sp-1-(fluorenyl)naphthalene-2-carboxylic acid | 78705-59-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: sp-1-(fluorenyl)naphthalene-2-carboxylic acid
• 英文别名: 1-(9-fluorenyl)naphthalene-2-carboxylic acid；9-(2-carboxy-1-naphthyl)fluorene；1-(9H-fluoren-9-yl)naphthalene-2-carboxylic acid
• CAS: 78705-59-6；84048-78-2；345976-81-0
• 化学式: C₂₄H₁₆O₂
• 分子量: 336.39
• InChiKey: VDIOVVNEXLAQQL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  sp-1-(fluorenyl)naphthalene-2-carboxylic acid 在 氯化亚砜 、 sodium azide 、 氢溴酸 作用下， 以 乙二醇二甲醚 为溶剂， 反应 4.42h， 生成 1-(9-fluorenyl)-2-naphthalenamine
  参考文献：
  名称：

  Moriyama, Kazuhiro; Nakamura, Nobuo; Nakamura, Mikio, Gazzetta Chimica Italiana, 1987, vol. 117, # 11, p. 655 - 660

  摘要：

  DOI：
• 作为产物：
  描述：

  1-溴-2-甲氧基甲基萘 在 palladium on activated charcoal chromium(VI) oxide 、 盐酸 、 正丁基锂 、 氢气 作用下， 以 乙醇 、 水 、 溶剂黄146 为溶剂， 反应 3.17h， 生成 sp-1-(fluorenyl)naphthalene-2-carboxylic acid
  参考文献：
  名称：

  Moriyama, Kazuhiro; Nakamura, Nobuo; Nakamura, Mikio, Gazzetta Chimica Italiana, 1987, vol. 117, # 11, p. 655 - 660

  摘要：

  DOI：

文献信息

• Reactivities of Stable Rotamers. XI. Rotamer Distributions and Some Addition Reactions to the Carbonyl in 9-[2-(Substituted carbonyl)-1-naphthyl]fluorene Rotamers
  作者：Ryo Saito、Michinori Oki

  DOI：10.1246/bcsj.55.3273

  日期：1982.10

  Rotational isomers (sp and ap) of several 9-[2-(substituted carbonyl)-1-naphthyl]fluorenes where the substituent is methyl, phenyl, hydroxyl, methoxyl, 1-imidazolyl, or others have been obtained as stable entities. Barriers to rotation in these compounds were ca. 26.5 kcal for the process sp→ap but those for the reverse (ap→sp) were dependent on the substituent, ranging from 23.8 to 25.3 kcal/mol at 55 °C. The difference is reflected in the populations of rotamers: if the substituent is a hydroxyl, the sp/ap value becomes as large as ca. 20. The relative instability of the ap form was attributed to twisting of the carbonyl plane from that of naphthalene. Infrared spectra support the twisting. Addition reactions to the carbonyl occur smoothly in the sp conformation but they do not occur to a detectable extent in the ap conformation, if the substituent on the carbonyl is larger than hydrogen. The results are attributed to the steric effect of the fluorene ring.

  几种9-[2-(取代的羰基)-1-萘基]芴的旋转异构体(sp和ap)已作为稳定的实体获得，其中取代基是甲基、苯基、羟基、甲氧基、1-咪唑基或其他基团。这些化合物中的旋转障碍约为。 sp→ap 过程为 26.5 kcal，但相反过程 (ap→sp) 则取决于取代基，在 55 °C 时范围为 23.8 至 25.3 kcal/mol。这种差异反映在旋转异构体的数量上：如果取代基是羟基，则 sp/ap 值变得约大。 20. ap 形式的相对不稳定归因于羰基平面相对于萘的扭曲。红外光谱支持这种扭曲。羰基的加成反应在 sp 构象中顺利发生，但如果羰基上的取代基大于氢，则在 ap 构象中不会发生可检测的程度。该结果归因于芴环的空间效应。
• ISOLATION AND RELATIVE REACTIVITIES IN CHROMIUM(VI) OXIDE OXIDATION OF THE ROTAMERS OF 9-(2-FORMYL-1-NAPHTHYL)FLUORENE AND RELATED ALCOHOLS
  作者：Michinori Oki、Ryo Saito

  DOI：10.1246/cl.1981.649

  日期：1981.5.5

  and 9-[2-(α-hydroxybenzyl)-1-naphthyl]fluorene showed that the relative reactivities of the rotamers of the former were almost the same, while those of the latter differed to a great extent. The results suggest that the steric hindrance to the approach of a base to a proton in E2 elimination is the cause of poor reactivities of the ap forms of the aldehyde and the benzylic alcohol.

