4-(2,3-Dihydro-indol-1-yl)-1-[(Z)-1,3,3-trimethyl-1,3-dihydro-indol-(2E)-ylidenemethylimino]-1H-naphthalen-2-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 4-(2,3-Dihydro-indol-1-yl)-1-[(Z)-1,3,3-trimethyl-1,3-dihydro-indol-(2E)-ylidenemethylimino]-1H-naphthalen-2-one
• 英文别名: 4-(2,3-Dihydroindol-1-yl)-1-[(1,3,3-trimethylindol-2-ylidene)methylimino]naphthalen-2-one
• 化学式: C₃₀H₂₇N₃O
• 分子量: 445.564
• InChiKey: XTARLDHTHIAOSF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  35.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  螺[2H-吲哚-2,3'-[3H]萘并[2,1-b][1,4]恶嗪],6'-(2,3-二氢-1H-吲哚-1-基)-1,3-二氢-1,3,3-三甲基- 以 甲苯 为溶剂， 生成 4-(2,3-Dihydro-indol-1-yl)-1-[(Z)-1,3,3-trimethyl-1,3-dihydro-indol-(2E)-ylidenemethylimino]-1H-naphthalen-2-one
  参考文献：
  名称：

  Photochromism of naphthoxazine-spiro-indolines by direct excitation and following sensitisation by triplet-energy donors

  摘要：

  我们测量了几种萘氧螺吲哚啉（NOSIs）在多种溶剂和几种具有不同玻璃跃迁温度的聚氨酯基质中形成美拉德腈的量子效率（ΦA）。在甲苯溶液中，ΦA 值从 0.74 到 0.33 不等，其中在噁嗪环的 6′-位上取代电子的化合物产量最高。形成美拉德菁的量子产率对溶剂的变化也很敏感，在甲苯中最高，在甲醇中最低。有趣的是，在高粘度聚氨酯基质中，量子产率通常在 0.1 到 0.2 之间。令人惊讶的是，用异丁基取代分子中吲哚啉部分氮上的甲基对甲苯和聚氨酯基质中的量子产率都没有影响。通过三重能捐献，我们确定了美拉德菁形成的三重态途径，而且在甲苯溶剂中研究的三种衍生物中，通过三重态敏化形成美拉德菁的效率都接近于统一。通过使用各种三重态能量供体并测量由此产生的淬灭速率常数的值，确定 1,3,3-三甲基螺（吲哚啉-2,3′[3H]萘并[2,1-b]-6′-吲哚啉并[1,4]恶嗪）的最低三重态能量为 200 ± 5 kJ mol-1，这与通过与分子中的恶嗪部分相关的三重态敏化是一致的。对于三重态能量大于 210 kJ mol-1 的供体，淬灭常数达到了 4.5 ± 0.3 × 109 dm3 mol-1 s-1 的高原值。

  DOI：

  10.1039/ft9969201323

文献信息

• Picosecond time-resolved spectroscopy of the photocolouration reaction of photochromic naphthoxazine-spiro-indolines
  作者：Francis Wilkinson、David R. Worrall、Jonathan Hobley、Lisinka Jansen、Si�n L. Williams、Andrew J. Langley、Pavel Matousek

  DOI：10.1039/ft9969201331

  日期：——

  The photochemical formation of the open merocyanine forms of several naphthoxazine-spiro-indolines in different solvents have been studied using both picosecond transient absorption (PTA) and picosecond time-resolved resonance Raman (PTR3) methods. The PTA studies have established the presence of several metastable species in the photochemical formation of the coloured merocyanine form of these photochromic compounds. The primary photochemical step occurs on the sub-ps timescale and is followed by the formation of a cisoid intermediate over the next 6–30 ps. This cisoid species then isomerises to the equilibrated distribution of transoid isomers of the merocyanine form with a lifetime that is dependent upon both solvent viscosity and polarity as well as the nature of the substituents on the naphthalene part of the molecule. However, the rate of this cis → trans isomerisation is unaffected on changing the N-alkyl group on the indoline part of the molecule from a methyl to an isobutyl group. The PTR3 studies have demonstrated that, in butan-1-ol, there are at least three different transient species with characteristic vibrational spectra which evolve with different lifetimes to give the final isomeric distribution over the first few ns of the reaction. In cyclohexane it is likely that the formation of a single species is being probed, which is fully developed after the first 200 ps of the reaction. This single species has a spectrum which is the same as the equilibrated steady-state resonance Raman merocyanine spectrum. It is likely that the evolution in the PTR3 spectra obtained here, in butan-1-ol, results from an equilibration of initially formed transoid merocyanine isomers to give a more stable distribution in this polar hydrogen-bonded solvent. Such an equilibration appears to be unnecessary in a non-polar solvent such as cyclohexane and it is suggested that this is because the transoid isomer, initially formed, is already in its most stable form.

