9,9-dimethyl-9H-xanthene-4,5-dicarbaldehyde | 261724-74-7

• 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: 9,9-dimethyl-9H-xanthene-4,5-dicarbaldehyde
• 英文别名: 4,5-diformyl-9,9-dimethylxanthene；9,9-dimethylxanthene-4,5-dicarbaldehyde
• CAS: 261724-74-7
• 化学式: C₁₇H₁₄O₃
• 分子量: 266.296
• InChiKey: MJDDWPSHCZGWKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  9,9-dimethyl-9H-xanthene-4,5-dicarbaldehyde 在 氢氧化钾 、 jones reagent 、 二苯基膦叠氮化物 、 三乙胺 作用下， 以 乙醇 、 丙酮 、 甲苯 为溶剂， 反应 46.0h， 生成 9,9-dimethyl-9H-xanthene-4,5-diamine
  参考文献：
  名称：

  Photoinduced Hinge-Like Molecular Motion:  Studies on Xanthene-Based Cyclic Azobenzene Dimers

  摘要：

  Molecular devices incorporating azobenzene units represent active components of smart systems, as they are capable of exhibiting photoregulated cooperative molecular motion. Herein, we describe the synthesis, X-ray crystal analysis, and photochemical and thermal studies of a xanthene based cyclic azobenzene dimer and its precursor. The trans-trans isomer of the azobenzene dimer upon photoirradiation transforms to the cis-cis isomer through an intermediate trans-cis isomer. The X-ray crystal structures of the trans-trans isomer (open) and the cis-cis isomer (closed) provide unambiguous proof for the hinge-like molecular motion in this class of molecules. The inferences drawn from photochemical and thermal studies shed light on the effect of varied substitution and cyclic structures on the different transitions. The lifetime of the cis-cis isomer is estimated to be 6.43 years, whereas the trans-cis isomer is short-lived (2.73 min) at 303 K. A rational explanation for the relative stability of the different isomers is derived from the isokinetic plot and theoretical calculations.

  DOI：

  10.1021/jo0513616
• 作为产物：
  描述：

  9,9-二甲基氧杂蒽 在 正丁基锂 、 四甲基乙二胺 、 盐酸 、 N,N-二甲基甲酰胺 作用下， 以 正己烷 、 水 为溶剂， 反应 1.5h， 以91%的产率得到9,9-dimethyl-9H-xanthene-4,5-dicarbaldehyde
  参考文献：
  名称：

  A new xantphos-type ligand and its gold(I) complexes: Synthesis, structure, luminescence

  摘要：

  A novel xantphos analog diphosphine ligand, 9,9-dimethyl-4,5-bis(diphenylphosphinomethyl)-9H-xanthene (X(CP)(2)), with methylene groups inserted between the xanthene skeleton and the two diphenylphosphine units, has been synthesized. A two-coordinate and a three-coordinate gold(I) complex of the ligand, [Au2Cl2(X(CP)(2))] and [AuCl(X(CP)(2))], have been prepared and studied by X-ray diffraction, NMR and optical spectroscopy. In the solid state, [AuCl(X(CP)(2))] adopts a highly ordered structure with a planar xanthene skeleton that faces another plane composed of two phenyl rings and the AuCl moiety. The structure of [Au2Cl2(X(CP)(2))] is much less regular, the two P-Au-Cl vectors point to the opposite sides of the folded xanthene backbone. The exchange-broadened resonances in the NMR spectra of [AuCl(X(CP)(2)))] indicate that this complex exists as a mixture of various chemical species and/or conformers in solution. In contrast, the NMR spectra of [Au2Cl2(X(CP)(2))] exclude any medium-range exchange processes. Aurophilic interactions are absent in both X(CP)(2) complexes. X(CP)(2), as well as its two gold complexes, is phosphorescent in the solid state; the complexes emit at higher wavelengths and with longer lifetimes than the free ligand. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2013.02.052

文献信息

• Design and Photophysical Properties of Zinc(II) Porphyrin-Containing Dendrons Linked to a Central Artificial Special Pair
  作者：Frédérique Brégier、Shawkat M. Aly、Claude P. Gros、Jean-Michel Barbe、Yoann Rousselin、Pierre D. Harvey

