(2,7-di-tert-butyl-9,9-dimethyl)-9H-xanthene-4,5-dicarbaldehyde | 650599-75-0

• 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: (2,7-di-tert-butyl-9,9-dimethyl)-9H-xanthene-4,5-dicarbaldehyde
• 英文别名: 2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-dicarbaldehyde；2,7-di-tert-butyl-4,5-diformyl-9,9-dimethylxanthen；2,7-Ditert-butyl-9,9-dimethylxanthene-4,5-dicarbaldehyde
• CAS: 650599-75-0
• 化学式: C₂₅H₃₀O₃
• 分子量: 378.511
• InChiKey: QMQXFWRMEBVAIE-UHFFFAOYSA-N

物化性质

• 熔点：
  248-249 °C(Solv: toluene (108-88-3); hexane (110-54-3))
• 沸点：
  454.8±45.0 °C(Predicted)
• 密度：
  1.074±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  (2,7-di-tert-butyl-9,9-dimethyl)-9H-xanthene-4,5-dicarbaldehyde 在 过氧乙酸 、 溶剂黄146 、 氢氧化钾 、 水 、 盐酸 作用下， 以 氯仿 、 甲苯 为溶剂， 反应 20.0h， 以69%的产率得到4,5-dihydroxy-2,7-di-tert-butyl-9,9-dimethyl-xanthene
  参考文献：
  名称：

  [DE] VERFAHREN ZUR HERSTELLUNG VON IN 2,7-POSITION SUBSTITUIERTEN XANTHEN-4,5-DIOLEN
  [EN] METHOD FOR THE PRODUCTION OF XANTHENE-4,5-DIOLES SUBSTITUTED IN POSITION 2.7
  [FR] PROCEDE DE PRODUCTION DE XANTHEN-4,5-DIOLS SUBSTITUES EN POSITION 2,7

  摘要：

  制备2,7-位取代的Xanthen-4,5-二醇的方法，其通式为（I），其中基团R1相同或不同，代表C1至C20烷基、C1至C20烷氧基、C1至C20全氟烷基、C3至C10环烷基、C6至C10芳基、C6至C10芳氧基、C7至C20烷基芳基、C7至C20芳基烷基、羧酰胺、R6O-(CH2CH2-O)n-和/或-COOR7-基团，其中指数n为1至10的整数，R6为C1至C4烷基，R7为C1至C10烷基、C6至C10芳基或苄基，基团R2和R3相同或不同，代表氢、C1至C20烷基、C3至C10环烷基、C6至C20芳基、C7至C20烷基芳基和/或C7至C20芳基烷基，或者R2和R3与它们结合的碳原子共同形成一个羰基或一个C3至C6环烷亚基，基团R4相同或不同，代表氢、C1至C20烷基、C3至C10环烷基、C6至C10芳基、C7至C20烷基芳基和/或C7至C20芳基烷基。方法包括对通式（II）的Xanthen进行酰化，其中基团R1、R2、R3和R4具有上述含义，以制备通式（III）的4,5-二酰基Xanthen，其中基团R5相同或不同，代表氢、C1至C4烷基、C1至C4卤代烷基、C1至C4烷氧甲基和/或C6至C10芳基。然后，将通式（III）的4,5-二酰基Xanthen氧化为相应的Xanthen-4,5-氧羰基化合物，其通式为（IV），其中基团R1、R2、R3、R4和R5具有上述含义，通过氧化反应或在单独的步骤中通过酯解来释放通式（I）的Xanthen-4,5-二醇。

  公开号：

  WO2005063730A1
• 作为产物：
  描述：

  2,7-di-tert-butyl-4,5-bis(chloromethyl)-9,9-dimethyl-9H-xanthene 在 碳酸氢钠 、 二甲基亚砜 作用下， 反应 72.0h， 以324.7 mg的产率得到(2,7-di-tert-butyl-9,9-dimethyl)-9H-xanthene-4,5-dicarbaldehyde
  参考文献：
  名称：

  Excimer emission and energy transfer in cofacial boradiazaindacene (BODIPY) dimers built on a xanthene scaffold

  摘要：

  Using a rigid xanthene scaffold, a series of boradiazaindacene derivatives were synthesized. In some of these compounds, two boradiazaindacene derivatives were placed cofacially, resulting in significant inter-chromophoric interactions, including excimer emission. A simple modification of boradiazaindacene structure leads to formation of an ICT dye, which has distinct spectral properties. Energy transfer between two BODIPY dyes was demonstrated as well. In addition, the spectral properties of ICT dye can be modulated by the addition of the acid leading to an acid switchable, energy transfer cassette. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.12.021

文献信息

• Supramolecular Control of the Template-Induced Selective Photodimerization of 4-Methyl-7-O-hexylcoumarin
  作者：William G. Skene、Emilie Couzigné、Jean-Marie Lehn

  DOI：10.1002/chem.200305268

  日期：2003.11.21

  are capable of binding substrates with complementary donor and acceptor sites to form a supramolecular complex through hydrogen bonding. Receptor 3 was designed to accept two guest molecules, which are held in close proximity within the supramolecular species. The substrate molecule, 4-methyl-7-O-hexylcoumarin (1 c), forms a 2:1 complex with a binding constant of 150 m(-1) for the second substrate