  利用皮秒瞬态吸收（PTA）和皮秒时间分辨共振拉曼（PTR3）方法，研究了几种萘并恶嗪-螺吲哚在不同溶剂中形成开放的梅花菁形式的光化学过程。皮秒瞬时吸收研究证实，在这些光致变色化合物的彩色梅花苷形式的光化学形成过程中，存在几种可转移的物种。主要的光化学步骤发生在亚 ps 时间尺度上，然后在接下来的 6-30 ps 内形成顺式中间体。然后，这种顺式异构体会异构化为平衡分布的美花青素形式的横向异构体，其寿命取决于溶剂的粘度和极性以及分子中萘部分取代基的性质。不过，当分子中吲哚啉部分的 N-烷基从甲基变为异丁基时，顺式 → 反式异构化的速率不会受到影响。PTR3 研究表明，在丁-1-醇中，至少有三种不同的瞬态物种具有特征性的振动光谱，它们以不同的生命周期演变，从而在反应的最初几毫秒内形成最终的异构体分布。在环己烷中，可能正在检测的是单一物种的形成，该物种在反应的前 200 ps 后得到充分发展。这种单一物种的光谱与平衡稳态共振拉曼美拉曼光谱相同。这里获得的 PTR3 光谱在丁-1-醇中的演变很可能是最初形成的横向美拉曼异构体在这种极性氢键溶剂中进行平衡以获得更稳定分布的结果。在环己烷等非极性溶剂中，这种平衡似乎是不必要的，这是因为最初形成的横轴异构体已经是最稳定的形式。
• Photochromism of naphthoxazine-spiro-indolines by direct excitation and following sensitisation by triplet-energy donors
  作者：Jonathan Hobley、Francis Wilkinson

  DOI：10.1039/ft9969201323

  日期：——

  Quantum efficiencies of merocyanine formation, (ΦA), have been measured for several naphthoxy-spiro-indolines, (NOSIs) in a variety of solvents as well as in several polyurethane matrices having different glass-transition temperatures. In toluene solution ΦA values range from 0.74 to 0.33 with those compounds substituted with electron-donating substituents in the 6′-position on the oxazine ring giving the highest yields. Quantum yields for merocyanine formation are also sensitive to change of solvent, being the highest in toluene and the lowest in methanol. Interestingly, in highly viscous polyurethane matrices quantum yields are typically in the range 0.1 to 0.2. Surprisingly, replacing the methyl group on the nitrogen in the indoline part of the molecule with an isobutyl group has no effect on the quantum yield in either toluene or in a polyurethane matrix. Triplet-energy donation has been used to establish that a triplet pathway leading to merocyanine formation is available and that the efficiency of merocyanine formation via triplet-state sensitization is close to unity for each of the three derivatives studied in toluene as solvent. By using various triplet-energy donors and measuring the values of the resulting quenching rate constants the lowest triplet energy of 1,3,3-trimethylspiro(indoline-2,3′[3H]naphth[2,1-b]-6′-indolino[1,4]oxazine) has been determined as 200 ± 5 kJ mol–1 which is consistent with sensitization via the triplet state associated with the oxazine part of the molecule. For donors with triplet-state energies > 210 kJ mol–1 quenching constants were shown to reach a plateau value of 4.5 ± 0.3 × 109 dm3 mol–1 s–1.

  我们测量了几种萘氧螺吲哚啉（NOSIs）在多种溶剂和几种具有不同玻璃跃迁温度的聚氨酯基质中形成美拉德腈的量子效率（ΦA）。在甲苯溶液中，ΦA 值从 0.74 到 0.33 不等，其中在噁嗪环的 6′-位上取代电子的化合物产量最高。形成美拉德菁的量子产率对溶剂的变化也很敏感，在甲苯中最高，在甲醇中最低。有趣的是，在高粘度聚氨酯基质中，量子产率通常在 0.1 到 0.2 之间。令人惊讶的是，用异丁基取代分子中吲哚啉部分氮上的甲基对甲苯和聚氨酯基质中的量子产率都没有影响。通过三重能捐献，我们确定了美拉德菁形成的三重态途径，而且在甲苯溶剂中研究的三种衍生物中，通过三重态敏化形成美拉德菁的效率都接近于统一。通过使用各种三重态能量供体并测量由此产生的淬灭速率常数的值，确定 1,3,3-三甲基螺（吲哚啉-2,3′[3H]萘并[2,1-b]-6′-吲哚啉并[1,4]恶嗪）的最低三重态能量为 200 ± 5 kJ mol-1，这与通过与分子中的恶嗪部分相关的三重态敏化是一致的。对于三重态能量大于 210 kJ mol-1 的供体，淬灭常数达到了 4.5 ± 0.3 × 109 dm3 mol-1 s-1 的高原值。