、D. Quentin McDonald、Peter J. Steel

  DOI：10.1021/jo00007a051

  日期：1991.3

  Reactions of 2a-c with maleic anhydride (MA) and benzoquinone (BQ) show strong preference for addition to the ''carbonyl'' face of the diene. For dimethyl acetylenedicarboxylate (DMAD), attack from this face decreases with successive methylidene substitution while for N-phenyl-1,2,4-triazolinedione (PTAD) the reverse occurs. The consequence of orbital tilting and transition-state steric and torsional interactions cannot alone account for the facial selectivity for the reactions with DMAD and PTAD. Unfavorable orbital interaction of the closed shells of the carbonyl(s) and methylidene(s) syn to the incoming orthogonal pi orbital of DMAD is considered to be important.