  分离出9-(2-甲酰基-1-萘基)芴的旋转异构体(sp 和ap)。旋转（sp → ap）的ΔH\eweq 和ΔS\eweq 分别为24.0 kcal mol-1 和-7.9 eu。sp 形式的氧化平稳地提供相应的羧酸，而 ap 形式反应非常缓慢，得到内酯。9-(2-羟甲基-1-萘基)芴和9-[2-(α-羟基苄基)-1-萘基]芴的氧化表明,前者的旋转异构体的相对反应活性几乎相同,而后者差别很大。结果表明，在 E2 消除中，碱基接近质子的空间位阻是醛和苯甲醇的 ap 形式反应性差的原因。
• Reactivities of Stable Rotamers. XLII. Generation and Fates of Rotameric [1-(9-Fluorenyl)-2-naphthyl]methyl Radicals
  作者：Michinori Oki、Takanori Hirose、Kei Kaneko、Tsutomu Hidaka、Hirotaka Ozaki、Mitsuhiro Asakura、Shinji Toyota、Tomoyo Ishiguro (née Yamada)、Nobuo Nakamura

  DOI：10.1246/bcsj.72.2327

  日期：1999.10

  The title radical rotamers were generated by thermolyses of the corresponding t-butyl peroxycarboxylates or photolyses of the corresponding 2(1H)-thioxo-1-pyridyl carboxylates. Products from the t-butyl peroxyesters were t-butoxy compounds, dimers, and colligation products with a benzyl radical, when the reactions were carried out in toluene. In carbon tetrachloride, chlorine-abstraction products and

  标题自由基旋转异构体通过相应的过氧羧酸叔丁酯的热解或相应的 2(1H)-硫代-1-吡啶基羧酸酯的光解产生。当反应在甲苯中进行时，来自叔丁基过氧化酯的产物是叔丁氧基化合物、二聚体和具有苄基的共聚产物。在四氯化碳中，除二聚体外，还得到氯提取产物和与三氯甲基自由基结合的产物。2(1H)-thioxo-1-pyridyl 酯的光解提供了预期的产物、二聚体和 2-pyridylthio 衍生物。通常，一种旋转异构体与另一种旋转异构体的差异会导致产品分布的微小差异。微小的差异归因于在产生自由基的部位起作用的空间效应。
• Reactivities of Stable Rotamers. X. Reactions of 9-(2-Formyl-1-naphthyl)fluorene Rotamers and Related Compounds
  作者：Ryo Saito、Michinori Oki

  DOI：10.1246/bcsj.55.3267

  日期：1982.10

  Rotational barrier (ap→sp) in 9-(2-formyl-1-naphthyl)fluorene was determined: ΔH\eweq24.0 kcal/mol and ΔS\eweq−7.9 e.u. Oxidation of the aldehyde with chromium(VI) oxide was extremely slow in the ap form, whereas it proceeded smoothly in the sp form. As models of the 2 steps involved in the aldehyde oxidation, oxime formation of the aldehyde and oxidation of related alcohols were carried out to conclude that the second elimination step in the aldehyde oxidation is slow in the ap form because of the steric effect. Dehydration of the oxime of the aldehyde exhibited a large ksp/kap value as well. Sodium tetrahydridoborate reduction and Grignard additions of the aldehyde were also carried out to show that the former gave a large ksp/kap value whereas the latter exhibited rather a small ksp/kap. The implication of the results is discussed.

  9-(2-甲酰基-1-萘基)芴的旋转屏障（ap→sp）被测定为：ΔH=24.0 kcal/mol，ΔS=-7.9 e.u.。醛与氧化铬（VI）的氧化在ap形式下极为缓慢，而在sp形式下则进展顺利。作为醛氧化中涉及的2个步骤的模型，进行了醛的肟形成和相关醇的氧化，以得出结论：由于空间位阻效应，醛氧化中的第二个消除步骤在ap形式下很慢。醛的肟脱水也表现出很大的ksp/kap值。还进行了醛的四氢硼酸钠还原和格氏加成，以表明前者给出了很大的ksp/kap值，而后者则表现出相当小的ksp/kap。讨论了结果的含义。
• OEKI MICHINORI; SAITO RYO, CHEM. LETT., 1981, NO 5, 649-652
  作者：OEKI MICHINORI、 SAITO RYO

  DOI：——

  日期：——