1,3,3-三甲基吲哚啉-6’-(1-哌啶基)螺吩恶嗪 | 114747-45-4

• 物质功能分类: 有机原料 - 螺环化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 中文名称: 1,3,3-三甲基吲哚啉-6’-(1-哌啶基)螺吩恶嗪
• 中文别名: 1,3-二氢-1,3,3-三甲基-6'-(1-哌啶基)螺[2H-吲哚-2,3'-[3H]萘并[2,1-b][1,4]恶嗪]；1,3,3-三甲基吲哚啉-6'-(1-哌啶基)螺吩恶嗪；1,3-二氢-1,3,3-三甲基-6'-(1-哌啶基)螺[2H-吲哚-2,3'-[3H]萘并[2,1-B][1,4]恶嗪]
• 英文名称: 6'-piperidine-1,3,3-trimethylspiro(indoline-2,3'[3H]naphth[2,1-b][1,4]oxazine)
• 英文别名: 6'-Piperidino-1,3,3-trimethylspironaphth<2,1-b><1,4>oxazine>；6'-piperidine-1,3,3-trimethylspironaphth<2,1-b><1,4>oxazine>；1',3',3'-trimethyl-6-piperidinospiro<1,4>-oxazine>；1',3',3'-trimethyl-6-piperidinospiro<1,4>oxazine>；1,3,3-trimethyl-6'-piperidinylspironaphtoxazine>；1,3,3-trimethyl-6'-piperidinospiro(indoline-2,3'-3H-naphtho[2,1-b][1,4]-oxazine)；Spiro[2H-indole-2,3'-[3H]naphth[2,1-b][1,4]oxazine], 1,3-dihydro-1,3,3-trimethyl-6'-(1-piperidinyl)-；1',3',3'-trimethyl-6-piperidin-1-ylspiro[benzo[f][1,4]benzoxazine-3,2'-indole]
• CAS: 114747-45-4
• 化学式: C₂₇H₂₉N₃O
• 分子量: 411.547
• InChiKey: YAWJWXXKKHOMQT-UHFFFAOYSA-N

物化性质

• 熔点：
  228-230 °C
• 沸点：
  637.2±55.0 °C(Predicted)
• 密度：
  1.22

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  31
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  28.1
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

反应信息

• 作为反应物：
  描述：

  1,3,3-三甲基吲哚啉-6’-(1-哌啶基)螺吩恶嗪 以 乙醇 为溶剂， 生成 4-Piperidin-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, thermochromism and solvatochromism of some spiro[indolinoxazine]-photomerocyanine systems: effects of structure and solvent

  摘要：

  对三个吡咯并萘并噁嗪和一个吡咯并菲并噁嗪进行了研究,这些化合物具有光致变色和热致变色性质。研究了溶剂和结构对紫外照射下产生的甲罗花青素吸收光谱的影响,以及开环和闭环反应的动力学参数。发现正溶剂变色作用,表明开环形式是一种弱极性物种。随着溶剂极性的增加和噁嗪部分电子供体基团的存在,螺噁嗪⇄甲罗花青素反应的平衡常数和正反应速率常数都增加。该反应吸热10-20 kJ mol-1,几乎是等熵的。活化熵通常为负值,而活化吉布斯自由能基本上不受溶剂和结构的影响。

  DOI：

  10.1039/ft9949000333
• 作为产物：
  描述：

  1-亚硝基-2-萘酚 以 1,4-二氧六环 、 甲醇 为溶剂， 生成 1,3,3-三甲基吲哚啉-6’-(1-哌啶基)螺吩恶嗪
  参考文献：
  名称：

  Red Colouring Photochromic 6′-Substituted Spiroindolinon Aphth[2,1-b][1,4]Oxazines

  摘要：

  Electron donating/withdrawing substituents and electronegative centres have been successfully employed in substantially widening the range of photo-generated colours available in the spiroindolinonaphthoxazine class of photochromic materials.

