6-chloro-1',3',3'-trimethylspiro[chromene-2,2'-indoline] | 61431-10-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 6-chloro-1',3',3'-trimethylspiro[chromene-2,2'-indoline]
• 英文别名: 1,3,3-trimethyl-6'-chlorospiro[indoline-2,2′-2H-chromene]；6-chloro-1',3',3'-trimethyl-1',3'-dihydro-spiro[chromene-2,2'-indole]；1,3,3-Trimethyl-6'-chlorospiro[indoline-2,2'-2h-chromene]；6-chloro-1',3',3'-trimethylspiro[chromene-2,2'-indole]
• CAS: 61431-10-5
• 化学式: C₁₉H₁₈ClNO
• 分子量: 311.811
• InChiKey: HVKJBDSEBQHXFO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-chloro-1',3',3'-trimethylspiro[chromene-2,2'-indoline] 反应 0.17h， 生成 4-Chloro-6-[2-[1,3,3-trimethyl-1,3-dihydro-indol-(2E)-ylidene]-eth-(Z)-ylidene]-cyclohexa-2,4-dienone
  参考文献：
  名称：

  Novel Syntheses of Spiropyran Photochromatic Compounds Using Ultrasound

  摘要：

  DOI：

  10.1080/00397919508010795
• 作为产物：
  描述：

  1,3,3-三甲基-2-亚甲基吲哚啉 以34%的产率得到
  参考文献：
  名称：

  Torres R. Silvia, Vazquez S. Ana L., Gonzalez S. Eduardo A., Synth. Commun, 25 (1995) N 1, S 105-110

  摘要：

  DOI：

文献信息

• Thermal Racemization of Substituted Indolinobenzospiropyrans:  Evidence of Competing Polar and Nonpolar Mechanisms
  作者：Susan Swansburg、Erwin Buncel、Robert P. Lemieux

  DOI：10.1021/ja0001613

  日期：2000.7.1

  σp constants in 90:10 hexanes/2-propanol and acetonitrile suggest that thermal racemization of the 6-substituted spiropyrans proceed via two competing mechanisms: a polar mechanism involving heterolytic C(sp3)−O bond cleavage with anchimeric assistance from the indoline nitrogen and a nonpolar electrocyclic ring opening mechanism with no anchimeric assistance from the indoline nitrogen. The outcome

  通过手性固定相 HPLC 拆分了一系列 6-取代的吲哚并苯并螺吡喃，并通过圆二色谱法在 60 °C 下在三种不同溶剂中测量了其热外消旋化的速率常数 krac 测量：环己烷、90:10 己烷/2-丙醇和乙腈. 结果表明，螺吡喃在乙腈中的热外消旋化速度最快，krac 值范围为 9.3 × 10-5 至 >5.0 × 10-3 s-1，而在环己烷中的热外消旋化速度最慢，krac 值范围为 6.8 × 10-6到 4.6 × 10-4 s-1。在 90:10 己烷/2-丙醇和乙腈中 log krac 与 Hammett σp 常数的 V 形图表明 6-取代螺吡喃的热外消旋化通过两种竞争机制进行：一种极性机制涉及异裂 C(sp3)-O 键断裂，二氢二氢氮的嵌合辅助和非极性电环开环机制，没有二氢吲哚氮的嵌合辅助。这场比赛的结果出现了……
• Thermo- and photochromic dyes: Spiro(indolinebenzopyrans). 2—detailed assignment of the1H NMR spectra and structural aspects of the closed form of 1,3,3-trimethylspiro(indoline-2,2′-benzopyrans)
  作者：Sam-Rok Keum、Ki-Bong Lee、Peter M. Kazmaier、Richard A. Manderville、Erwin Buncel

  DOI：10.1002/mrc.1260301119

  日期：1992.11

  The proton NMR assignments for a series of 12 thermo- and photochromic 1,3,3-trimethylspiro(indoline-2,2′-benzopyrans) dyes is reported. All of the protons in the dye molecule were assigned through a combination of homonuclear decoupling experiments and correlation spectroscopy. The relative stereochemistry of the indolino gem-dimethyl groups was assigned so that, for the S-epimer, the pro-R methyl was found to resonate at 1.24 ppm while the pro-S methyl appeared at 1.37 ppm for compound 1.

