3',6'-bis(diethylamino)-2-(4-methylphenyl)-2,3-dihydrospiro-[isoindole-1,9'-xanthene]-3-one

• 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: 3',6'-bis(diethylamino)-2-(4-methylphenyl)-2,3-dihydrospiro-[isoindole-1,9'-xanthene]-3-one
• 英文别名: 3',6'-bis-diethylamino-2-p-tolyl-spiro[isoindoline-1,9'-xanthen]-3-one；3',6'-Bis-diaethylamino-2-p-tolyl-spiro[isoindolin-1,9'-xanthen]-3-on；3',6'-Bis(diethylamino)-2-(4-methylphenyl)spiro[isoindole-3,9'-xanthene]-1-one；3',6'-bis(diethylamino)-2-(4-methylphenyl)spiro[isoindole-3,9'-xanthene]-1-one
• 化学式: C₃₅H₃₇N₃O₂
• 分子量: 531.698
• InChiKey: CMOMMUUKABYVDM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  40
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  36
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3',6'-bis(diethylamino)-2-(4-methylphenyl)-2,3-dihydrospiro-[isoindole-1,9'-xanthene]-3-one 在 盐酸 作用下， 以 乙醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  Substituent effects on the turn-on kinetics of rhodamine-based fluorescent pH probes

  摘要：

  基于罗丹明螺内酰胺（RSL）结构的荧光开启探针近来已成为检测 pH 值、金属离子和其他相关分析物的常用方法。RSL 是无色无荧光的，直到目标分析物诱导螺环系统打开，露出完全共轭的高荧光罗丹明染料。在被酸打开的 RSL 中，我们观察到荧光开启过程的动力学差异很大，因此有些探针在需要快速读数或 pH 值随时间波动的情况下无法使用。在此，我们对 RSL 的荧光开启动力学进行了系统研究，以探索反应速率受螺内酰胺环系统电子特性影响的假设。研究人员利用罗丹明 B 制备了一系列 8 种苯胺衍生的 RSL，这些 RSL 的对位取代基的范围从给电子到抽电子不等。这种效应的原因是取代基破坏了反应中间体的稳定性。随着各系列反应速率的增加，荧光强度也随之增加。这一结果归因于染料荧光形式浓度的增加，并与该体系的预期平衡特性相一致。这些发现被应用于设计反应更快、荧光更强的 RSL pH 探针。

  DOI：

  10.1039/c3ob42089b
• 作为产物：
  描述：

  罗丹明B 在 三氯氧磷 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 28.0h， 生成 3',6'-bis(diethylamino)-2-(4-methylphenyl)-2,3-dihydrospiro-[isoindole-1,9'-xanthene]-3-one
  参考文献：
  名称：

  Anilinomethylrhodamines: pH Sensitive Probes with Tunable Photophysical Properties by Substituent Effect

  摘要：

  A series of pH dependent rhodamine analogues possessing an anilino-methyl moiety was developed and shown to exhibit a unique photophysical response to pH. These anilinomethylrhodamines (AnMR) maintain a colorless, non-fluorescent spirocyclic structure at high pH. The spirocyclic structures open in mildly acidic conditions and are weakly fluorescent; however, at very low pH, the fluorescence is greatly enhanced. The equilibrium constants of these processes show a linear response to substituent effects, which was demonstrated by the Hammett equation.

  DOI：

  10.1021/jo401323g

文献信息

• Substituent effects on the turn-on kinetics of rhodamine-based fluorescent pH probes
  作者：William L. Czaplyski、Grace E. Purnell、Courtney A. Roberts、Rebecca M. Allred、Elizabeth J. Harbron

  DOI：10.1039/c3ob42089b

  日期：——

  Fluorescent turn-on probes based on a rhodamine spirolactam (RSL) structure have recently become a popular means of detecting pH, metal ions, and other analytes of interest. RSLs are colorless and non-fluorescent until the target analyte induces opening of the spirocyclic ring system, revealing the fully conjugated and highly fluorescent rhodamine dye. Among RSLs opened by acid, we have observed wide variation in the kinetics of the fluorescence turn-on process such that some probes would not be usable in situations where a rapid reading is desired or the pH fluctuates temporally. Herein we present a systematic investigation of the fluorescence turn-on kinetics of RSLs to probe the hypothesis that the reaction rates are influenced by the electronic properties of the spirolactam ring system. A series of 8 aniline-derived RSLs with para substituents ranging from electron-donating to electron-withdrawing was prepared from rhodamine B. The fluorescence turn-on rates are observed to increase by a factor of four as the substituent is tuned from methoxy to nitro. This effect is explained in terms of the destabilization of the reaction intermediate by the substituent. As the reaction rates increase across the series, a concomitant increase in fluorescence intensity is also observed. This result is attributed to an increase in the concentration of the fluorescent form of the dye and is consistent with the expected equilibrium properties of this system. These findings are applied to the design of a faster-reacting and more intensely fluorescent RSL pH probe.

  基于罗丹明螺内酰胺（RSL）结构的荧光开启探针近来已成为检测 pH 值、金属离子和其他相关分析物的常用方法。RSL 是无色无荧光的，直到目标分析物诱导螺环系统打开，露出完全共轭的高荧光罗丹明染料。在被酸打开的 RSL 中，我们观察到荧光开启过程的动力学差异很大，因此有些探针在需要快速读数或 pH 值随时间波动的情况下无法使用。在此，我们对 RSL 的荧光开启动力学进行了系统研究，以探索反应速率受螺内酰胺环系统电子特性影响的假设。研究人员利用罗丹明 B 制备了一系列 8 种苯胺衍生的 RSL，这些 RSL 的对位取代基的范围从给电子到抽电子不等。这种效应的原因是取代基破坏了反应中间体的稳定性。随着各系列反应速率的增加，荧光强度也随之增加。这一结果归因于染料荧光形式浓度的增加，并与该体系的预期平衡特性相一致。这些发现被应用于设计反应更快、荧光更强的 RSL pH 探针。
• Anilinomethylrhodamines: pH Sensitive Probes with Tunable Photophysical Properties by Substituent Effect
  作者：Quinn A. Best、Chuangjun Liu、Paul D. van Hoveln、Matthew E. McCarroll、Colleen N. Scott

  DOI：10.1021/jo401323g

  日期：2013.10.18

  A series of pH dependent rhodamine analogues possessing an anilino-methyl moiety was developed and shown to exhibit a unique photophysical response to pH. These anilinomethylrhodamines (AnMR) maintain a colorless, non-fluorescent spirocyclic structure at high pH. The spirocyclic structures open in mildly acidic conditions and are weakly fluorescent; however, at very low pH, the fluorescence is greatly enhanced. The equilibrium constants of these processes show a linear response to substituent effects, which was demonstrated by the Hammett equation.