(5-Bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)-carbamic acid benzyl ester | 389827-70-7

• 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: (5-Bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)-carbamic acid benzyl ester
• 英文别名: 5-Bromo-2,7-di-tert-butyl-N-Cbz-9,9-dimethyl-9H-xanthen-4-amine；benzyl N-(5-bromo-2,7-ditert-butyl-9,9-dimethylxanthen-4-yl)carbamate
• CAS: 389827-70-7
• 化学式: C₃₁H₃₆BrNO₃
• 分子量: 550.536
• InChiKey: CYLOEDMCDBYASI-UHFFFAOYSA-N

物化性质

• 熔点：
  136-138 °C(Solv: ethanol (64-17-5))
• 沸点：
  534.2±50.0 °C(Predicted)
• 密度：
  1.236±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (5-Bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)-carbamic acid benzyl ester 在 氢氧化钾 、 四氯化钛 、 三乙胺 作用下， 以 乙醇 、 甲苯 为溶剂， 生成 (5-Bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)-[(1R,4R)-1,7,7-trimethyl-bicyclo[2.2.1]hept-(2E)-ylidene]-amine
  参考文献：
  名称：

  Synthesis of xanthene-derived diimine and iminophosphine compounds as potential chiral bidentate ligands

  摘要：

  The synthesis of one diimine and two iminophosphine chiral ligands bearing a xanthene backbone in, respectively, four and five steps is described. The diimine is characterised by X-ray crystallography. A preliminary test in palladium-catalysed asymmetric allylic alkylation is reported. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01588-x
• 作为产物：
  描述：

  4,5-二溴-2,7-二叔丁基-9,9-二甲基呫吨 在 正丁基锂 、 叠氮磷酸二苯酯 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 17.25h， 生成 (5-Bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)-carbamic acid benzyl ester
  参考文献：
  名称：

  π-聚集体的共面和滑动堆叠苝-3,4-二甲酰亚胺二聚体模型中的能量流动动力学

  摘要：

  稳健的苝-3,4-二甲酰亚胺 (PMI) π-聚集体在有机光伏和相关应用中提供了重要的光捕获和电子-空穴对生成优势，但相对较少的研究关注 PMI 生色团之间的电子相互作用。相比之下，相关的苝-3,4:9,10-双（二甲酰亚胺）（PDI）中基于 π-π 堆积的结构-功能关系已得到广泛研究。PMI 和 PDI 衍生物在有机器件中的性能可能受到在发色团间耦合很强的形态中形成低能准分子陷阱态的限制。在这里，研究了五种具有不同程度电子相互作用的共价结合 PMI 二聚体，以探测导致准分子能量陷阱状态的相对发色团方向。飞秒近红外瞬态吸收光谱用于观察在~1450-1520 nm 处低能量跃迁的生长，这些跃迁是这些共价二聚体中准分子态的特征。准分子态吸收出现在约 1 ps 内，然后在 8-17 ps 内出现构象松弛。准分子状态然后在 6.9-12.8 ns 内衰减，如通过时间分辨荧光光谱测量。对于滑动堆叠几何，准分子寿命达到最大值，其中两个

  DOI：

  10.1021/ja507653p

文献信息

• Singlet Fission in Covalent Terrylenediimide Dimers: Probing the Nature of the Multiexciton State Using Femtosecond Mid-Infrared Spectroscopy
  作者：Michelle Chen、Youn Jue Bae、Catherine M. Mauck、Aritra Mandal、Ryan M. Young、Michael R. Wasielewski

  DOI：10.1021/jacs.8b04830

  日期：2018.7.25

  a xanthene spacer (XanTDI2). Femtosecond mid-infrared (fsIR) spectroscopy shows that the multiexciton 1(T1T1) state has absorptions characteristic of the T1 state in the carbonyl stretch region of the IR spectrum, in addition to IR absorptions specific to the CT state in the C═C stretch region. The simultaneous presence of CT and triplet state features in both high dielectric constant CH2Cl2 and low