  设计并合成了包含两个相同的氢键识别亚基的对称的对位分子受体（3）。这些亚基能够结合具有互补供体和受体位点的底物以通过氢键形成超分子复合物。受体3被设计为接受两个客体分子，它们紧密地保持在超分子物种内。底物分子4-甲基-7-O-己基香豆素（1 c）与第二种底物形成2：1配合物，其结合常数为150 m（-1），首先通过1：1配合物与亲和常数510 m（-1）。当1 c的两个分子与模板结合时，其取向会导致在照射时选择性形成反式[2 + 2]光合产物2 cB。
• Selective product amplification of thymine photodimer by recognition-directed supramolecular assistance
  作者：W. G. Skene、Volker Berl、H?l?ne Risler、Richard Khoury、Jean-Marie Lehn

  DOI：10.1039/b605658j

  日期：——

  Two symmetric ditopic supramolecular templates (1 and 2) each presenting two hydrogen bonding recognition subunits were synthesized. Each such subunit comprises the same donor and acceptor pattern, capable of binding a substrate molecule with complementary hydrogen bonding groups to form a supramolecular complex. Substrate molecules, such as thymine or uracil derivatives, yield 2 : 1 complexes with the acceptors involving two hydrogen bonds to each subunit with ideal orientation for subsequent [2 + 2] dimerization upon photoirradiation. Selective syn photoproduct formation and concomitant suppression of the trans isomer are favored by orientation of the two guest nucleobases within the template cleft. Complementary donor and acceptor hydrogen bonding induced positioning of the two substrates and steric hindrance within the template clefts are responsible for the selective product formation.

  合成了两种对称的双位点超分子模板（1和2），每种模板都呈现出两个氢键识别子单元。每个这样的子单元包含相同的供体和受体模式，能够与具有互补氢键基团的底物分子结合，形成超分子复合物。例如胸腺嘧啶或尿嘧啶衍生物等底物分子，与受体形成2 : 1的复合物，每个子单元通过两个氢键在理想方向上结合，便于光照射后发生[2 + 2]二聚化反应。客体核碱基在模板裂隙内的定向排列有利于选择性syn光产物形成，同时抑制trans异构体。互补的供体和受体氢键诱导的底物定位以及模板裂隙内的空间位阻是选择性产物形成的原因。
• Shape-Persistent Binuclear Cyclometalated Platinum(II) Luminophores: Pushing π-Mediated Excimeric Fluid Emissions into the NIR Region and Ion-Induced Perturbations
  作者：Zhengqing Guo、Michael C. W. Chan

  DOI：10.1002/chem.200902328

  日期：2009.11.23

  which is selected to preclude excited states involving intramolecular metal–metal interactions, while allowing offset π‐stacking interactions, and this has pushed the associated excimeric‐type emissions into the near‐infrared region (see figure).

  你能走多低？标题x合物的[Pt–C，N，N] 2部分受刚性x吨单元束缚，该单元被选择为排除涉及分子内金属与金属相互作用的激发态，同时允许偏移的π堆积相互作用，这推动了相关的准分子型发射到近红外区域（见图）。
• Ag(III)···Ag(III) Argentophilic Interaction in a Cofacial Corrole Dyad
  作者：Christopher M. Lemon、David C. Powers、Michael Huynh、Andrew G. Maher、Austin A. Phillips、Brian P. Tripet、Daniel G. Nocera

  DOI：10.1021/acs.inorgchem.2c02285

  日期：2023.1.9

  are exemplified by d10 ions, with Au(I) aurophilic interactions as the archetype. Such an interaction extends to d8 species, and examples involving Au(III) are prevalent. Conversely, Ag(III) argentophilic interactions are uncommon. Here, we identify argentophilic interactions in silver corroles, which are authentic Ag(III) species. The crystal structure of a monomeric silver corrole is a dimer in the

  闭壳金属中心之间的亲金属相互作用以 d 10离子为例，其中 Au(I) 亲金相互作用为原型。这种相互作用延伸到 d 8物种和涉及 Au(III) 的例子很普遍。相反，Ag(III) 亲银相互作用并不常见。在这里，我们确定了银咯咯中的亲银相互作用，这是真正的 Ag(III) 物种。单体银咔咯的晶体结构在固态为二聚体，大环呈非典型圆顶构象。为了评估这是否代表真实的亲金属相互作用或晶体堆积人工制品，准备了类似的面部或“pacman”corrole。单体的构象在银 pacman corrole 中得到重现，金属中心之间的距离较短，为 3.67 Å，呫吨主链显着压缩。理论计算支持 pacman 复合物中存在罕见的 Ag(III)···Ag(III) 亲银相互作用。
• Excimer emission and energy transfer in cofacial boradiazaindacene (BODIPY) dimers built on a xanthene scaffold
  作者：Neslihan Saki、Tarik Dinc、Engin U. Akkaya

  DOI：10.1016/j.tet.2005.12.021

  日期：2006.3

  Using a rigid xanthene scaffold, a series of boradiazaindacene derivatives were synthesized. In some of these compounds, two boradiazaindacene derivatives were placed cofacially, resulting in significant inter-chromophoric interactions, including excimer emission. A simple modification of boradiazaindacene structure leads to formation of an ICT dye, which has distinct spectral properties. Energy transfer between two BODIPY dyes was demonstrated as well. In addition, the spectral properties of ICT dye can be modulated by the addition of the acid leading to an acid switchable, energy transfer cassette. (c) 2005 Elsevier Ltd. All rights reserved.