  DOI：10.1002/chem.201101832

  日期：2011.12.16

  act as singlet and triplet energy acceptors or donors, depending on the dendrimeric systems. The presence of the paramagnetic d9 copper(II) in the dendrimers promotes singlet–triplet energy transfer from the zinc(II) tetra‐meso‐arylporphyrin to the bis(copper(II) porphyrin) unit and slow triplet–triplet energy transfer from the central bis(copper(II) porphyrin) fragment to the peripheral zinc(II)

  点击化学的合成和光物理性质，特别是一系列人造特殊对-树枝状体系（树枝状= G1，G2，G3；G x =锌（II））的中心核与周围发色团之间的光诱导能量和电子转移据报道，在二甲基黄嘌呤双（金属（II）卟啉）（金属=锌，铜）的中心核上构建了含四-内消旋-芳基卟啉的聚酰亚胺）。根据树状体系，树状体充当单线态和三线态能量受体或供体。顺磁性d的存在9铜（II）在树枝状聚合物促进了从锌（II）四-单线态-三线态能量传递的内消旋-芳基卟啉转移到双（铜（II）卟啉）单元，并且三重态-三重态能量从中心双（铜（II）卟啉）片段转移到周围的锌（II）四内消旋-芳基卟啉。如果以bis（锌（II）卟啉）为中心核，则观察到链折叠的证据；异双金属系统中三重态-三重态能量传递的存在清楚地证明了这一点，该过程只能在短距离内发生。
• Electronic Structures and Reactivity Profiles of Aryl Nitrenoid-Bridged Dicopper Complexes
  作者：Kurtis M. Carsch、James T. Lukens、Ida M. DiMucci、Diana A. Iovan、Shao-Liang Zheng、Kyle M. Lancaster、Theodore A. Betley

  DOI：10.1021/jacs.9b09616

  日期：2020.2.5

  indicate that the formally Class IIIA mixed valence complexes of the type [(Rdmx)Cu2(µ2-NAr)]-, featuring significant NAr-localized spin following reduction from electronic population of the [Cu2(µ2-NAr)] π* manifold and contrasting previ-ous methods for engendering iminyl character through chemical oxidation. The reactivity of the isolable imido and iminyl complexes are examined for prototypical radical-promoted

  以双核 pacman 二吡啉配体支架（Mesdmx、tBudmx：二甲基黄嘌呤桥接、共面双二吡啶）为模板的二铜配合物是通过用均三甲苯（CuMes；Mes：均三甲苯）去质子化/金属化或通过用来自相应去质子化配体的亚铜前体进行金属转移来合成的。通过用芳基叠氮化物处理相应的二铜配合物合成中性酰亚胺配合物(Rdmx)Cu2(μ2-NAr)(R: Mes, tBu; Ar: 4-MeOC6H4, 3,5-(F3C)2C6H3)。虽然 (Mesdmx)Cu2(μ2-N(C6H4OMe)) 用钾石墨进行单电子还原会在室温下引发分子内苄基 CH 胺化，但 (tBudmx)Cu2(μ2-NAr) 的化学还原会导致可分离的 [ (tBudmx)Cu2(μ2-NAr)]-产物盐。通过变温电子顺磁共振光谱、X射线吸收光谱（Cu L2,3/K-edge、N K -edge）、光谱学和 DFT/CASSCF 计算。这
• Bimetallic Complexes for Enhancing Catalyst Efficiency: Probing the Relationship between Activity and Intermetallic Distance
  作者：Marina G. Timerbulatova、Mark R. D. Gatus、Khuong Q. Vuong、Mohan Bhadbhade、Andrés G. Algarra、Stuart A. Macgregor、Barbara A. Messerle

  DOI：10.1021/om4005059

  日期：2013.9.23

  monometallic complexes [Rh(CO)2(LPh)][BArF4] (7, LPh = α,α-bis(pyrazol-1-yl)toluene) and [Rh(COD)(LPh)][BArF4] (20) were synthesized. The solid-state structures of 8, 10, 16, 17, and 21 were determined using single-crystal X-ray diffraction analysis. The catalytic activity of complexes 7–12 was established for the dihydroalkoxylation of the alkynediols 2-(5-hydroxypent-1-ynyl)benzyl alcohol (I) and 2-(

