aminobenzopyrano-xanthene 01 | 1259300-20-3

• 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: aminobenzopyrano-xanthene 01
• 英文别名: 3',3-bis(oxospiroisobenzofuran)-3,7-bis(diethylamino)benzopyranoxanthene
• CAS: 1259300-20-3
• 化学式: C₄₂H₃₆N₂O₆
• 分子量: 664.758
• InChiKey: SCNZAHOCNVORBJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  50
• 可旋转键数：
  6
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  77.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  aminobenzopyrano-xanthene 01 在 三氟乙酸 作用下， 以 四氢呋喃 为溶剂， 生成 2-[14-(2-Carboxyphenyl)-3,9-bis(diethylamino)chromeno[3,2-b]xanthene-5,7-diium-12-yl]benzoic acid
  参考文献：
  名称：

  Compound and use thereof

  摘要：

  由以下化学式（1）或（2）表示的化合物：

  公开号：

  US08134017B1
• 作为产物：
  描述：

  苯酐 在 aluminum (III) chloride 、 甲烷磺酸 、 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 反应 6.5h， 生成 aminobenzopyrano-xanthene 01
  参考文献：
  名称：

  Compound and use thereof

  摘要：

  由以下化学式（1）或（2）表示的化合物：

  公开号：

  US08134017B1

文献信息

• 新規化合物及びその製造方法
  申请人：国立研究開発法人理化学研究所

  公开号：JP2020033489A

  公开（公告）日：2020-03-05

  【課題】新規な近赤外有機発光化合物及びその製造方法の提供。【解決手段】式（１）で表される化合物。（Ｒ1及びＲ2は、独立にＨ、Ｃ1〜Ｃ6のアルキル基等；Ｒ3及びＲ4は、独立に置換/無置換のＣ6〜Ｃ14のアリール基等；Ｒ5及びＲ6は、独立にハロゲン原子、Ｃ1〜Ｃ6のアルキル基等；ｍ及びｎは独立に０〜３；Ｘは、Ｃ1〜Ｃ4のアルキル基、（ＣＨ2）Ｃ（＝Ｏ）Ｒで表されるカルボニル基（ＲはＨ又はＣ1〜Ｃ4のアルキル基を示す）等）【選択図】図１

  题目：提供一种新的近红外有机发光化合物及其制备方法。 解决方案：化合物如式（1）所示。（其中，R1和R2分别独立表示氢、C1-C6烷基等；R3和R4分别独立表示取代/未取代的C6-C14芳基等；R5和R6分别独立表示卤素原子、C1-C6烷基等；m和n分别独立表示0-3；X表示C1-C4烷基、由（CH2）C（=O）R表示的羰基（其中R表示氢或C1-C4烷基）等）【选图】图1
• A red-emissive aminobenzopyrano-xanthene dye: elucidation of fluorescence emission mechanisms in solution and in the aggregate state
  作者：Shinichiro Kamino、Atsuya Muranaka、Miho Murakami、Asana Tatsumi、Noriyuki Nagaoka、Yoshinao Shirasaki、Keiko Watanabe、Kengo Yoshida、Jun Horigome、Seiji Komeda、Masanobu Uchiyama、Shuichi Enomoto

  DOI：10.1039/c2cp43503a

  日期：——

  We have designed and synthesized a new class of rhodamine dyes with an extended π-conjugated system and named them 3′,3′′-bis(oxospiroisobenzofuran)-3,7-bis(diethylamino)benzopyrano-xanthene (ABPX01) dyes. ABPX01 exhibits fluorescence emission in both dilute solution and the aggregate state, whereas conventional rhodamine dyes show aggregation-induced quenching (AIQ). The chemical species of ABPX01 in solution were determined by spectrophotometric measurements and density functional theory (DFT) calculations to study the relationship among chemical species, color, and fluorescence emission. ABPX01 has various forms: the spirolactone form (ABPX010), which is colorless; and the monocationic form (ABPX01H+) and the dicationic form (ABPX01H22+), which are colored. By orienting a pair of spirolactone benzene moieties differently, the stereoisomers of trans- and cis-ABPX010 were separated and their crystal structures determined. ABPX01H22+ was identified to be a red fluorescent species. Detailed spectroscopic and electron microscopic investigations led to the assumption that the ABPX01H22+ formed ion associates with Cl− as counter anions in HCl aqueous solution, and the nano- and submicrometer-sized colloidal aggregates of ABPX01 hydrochloride exhibit fluorescence emission. To further verify the aggregation-induced emission enhancement (AIEE) mechanism, ABPX01 hydrochloride was synthesized and its fluorescence was similarly checked in the powder state. AIEE in ABPX01 might be attributed to the synergistic combination of the restriction of dye–dye interaction induced dimer formation by sterically hindered ion associates and carboxylic benzene moieties, and the structural rigidity and intermolecular arrangement of the xanthene moiety. We expect that the design strategy of ABPX dyes will be extended to the development of a wide variety of functional organic-dye-based fluorophores (ODFs) with suitable fluorescence-emission controlled mechanisms for many useful applications in new electroluminescent devices.

