2-<(triphenylphosphoranylidene)amino>-1,6-methano<10>annulene | 134858-17-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-<(triphenylphosphoranylidene)amino>-1,6-methano<10>annulene
• 英文别名: 2-triphenylphosphoranylideneamino-1,6-methano<10>annulene；2-triphenylphosphoranylideneamino-1,6-methano[10]annulene；2-Bicyclo[4.4.1]undeca-1(10),2,4,6,8-pentaenylimino(triphenyl)-lambda5-phosphane；2-bicyclo[4.4.1]undeca-1(10),2,4,6,8-pentaenylimino(triphenyl)-λ5-phosphane
• CAS: 134858-17-6
• 化学式: C₂₉H₂₄NP
• 分子量: 417.49
• InChiKey: DEANECIYKJFCNZ-UHFFFAOYSA-N

物化性质

• 沸点：
  633.9±48.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  二硫化碳 、 2-<(triphenylphosphoranylidene)amino>-1,6-methano<10>annulene 反应 48.0h， 以75%的产率得到2-Isothiocyanato-1,6-methano<10>annulen
  参考文献：
  名称：

  On the reaction of (vinylimino)phosphoranes and related compounds. 20. Syntheses and properties of methanocyclodeca[b]pyridine ring systems

  摘要：

  Novel 2-[(triphenyl- and 2-[(tributylphosphoranylidene)amino]-1,6-methanol[10]annulenes (8x,y) and 3-[(triphenyl- and 3-[(tributylphosphoranylidene)amino]-1,6-methano[10]annulenes (9x,y) were generated by the Staudinger reaction of 2- and 3-azido-1,6-methano[10]annulenes (5 and 6). The compound 8x was inert to alpha,beta-unsaturated ketones, while compounds 8y and 9y were found to react with alpha,beta-unsaturated ketones in enamine-alkylation process followed by aza-Wittig reaction and dehydrogenation to give 7,12- and 5,10-methanocyclodeca[b]pyridines 20a-f and 26a,f, respectively. The reactivity of 8 and 9 as well as the site selectivity of 9 was suggested by their C-13 NMR spectra, in which the carbon signals of the nucleophilic center appear at higher field as compared to those of 1,6-methano[10]annulene. Structural properties of 20a-f and 26a,f were examined by H-1 NMR and UV spectra. The H-1 NMR spectra analyzing aromatic characters clarified both remarkable reduction of a ring current and appearance of bond alternation as compared to the parent 1,6-methano[10]annulene (1). The UV spectra exhibiting a prolonged cyclic conjugation are in contrast to their 10-pi electron analogues, 1,6-methano[10]annulene (1) and quinoline derivatives.

  DOI：

  10.1021/jo00028a040
• 作为产物：
  描述：

  2-bromo-1,6-methano[10]annulene 在 正丁基锂 、 对甲苯磺酰叠氮 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 2-<(triphenylphosphoranylidene)amino>-1,6-methano<10>annulene
  参考文献：
  名称：

  Suschitzky, Hans; Kramer, Walter; Neidlein, Richard, Journal of the Chemical Society. Perkin transactions I, 1991, # 4, p. 923 - 927

  摘要：

  DOI：

文献信息

• Bohn, Thomas; Kramer, Walter; Neidlein, Richard, Journal of the Chemical Society. Perkin transactions I, 1994, # 8, p. 947 - 952
  作者：Bohn, Thomas、Kramer, Walter、Neidlein, Richard、Suschitzky, Hans

  DOI：——

  日期：——
• Suschitzky, Hans; Kramer, Walter; Neidlein, Richard, Journal of the Chemical Society. Perkin transactions I, 1991, # 4, p. 923 - 927
  作者：Suschitzky, Hans、Kramer, Walter、Neidlein, Richard、Rosyk, Peter、Bohn, Thomas

  DOI：——

  日期：——
• On the reaction of (vinylimino)phosphoranes and related compounds. 20. Syntheses and properties of methanocyclodeca[b]pyridine ring systems
  作者：Nobuhiro Kanomata、Hiroyuki Kawaji、Makoto Nitta

  DOI：10.1021/jo00028a040

  日期：1992.1

  Novel 2-[(triphenyl- and 2-[(tributylphosphoranylidene)amino]-1,6-methanol[10]annulenes (8x,y) and 3-[(triphenyl- and 3-[(tributylphosphoranylidene)amino]-1,6-methano[10]annulenes (9x,y) were generated by the Staudinger reaction of 2- and 3-azido-1,6-methano[10]annulenes (5 and 6). The compound 8x was inert to alpha,beta-unsaturated ketones, while compounds 8y and 9y were found to react with alpha,beta-unsaturated ketones in enamine-alkylation process followed by aza-Wittig reaction and dehydrogenation to give 7,12- and 5,10-methanocyclodeca[b]pyridines 20a-f and 26a,f, respectively. The reactivity of 8 and 9 as well as the site selectivity of 9 was suggested by their C-13 NMR spectra, in which the carbon signals of the nucleophilic center appear at higher field as compared to those of 1,6-methano[10]annulene. Structural properties of 20a-f and 26a,f were examined by H-1 NMR and UV spectra. The H-1 NMR spectra analyzing aromatic characters clarified both remarkable reduction of a ring current and appearance of bond alternation as compared to the parent 1,6-methano[10]annulene (1). The UV spectra exhibiting a prolonged cyclic conjugation are in contrast to their 10-pi electron analogues, 1,6-methano[10]annulene (1) and quinoline derivatives.