  DOI：

  10.1080/10587259408037780

文献信息

• One-Pot Synthesis of 6′-Amino-Substituted Spirooxazines
  作者：O. A. Fedorova、A. V. Koshkin、V. Lokshin、A. Samat、S. P. Gromov

  DOI：10.1055/s-2005-870006

  日期：——

  A one-pot synthesis of 6'-amino-substituted spiroindolinonaphth[2,1-b][1,4]oxazines is developed through the condensation of 2-methylene-1,3,3-trimethylindoline derivatives and 1-amino-2-naphthol in the presence of different secondary amines and oxidizing agents using methanol or toluene as the solvent. The main advantage of the method is its simplicity, and starting from readily accessible reagents

  通过 2-methylene-1,3,3-trimethylindoline 衍生物与 1-amino-2 的缩合，一锅法合成 6'-氨基取代的螺吲哚啉萘 [2,1-b][1,4] 恶嗪-萘酚在不同的仲胺和氧化剂的存在下使用甲醇或甲苯作为溶剂。该方法的主要优点是简单，并且从容易获得的试剂开始，它可以在温和的反应条件下以良好的收率制备螺萘恶嗪的氨基衍生物。
• One-Pot Synthesis of Photochromic 6′-Amino-Substituted Spirooxazines from 1-Nitroso-2-naphthol Zinc Chelate and Indoline Base
  作者：Mei-Li Pang、Ji-Ben Meng、Hui-Juan Zhang、Pei-Pei Liu、Zhi-Hong Zou、Jie Han

  DOI：10.1055/s-0030-1258197

  日期：2010.10

  A series of spirooxazine derivatives containing nitrogen heterocycles were synthesized through the condensation of 2-methylene-1,3,3-trimethylindoline derivatives with the zinc salt of 1-nitroso-2-naphthol using ethanol as solvent. The method is simple, starts from readily accessible and inexpensive reagents, and leads to the synthesis of 6′-substituted spirooxazines in moderate to good yields. We simplified the workup and found that, for some target compounds, recrystallization can effectively improve efficiency of the separation and purification.

  以乙醇为溶剂，通过 2-亚甲基-1,3,3-三甲基吲哚啉衍生物与 1-亚硝基-2-萘酚锌盐的缩合，合成了一系列含氮杂环的螺噁嗪衍生物。该方法简单易行，从容易获得且价格低廉的试剂开始，以中等至良好的收率合成 6′-取代的螺噁嗪。我们简化了操作步骤，并发现对于某些目标化合物，重结晶可以有效提高分离和纯化的效率。
• 一种利用微通道反应器合成螺噁嗪类光致变色染料的方法
  申请人：广州盛色科技有限公司

  公开号：CN113943493A

  公开（公告）日：2022-01-18

  本发明涉及一种利用微通道反应器合成螺噁嗪光致变色染料的方法。在染料合成后期的偶联成环过程中，通过预反应系统分别将含有反应原料的流动相体系温度调整至反应温度后，利用恒流泵将上述流动相分别泵入微通道反应器内进行混合控温反应，得到含有光变染料的溶液，通过浓缩、重结晶、脱色和干燥，获得光致变色染料。本方法利用微通道较高的混合和热交换效率，保证了反应物的充分混合和控温的精确，节能效果好，降低了生产成本，产物纯度高，降低后续处理难度，流动相可重复利用，方便规模化生产，具有广大的应用前景。
• Photochromism and solvatochromism of push–pull or pull–push spiroindolinenaphthoxazines
  作者：A. V. Metelitsa、V. Lokshin、J. C. Micheau、A. Samat、R. Guglielmetti、V. I. Minkin

  DOI：10.1039/b204603b

  日期：——

  The photochromic and solvatochromic behaviour of 17 variously substituted spiroindoline naphthoxazines has been investigated in cyclohexane, toluene, acetonitrile and methanol in fluid solution. Specific parameters such as the wavelengths and the molar absorption coefficients of the closed spiro- and open merocyanine forms, together with the photocoloration and photobleaching quantum yields, rate constants and activation energies of thermal fading have been determined under continuous monochromatic irradiation. It has been shown that most of these parameters are closely related to the electron distribution on the highly conjugated photomerocyanines and on their quinoidal or zwitterionic character. Depending on the acceptor or donor properties and on the position of their substituents, three classes of compounds have been detected.

  研究了 17 种不同取代形式的螺吲哚啉萘噁嗪在环己烷、甲苯、乙腈和甲醇的流体溶液中的光致变色和溶致变色行为。在连续单色辐照条件下，确定了封闭螺吲哚菁和开放美拉德菁形式的波长和摩尔吸收系数等具体参数，以及光变色和光漂白量子产率、热褪色速率常数和活化能。结果表明，这些参数大多与高度共轭的光致花青素上的电子分布以及它们的类醌或齐聚物特性密切相关。根据受体或供体的特性及其取代基的位置，可以检测到三类化合物。
• 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。