  我们设计并合成了一类具有扩展π共轭体系的新型罗丹明染料，并将其命名为 3′,3′′-双（氧代异苯并呋喃）-3,7-双（二乙基氨基）苯并吡喃-氧杂蒽染料（ABPX01）。ABPX01 在稀溶液和聚集状态下都能发出荧光，而传统的罗丹明染料则会出现聚集诱导淬灭（AIQ）。通过分光光度测量和密度泛函理论（DFT）计算，确定了 ABPX01 在溶液中的化学种类，从而研究了化学种类、颜色和荧光发射之间的关系。ABPX01 有多种形态：螺内酯形态（ABPX010）是无色的；单内酯形态（ABPX01H+）和双内酯形态（ABPX01H22+）是有色的。通过改变一对螺内酯苯分子的方向，反式和顺式 ABPX010 的立体异构体被分离出来，并确定了它们的晶体结构。经鉴定，ABPX01H22+ 是一种红色荧光物种。通过详细的光谱和电子显微镜研究，可以推测 ABPX01H22+ 形成的离子在盐酸水溶液中与作为反阴离子的 Cl- 结合，ABPX01 盐酸盐的纳米级和亚微米级胶体聚集体呈现荧光发射。为了进一步验证聚集诱导发射增强（AIEE）机制，我们合成了 ABPX01 盐酸盐，并同样检测了其在粉末状态下的荧光。ABPX01 中的 AIEE 可能归因于立体受阻离子缔合物和羧基苯分子对染料-染料相互作用诱导的二聚体形成的限制，以及呫吨分子的结构刚性和分子间排列的协同作用。我们希望 ABPX 染料的设计策略能够扩展到开发各种功能性有机染料荧光团（ODF），这些荧光团具有合适的荧光发射控制机制，可用于新型电致发光器件中的许多有用应用。
• Nucleophile‐Triggered π‐Topological Transformation: A New Synthetic Approach to Near‐Infrared‐Emissive Rhodamines
  作者：Mei Harada、Misa Kutsuna、Taichi Kitamura、Yusuke Usui、Masayoshi Ujiki、Yuka Nakamura、Tohru Obata、Masaru Tanioka、Masanobu Uchiyama、Daisuke Sawada、Shinichiro Kamino

  DOI：10.1002/chem.202301969

  日期：2023.10.23

  π-Topological transformation-based synthetic method: A new type of near-infrared (NIR)-emissive rhodamine dye, called Polymethine-embedded Rhodamine Fluorophore (PeR Fluor), has been developed. Linear fully π-conjugated PeR Fluor is prepared in one step by mixing different nucleophiles (Nu−) with ABPXs, a family of rhodamines with a cross-conjugated structure. PeR Fluor exhibits bright NIR fluorescence

  基于π拓扑变换的合成方法：开发了一种新型近红外（NIR）发射罗丹明染料，称为聚次甲基嵌入罗丹明荧光团（PeR Fluor ）。通过将不同的亲核试剂 (Nu - ) 与 ABPX（一种具有交叉共轭结构的罗丹明家族）混合，一步制备线性完全 π 共轭PeR Fluor 。PeR Fluor具有明亮的近红外荧光发射和高光稳定性。
• Selective Hg²⁺ Sensing Behaviors of Rhodamine Derivatives with Extended Conjugation Based on Two Successive Ring-Opening Processes
  作者：Chunyan Wang、Keith Man-Chung Wong

  DOI：10.1021/ic401810x

  日期：2013.12.2

  A novel class of rhodamine derivatives with two spirolactam moieties have been synthesized, and their two stereoisomers of cis- and trans-forms have been successfully separated and isolated, as well as structurally characterized by X-ray crystallography. Attributed to the successive ring-openings of two spirolactam moieties, different solution color, electronic absorption and emission responses were exhibited upon addition of various concentrations of mercury(II) ion. Arising from two successive ring-opening processes in the presence of various concentration of Hg(II) ion, two reporting states with different spectroscopic properties were suggested, that is, the first state showing pink color (absorption maximum at 496 nm) but no emission, while the second state giving purple color (absorption maximum at 593 nm) and red emission (emission maximum at 620 nm). The mechanism of such different spectroscopic responses was also proposed and has also been supported by computational studies. An extension of the present work to the study of the corresponding chemodosimeters from the compounds with two spirolactam groups has been made, in which a stoichiometric and irreversible Hg(II)-promoted reaction of thiosemicarbazides was utilized to form 1,3,4-oxadiazoles.
• US8134017B1
  申请人：——

  公开号：US8134017B1

  公开（公告）日：2012-03-13