1'-acetoxyspiro-1,2,3,6-tetrahydropyrene> | 149296-32-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 1'-acetoxyspiro-1,2,3,6-tetrahydropyrene>
• 英文别名: 1'-acetoxyspiro(cyclopentane-6,6'-[6H]-1,2,3,6-tetrahydropyrene)；spiro[2,3-dihydro-1H-pyrene-6,1'-cyclopentane]-1-yl acetate
• CAS: 149296-32-2
• 化学式: C₂₂H₂₂O₂
• 分子量: 318.415
• InChiKey: HQLUTVKTNOBXGQ-UHFFFAOYSA-N

物化性质

• 沸点：
  493.5±44.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1'-acetoxyspiro-1,2,3,6-tetrahydropyrene> 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以87%的产率得到1'-hydroxyspiro-1,2,3,6-tetrahydropyrene>
  参考文献：
  名称：

  Spectrometry and reactivity of the 1-hydropyrenyl anion

  摘要：

  A study of the charge distribution in the 1-hydropyrenyl anion (2-), and of its regioselectivity toward electrophilic attack was undertaken. In order to obtain reliable information on the reactive positions in 2-, a model with the same conjugated system was prepared, which has its 1-position fixed with a spirocyclopentane ring. Highly resolved H-1 and C-13 NMR spectra of this spiro[cyclopentane-1,1'-[1H]pyrenyl] anion (1-) and of 2- were obtained. These spectra could be completely assigned by means of COSY, NOESY, and 2D H-1-C-13 COSY techniques. According to the C-13 NMR measurements, 5-C of 1- and 2- bears the highest negative charge. The results of PM3 semiempirical calculations support this finding and, furthermore, a large HOMO coefficient was calculated at the quaternary 3a-C of 2-, suggesting that this position is susceptible toward attack by soft electrophiles. In full agreement with the C-13 NMR and PM3 results, 5-C of 1- and 2- show the highest reactivity toward electrophilic attack, while the quaternary 3a-C of 1- and 2- is attacked by soft electrophiles. These new results contradict earlier findings because until now, carbon atom 9-C of the 1-hydropyrenyl anion (2-) was assumed to be the most reactive position, and soft electrophiles were thought to attack 10a-C of 2-.

  DOI：

  10.1021/jo00063a029
• 作为产物：
  描述：

  芘 在 copper diacetate 作用下， 以 溶剂黄146 为溶剂， 反应 0.5h， 生成 1'-acetoxyspiro-1,2,3,6-tetrahydropyrene>
  参考文献：
  名称：

  Spectrometry and reactivity of the 1-hydropyrenyl anion

  摘要：

  A study of the charge distribution in the 1-hydropyrenyl anion (2-), and of its regioselectivity toward electrophilic attack was undertaken. In order to obtain reliable information on the reactive positions in 2-, a model with the same conjugated system was prepared, which has its 1-position fixed with a spirocyclopentane ring. Highly resolved H-1 and C-13 NMR spectra of this spiro[cyclopentane-1,1'-[1H]pyrenyl] anion (1-) and of 2- were obtained. These spectra could be completely assigned by means of COSY, NOESY, and 2D H-1-C-13 COSY techniques. According to the C-13 NMR measurements, 5-C of 1- and 2- bears the highest negative charge. The results of PM3 semiempirical calculations support this finding and, furthermore, a large HOMO coefficient was calculated at the quaternary 3a-C of 2-, suggesting that this position is susceptible toward attack by soft electrophiles. In full agreement with the C-13 NMR and PM3 results, 5-C of 1- and 2- show the highest reactivity toward electrophilic attack, while the quaternary 3a-C of 1- and 2- is attacked by soft electrophiles. These new results contradict earlier findings because until now, carbon atom 9-C of the 1-hydropyrenyl anion (2-) was assumed to be the most reactive position, and soft electrophiles were thought to attack 10a-C of 2-.

  DOI：

  10.1021/jo00063a029

文献信息

• Spectrometry and reactivity of the 1-hydropyrenyl anion
  作者：Mark A. Hempenius、Cees Erkelens、Patrick P. J. Mulder、Han Zuilhof、Wouter Heinen、Johan Lugtenburg、Jan Cornelisse

  DOI：10.1021/jo00063a029

  日期：1993.5

  A study of the charge distribution in the 1-hydropyrenyl anion (2-), and of its regioselectivity toward electrophilic attack was undertaken. In order to obtain reliable information on the reactive positions in 2-, a model with the same conjugated system was prepared, which has its 1-position fixed with a spirocyclopentane ring. Highly resolved H-1 and C-13 NMR spectra of this spiro[cyclopentane-1,1'-[1H]pyrenyl] anion (1-) and of 2- were obtained. These spectra could be completely assigned by means of COSY, NOESY, and 2D H-1-C-13 COSY techniques. According to the C-13 NMR measurements, 5-C of 1- and 2- bears the highest negative charge. The results of PM3 semiempirical calculations support this finding and, furthermore, a large HOMO coefficient was calculated at the quaternary 3a-C of 2-, suggesting that this position is susceptible toward attack by soft electrophiles. In full agreement with the C-13 NMR and PM3 results, 5-C of 1- and 2- show the highest reactivity toward electrophilic attack, while the quaternary 3a-C of 1- and 2- is attacked by soft electrophiles. These new results contradict earlier findings because until now, carbon atom 9-C of the 1-hydropyrenyl anion (2-) was assumed to be the most reactive position, and soft electrophiles were thought to attack 10a-C of 2-.