2-<(tributylphosphoranylidene)amino>-1,6-methano<10>annulene | 137594-07-1

• 分子结构分类: 有机化合物 - 有机磷化合物 - 膦酰亚胺
• 英文名称: 2-<(tributylphosphoranylidene)amino>-1,6-methano<10>annulene
• 英文别名: 2-Bicyclo[4.4.1]undeca-1(10),2,4,6,8-pentaenylimino(tributyl)-lambda5-phosphane；2-bicyclo[4.4.1]undeca-1(10),2,4,6,8-pentaenylimino(tributyl)-λ5-phosphane
• CAS: 137594-07-1
• 化学式: C₂₃H₃₆NP
• 分子量: 357.519
• InChiKey: JOYMNNBOWGNPQT-UHFFFAOYSA-N

物化性质

• 沸点：
  520.2±43.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  25
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  2-<(tributylphosphoranylidene)amino>-1,6-methano<10>annulene 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲苯 、 苯 为溶剂， 反应 15.0h， 生成 7,12-亚甲基环癸五烯并[b]吡啶,2-(4-氯苯基)-4-苯基-
  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：

  双环[4.4.1]十一碳-1(10),2,4,6,8-五烯 在 溴叠氮化物 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.0h， 生成 2-<(tributylphosphoranylidene)amino>-1,6-methano<10>annulene
  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

文献信息

• On the reaction of (vinylimino)phosphoranes and related compounds synthesis and properties of novel 1,6-methanocyclodeca[b]cyclohepta[d]pyrrole
  作者：Makoto Nitta、Hiroyuki Kawaji、Nobuhiro Kanomata

  DOI：10.1016/0040-4039(92)88063-b

  日期：1992.1

  The title compound was synthesized by thermal reaction of 3-phosphoranylidene-amino-1,6-methano[10]annulene with 2-chlorotropone in a single step. The examination of 1H NMR spectrum revealed that there is little contribution of peripheral 18-π electron conjugation, but it is rather composed of 1-azaazulene and methano[10]annulene moieties.

  一步合成3-膦亚基-氨基-1,6-甲基[10]环戊烯与2-氯四氢萘酮进行热合成。1 H NMR光谱的检查表明，外围的18-π电子共轭几乎没有贡献，但是它由1-氮杂氮烯和甲醇[10]环戊烯部分组成。
• 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.