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- | 114747-44-3

• 物质功能分类: 化学试剂 - 有机试剂 - 多环化合物
• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 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-
• 英文名称: 6'-Indolino-1,3,3-trimethylspironaphth<2,1-b><1,4>oxazine>
• 英文别名: 1,3,3-trimethylspiro(indoline-2,3'<3H>naphth<2,1-b>-6'-indolino<1,4>oxazine)；1,3,3-trimethyl-6'-indolinospiro(indoline-2,3'-naphtho[2,1b][1,4]oxazine)；6'-indolino-1,3,3-trimethylspiro(indolino-2,3'-[3H]naphth[2,1-b]oxazine)；1,3-Dihydro-1,3,3-trimethyl-6'-(2,3-dihydroindol-1-yl) spiro[2H-indole-2,3'-3H-naphtho[2,1-b][1,4]oxazine]；6'-Indolino-1,3,3-trimethylspiro(indoline-2,3'-[3H]naphth[2,1-b][1,4]oxazine)；6'-(Indolin-1-yl)-1,3,3-trimethylspiro[indoline-2,3'-naphtho[2,1-b][1,4]oxazine]；6-(2,3-dihydroindol-1-yl)-1',3',3'-trimethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole]
• CAS: 114747-44-3
• 化学式: C₃₀H₂₇N₃O
• 分子量: 445.564
• InChiKey: PITZBBWQUBGWTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  34
• 可旋转键数：
  1
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.23
• 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：
  P280,P305+P351+P338
• 危险性描述：
  H302

反应信息

• 作为反应物：
  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
• 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， 反应 21.17h， 生成 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-
  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。
• Photo reactive spiro-benzoxazine compounds
  申请人：Pilkington plc

  公开号：US05446151A1

  公开（公告）日：1995-08-29

  A photo reactive material, such as a photochromic material, which has the following structure: ##STR1## where the variables, A, R, R', R", R*, R.sup.+, m, and n are defined in claim 1.

  一种光敏材料，例如光致变色材料，具有以下结构：##STR1## 其中变量A、R、R'、R"、R*、R.sup. +、m和n在权利要求1中定义。
• 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。
• Photo reactive material
  申请人：PILKINGTON PLC

  公开号：EP0600669A1

  公开（公告）日：1994-06-08

  A photo reactive material, such as a photochromic material, which has the following structure: where Ais a six membered carbocyclic or heterocyclic ring; each Ris alkyl, alkenyl, alkynyl, aryl, carbocyclic, heterocyclic, alkyl carbocyclic or alkyl heterocyclic or at least two of the R groups together form part of a carbocyclic or heterocyclic ring or one of the R groups is hydrogen with the other two being selected from the above; R*are independent of one another and are selected from branched or linear C₁-C₁₀ alkyls and carbocyclic or heterocyclic groups or both form part of a carbocyclic or heterocyclic ring; R⁺mis selected from alkyl alkoxy, amino, halogen, cyano, nitro, trifluoromethyl or aryl and m has a value between 0 and 4; R⁺nis selected from carbocyclic and heterocyclic groups which are fused to A and n has a value between 0 and 2. R'is selected from hydrogen, alkyl, alkoxy, amino, carbocylic or heterocyclic. R''is selected from hydrogen, alkyl, aryl, heteroaryl, alkenyl, alkynyl, alkoxy, aryloxy, amino, halogen, cyano, nitro, trifluoromethyl, imino, azo, carboxy ester or amide or is a carbocyclic or heterocyclic group fused to the moiety.

  光反应材料，如光致变色材料，其结构如下： 其中 A 是六分子碳环或杂环； 每个 Ris 烷基、烯基、炔基、芳基、 碳环、杂环、烷基碳环或烷基杂环 或至少两个 R 基团共同构成碳环或杂环的一部分 或其中一个 R 基团为氢，另外两个从上述基团中选出； R* 相互独立，选自支链或线性 C₁-C₁₀烷基和碳环或杂环基团，或两个基团共同构成碳环或杂环的一部分； R⁺m 选自烷基烷氧基、氨基、卤素、氰基、硝基、三氟甲基或芳基，且 m 的值在 0 至 4 之间； R⁺n 选自与 A 融合的碳环和杂环基团，n 的值在 0 和 2 之间。 R'选自氢、烷基、烷氧基、氨基、羰基或杂环。 R''选自氢、烷基、芳基、杂芳基、烯基、炔基、烷氧基、芳氧基、氨基、卤素、氰基、硝基、三氟甲基、亚氨基、偶氮、羧基酯或酰胺，或者是与分子融合的碳环或杂环基团。