  报道了一系列 12 种热致变色和光致变色 1,3,3-三甲基螺（二氢吲哚-2,2'-苯并吡喃）染料的质子 NMR 归属。染料分子中的所有质子都是通过同核解耦实验和相关光谱的结合来分配的。吲哚啉偕二甲基的相对立体化学被指定，因此对于 S-差向异构体，发现前 R 甲基在 1.24 ppm 处共振，而对于化合物 1，前 S 甲基出现在 1.37 ppm 处。
• Structure and Properties of 1,3,3-Trimethyl-6′-chlorospiro[indoline-2,2′-2H-chromene]
  作者：A. D. Pugachev、V. V. Tkachev、S. M. Aldoshin、N. I. Makarova、I. A. Rostovtseva、A. V. Metelitsa、N. V. Stankevich、G. V. Shilov、B. S. Lukyanov

  DOI：10.1134/s1070363221070069

  日期：2021.7

  Indoline spiropyran containing an σ-acceptor chlorine atom in 6′ position of the 2H-chromene part of the molecule was synthesized and studied. The use of 1,2,3,3-tetramethyl-3H-indolium perchlorate as a starting compound made it possible to achieve higher product yields as compared to previous studies. The molecular structure of the compound was established by single crystal X-ray diffraction analysis. The features of the crystal structure and intermolecular interactions were investigated using CrystalExplorer17 software package. The photochromic behavior in acetonitrile solution was studied for the first time. It was found that the merocyanine form of spiropyran is characterized by an absorption maximum at 592 nm, which is 37 nm closer to the range of the “biological window” in comparison with the nitro-substituted analog.

  摘要 合成并研究了在分子 2H-Cromene 部分的 6′ 位含有一个 σ 受体氯原子的吲哚啉螺吡喃。与以前的研究相比，使用 1,2,3,3-四甲基-3H-吲哚鎓高氯酸盐作为起始化合物可以获得更高的产物收率。通过单晶 X 射线衍射分析，确定了该化合物的分子结构。利用 CrystalExplorer17 软件包研究了晶体结构的特征和分子间的相互作用。首次研究了乙腈溶液中的光致变色行为。研究发现，经花青素形式的螺吡喃在 592 纳米波长处具有吸收最大值，与硝基取代的类似物相比，其吸收最大值距离 "生物窗口 "范围更近 37 纳米波长。
• ‘Ship-in-a-Bottle’ Synthesis and Photochromism of Spiropyrans Encapsulated within Zeolite Y Supercages
  作者：Isabel Casades、Steven Constantine、David Cardin、Hermenegildo Garcı́a、Andrew Gilbert、Francisco Márquez

  DOI：10.1016/s0040-4020(00)00515-9

  日期：2000.9

  spectroscopies are compatible with the formation of the merocyanine form of the spiropyran photochromic system. Upon visible irradiation the solids bleach, and in some cases the coloration is regained upon standing in the dark for long periods. This abnormal photochromic behaviour is the reverse of that observed for the spiropyran/merocyanine system in ethanol and illustrates the possibility of zeolites

  NaY笼内的三个螺吡喃的瓶装合成是通过2-亚甲基-1,3,3-三甲基二氢吲哚与适当的取代苯甲醛缩合进行的。反应后，在上清液中检测到螺吡喃，并且沸石变色。燃烧化学和热重分析证实固体中存在有机物质。紫外可见光谱和拉曼光谱与螺吡喃光致变色系统的花青形式形成兼容。在可见光照射下，固体会漂白，在某些情况下，长时间在黑暗中放置会恢复颜色。这种异常 光致变色行为与在乙醇中的螺吡喃/花青素系统观察到的相反，并且说明了沸石作为介质改变掺入的客体的分子特性的可能性。
• A study of the spiropyran–merocyanine system using ion mobility-mass spectrometry: experimental support for the cisoid conformation
  作者：Robert A. Rogers、Allison R. Rodier、Jake A. Stanley、Nick A. Douglas、Xiaopeng Li、William J. Brittain

  DOI：10.1039/c3cc47697a

  日期：——

  The spiropyran–merocyanine system was studied using ion mobility-mass spectrometry (IM-MS) and three major conformers were identified. Assignment of conformers is based on DFT-B3LYP energy minimized structures and collision cross-sections as light-induced changes in IM-MS. The three conformers were assigned to the spiropyran, cisoid and transoid structures.

  使用离子迁移率质谱（IM-MS）研究了螺吡喃-氰胺系统，并确定了三种主要构象。构象的分配基于DFT-B3LYP能量最小化结构和碰撞截面，作为IM-MS中光诱导的变化。这三种构象被分配到螺吡喃、顺式和反式结构中。