spiro-1,2,3,6-tetrahydropyrene> | 149296-31-1

• 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: spiro-1,2,3,6-tetrahydropyrene>
• 英文别名: spiro[cyclopentane-6,6'-[6H]-1,2,3,6-tetrahydropyrene]；spiro[2,3-dihydro-1H-pyrene-6,1'-cyclopentane]
• CAS: 149296-31-1
• 化学式: C₂₀H₂₀
• 分子量: 260.379
• InChiKey: LCWPILNGLHBDCK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  spiro-1,2,3,6-tetrahydropyrene> 在 copper diacetate 、 二异丁基氢化铝 作用下， 以 溶剂黄146 、 甲苯 为溶剂， 反应 4.5h， 生成 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 、 alkaline earth salt of/the/ methylsulfuric acid 在 正丁基锂 、 sodium 、 异丙醇 作用下， 以 四氢呋喃 、 氨 为溶剂， 生成 spiro-1,2,3,6-tetrahydropyrene>
  参考文献：
  名称：

  苯二甲酰基阴离子的光谱法和反应性

  摘要：

  为了研究该共轭阴离子对甲基和甲氧基的扰动，制备了芳香族奇数交替的菲烯基阴离子及其许多衍生物。通过1 H和13 C NMR光谱，烷基化实验和半经验计算研究了共轭阴离子。发现带电碳原子上的取代基扰乱了整个共轭体系，而无活性（不带电）碳原子上的取代基对取代基邻位的影响很大。

  DOI：

  10.1002/poc.610070605

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

  DOI：10.1002/poc.610070605

  日期：1994.6

  The aromatic odd-alternant phenalenyl anion and a number of its derivatives were prepared in order to study the perturbation of this conjugated anion by methyl and methoxy groups. The conjugated anions were studied by means of 1H and 13C NMR spectrometry, alkylation experiments and semi-empirical calculations. It was found that a substituent at a charged carbon atom perturbs the entire conjugated system

  为了研究该共轭阴离子对甲基和甲氧基的扰动，制备了芳香族奇数交替的菲烯基阴离子及其许多衍生物。通过1 H和13 C NMR光谱，烷基化实验和半经验计算研究了共轭阴离子。发现带电碳原子上的取代基扰乱了整个共轭体系，而无活性（不带电）碳原子上的取代基对取代基邻位的影响很大。