  单线态裂变 (SF) 是一种允许自旋的过程，涉及两个电子相互作用的发色团吸收光子以产生单线态激子状态 1(S1S0)，如果单线态激子能量约为两倍，则随后快速形成两个三线态激子三重态激子的那个。多激子相关三重对态 1(T1T1) 的初始形成被认为涉及电荷转移 (CT) 态的代理。这些电子状态的动力学在共价滑动堆叠的 terrylene-3,4:11,12-bis(dicarboximide) (TDI) 二聚体中进行了研究，其中两个 TDI 分子的构象由呫吨间隔物 (XanTDI2) 决定。飞秒中红外 (fsIR) 光谱显示多激子 1(T1T1) 态在红外光谱的羰基拉伸区域具有 T1 态的吸收特征，除了 C=C 拉伸区域中 CT 状态特有的 IR 吸收之外。在整个多激子态寿命期间，高介电常数 CH2Cl2 和低介电常数 1,4-二恶烷中同时存在 CT 和三重态特征表明该状态具有 CT 和三重态特征。
• Triplet State Formation in Photoexcited Slip-Stacked Perylene-3,4:9,10-bis(dicarboximide) Dimers on a Xanthene Scaffold
  作者：Kelly M. Lefler、Kristen E. Brown、Walter A. Salamant、Scott M. Dyar、Kathryn E. Knowles、Michael R. Wasielewski

  DOI：10.1021/jp4083008

  日期：2013.10.10

  Two covalent perylene-3,4:9,10-bis(dicarboximide) (PDI) dimers in which the PDI molecules are attached to a xanthene (Xan) scaffold in which the long axes of the two pi-pi stacked PDI molecules are slipped by 4.3 and 7.9 angstrom were prepared. These dimers are designed to mimic J-aggregates and provide insights into the photophysics of triplet state formation in PDI aggregates that target organic electronics. Using ultrafast transient absorption and stimulated Raman spectroscopy, the mechanism of 3*PDI formation was found to depend strongly on a competition between the rate of Xan(circle+)-PDI circle- formation involving the spacer group and the rate of excimer-like state formation. Which mechanism is favored depends on the degree of electronic coupling between the two PDI molecules and/or solvent polarity. Singlet exciton fission to produce 3*PDI does not compete kinetically with these processes. The excimer-like state decays relatively slowly with tau = 28 ns to produce 3*PDI, while charge recombination of Xan(circle+)-PDI circle- yields 3*PDI more than an order of magnitude faster. The perpendicular orientation between the pi orbitals of PDI and the Xan bridge provides a large enough orbital angular momentum change to greatly increase the intersystem crossing rate via Xan(circle+)-PDI circle- -> (3)*PDI charge recombination. These results highlight the importance of understanding inter-chromophore electronic coupling in a wide range of geometries as well as the active role that molecular spacers can play in the photophysics of covalent models for self-assembled chromophore aggregates.
• Synthesis of xanthene-derived diimine and iminophosphine compounds as potential chiral bidentate ligands
  作者：Grégory Malaisé、Laurent Barloy、John A Osborn

  DOI：10.1016/s0040-4039(01)01588-x

  日期：2001.10

  The synthesis of one diimine and two iminophosphine chiral ligands bearing a xanthene backbone in, respectively, four and five steps is described. The diimine is characterised by X-ray crystallography. A preliminary test in palladium-catalysed asymmetric allylic alkylation is reported. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Energy Flow Dynamics within Cofacial and Slip-Stacked Perylene-3,4-dicarboximide Dimer Models of π-Aggregates
  作者：Rebecca J. Lindquist、Kelly M. Lefler、Kristen E. Brown、Scott M. Dyar、Eric A. Margulies、Ryan M. Young、Michael R. Wasielewski

  DOI：10.1021/ja507653p

  日期：2014.10.22

  strong. Here, five covalently bound PMI dimers with varying degrees of electronic interaction were studied to probe the relative chromophore orientations that lead to excimer energy trap states. Femtosecond near-infrared transient absorption spectroscopy was used to observe the growth of a low-energy transition at ~1450-1520 nm characteristic of the excimer state in these covalent dimers. The excimer-state

  稳健的苝-3,4-二甲酰亚胺 (PMI) π-聚集体在有机光伏和相关应用中提供了重要的光捕获和电子-空穴对生成优势，但相对较少的研究关注 PMI 生色团之间的电子相互作用。相比之下，相关的苝-3,4:9,10-双（二甲酰亚胺）（PDI）中基于 π-π 堆积的结构-功能关系已得到广泛研究。PMI 和 PDI 衍生物在有机器件中的性能可能受到在发色团间耦合很强的形态中形成低能准分子陷阱态的限制。在这里，研究了五种具有不同程度电子相互作用的共价结合 PMI 二聚体，以探测导致准分子能量陷阱状态的相对发色团方向。飞秒近红外瞬态吸收光谱用于观察在~1450-1520 nm 处低能量跃迁的生长，这些跃迁是这些共价二聚体中准分子态的特征。准分子态吸收出现在约 1 ps 内，然后在 8-17 ps 内出现构象松弛。准分子状态然后在 6.9-12.8 ns 内衰减，如通过时间分辨荧光光谱测量。对于滑动堆叠几何，准分子寿命达到最大值，其中两个