  一系列新的同位异位配体（14 – 17），包含两个双（吡唑-1-基）甲烷与柔性的（1,6-双（双（吡唑-1-基）甲基）己烷，L 6C（14））; 1,7-双（双（吡唑-1-基）甲基）庚烷，L 7C（15））或刚性支架（4,5-双（双（吡唑-1-基）甲基）-9,9合成了-二甲基x吨，L Xan（16）； 4,6-双（双（吡唑-1-基）甲基）二苯并呋喃，L Dib（17））。一系列双金属铑（I）配合物[Rh 2（CO）4（L X）] [BAr F 4 ] 2（X = Xan（8），Dib（9），Fc（（（1,1'-双（双（吡唑并1-基）甲基）二茂铁）（10）），6C（11），7C（12））和[Rh 2（COD）2（L X）] [BAr F 4 ] 2（COD = 1,5-环辛二烯，X = 6C（21），7C（22））以及单金属配合物[Rh（CO ）2（L Ph）] [BAr F 4 ]（7，L
• Efficient Two-Step Synthesis of Face-to-Facemeso-Substituted Bis(corrole) Dyads
  作者：Maya El Ojaimi、Claude P. Gros、Jean-Michel Barbe

  DOI：10.1002/ejoc.200700985

  日期：2008.3

  face-to-face meso-substituted bis(corrole) systems was revisited. By using a new synthetic pathway, the reaction was generalized to any type of linker and the yield was considerably increased. The dyads were obtained in yields up to 20 % from a dialdehyde linker and dipyrromethane in a one-step reaction. The best reaction conditions required a decreased amount of TFA catalyst (1.4 equiv.) and a large excess

  重新审视了面对面介观取代双（corrole）系统的合成。通过使用新的合成途径，该反应可以推广到任何类型的接头，并且产率显着提高。在一步反应中从二醛接头和二吡咯甲烷以高达 20% 的产率获得二元组。最佳反应条件需要减少 TFA 催化剂的用量（1.4 当量）和大量过量的二吡咯甲烷（高达 8 当量）。在这些条件下，合成了由 2,2'-二苯醚、9,9-二甲基呫吨、蒽和二苯并呋喃间隔物连接的四种双（corrole）。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451 Weinheim，德国, 2008)
• Cofacial Boron Dipyrromethene (Bodipy) Dimers: Synthesis, Charge Delocalization, and Exciton Coupling
  作者：Andrew C. Benniston、Graeme Copley、Anthony Harriman、David Howgego、Ross W. Harrington、William Clegg

  DOI：10.1021/jo1000803

  日期：2010.3.19

  BD4 show the methylene protons to be diastereotopic due to restricted rotation of the two Bodipy groups. For BD4 conformational rocking is invoked to explain the variable-temperature NMR spectra, whereby the methyl and methylene groups become inequivalent. Cyclic voltammetry indicates reversible oxidation and reduction of the Bodipy groups. However, the close proximity of the Bodipy groups in BD3 and

  已合成并充分表征了一系列包含两个硼二吡咯亚甲基（Bodipy）单元的化合物，其中两个Bodipy基团之间的间隔基从二苯并噻吩（BD1）到二苯并呋喃（BD2）到9,9-二甲基x吨（BD3）不等，最后是二苯醚（BD4和BD5）。对于BD1 - BD4，Bodipy单元在不同程度上采用了界面构象，从而可以系统地改变两个Bodipy残基的相互取向和平均间隔。在剩余的二聚体中，BD5，Bodipy单元间隔良好，无法靠近。已经确定了BD1 - BD3的单晶X射线结构，揭示了两个Bodipy残基之间的“咬合角”沿着该系列逐渐减小，其单个值为41.33（5）°，36.95（6）°和8.57。 （3）°。BD3和BD4的详细1 H和19 F NMR研究表明，由于两个Bodipy基团的旋转受限制，亚甲基质子为非对映体。对于BD4构象摇动被用来解释变温NMR光谱，由此甲基和亚甲基变得不等价。循环伏安法表明Bod