4-(5-bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)benzoic acid methyl ester | 851883-09-5

• 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: 4-(5-bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)benzoic acid methyl ester
• 英文别名: 4-bromo-2,7-di-tert-butyl-5-[4-(methoxycarbonyl)phenyl]-9,9-dimethyl-9H-xanthene；Methyl 4-(5-bromo-2,7-ditert-butyl-9,9-dimethylxanthen-4-yl)benzoate；methyl 4-(5-bromo-2,7-ditert-butyl-9,9-dimethylxanthen-4-yl)benzoate
• CAS: 851883-09-5
• 化学式: C₃₁H₃₅BrO₃
• 分子量: 535.521
• InChiKey: NQYDSDAOFZCJFR-UHFFFAOYSA-N

物化性质

• 沸点：
  554.9±50.0 °C(Predicted)
• 密度：
  1.194±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.8
• 重原子数：
  35
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(5-bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)benzoic acid methyl ester 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 sodium hydroxide 、 potassium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 76.0h， 生成
  参考文献：
  名称：

  刽子手沙罗芬

  摘要：

  我们在这里报告了一种用于构建一类新化合物 Hangman salophens 的模块化方法。在 Hangman 图案中，酸碱功能“悬挂”在氧化还原辅因子的表面。与更难合成的基于卟啉的 Hangman 系统相比，Hangman salophens 允许轻松控制其质子和氧化还原特性，用于研究小分子的质子耦合电子转移 (PCET) 活化。通过研究 H2O2 的过氧化氢酶样歧化，我们表明 (1) 强的给质子悬挂基团（即羧酸）和（2）氧化还原活性 salen 上的给电子基团的存在赋予了显着的催化作用。小分子底物的 OO 键活化的活性。

  DOI：

  10.1021/ja042849b
• 作为产物：
  描述：

  4,5-二溴-2,7-二叔丁基-9,9-二甲基呫吨 在 四(三苯基膦)钯 、 苯基锂 、 cesium fluoride 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醚 、 环己烷 为溶剂， 反应 24.67h， 生成 4-(5-bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)benzoic acid methyl ester
  参考文献：
  名称：

  刽子手沙罗芬

  摘要：

  我们在这里报告了一种用于构建一类新化合物 Hangman salophens 的模块化方法。在 Hangman 图案中，酸碱功能“悬挂”在氧化还原辅因子的表面。与更难合成的基于卟啉的 Hangman 系统相比，Hangman salophens 允许轻松控制其质子和氧化还原特性，用于研究小分子的质子耦合电子转移 (PCET) 活化。通过研究 H2O2 的过氧化氢酶样歧化，我们表明 (1) 强的给质子悬挂基团（即羧酸）和（2）氧化还原活性 salen 上的给电子基团的存在赋予了显着的催化作用。小分子底物的 OO 键活化的活性。

  DOI：

  10.1021/ja042849b

文献信息

• A Concise Synthesis of Asymmetrically 4,5-Disubstituted 9,9-Dimethyl-9H-xanthenes
  作者：Ryosuke Matsubara、Miki Koide、Yong-Soon Shin、Toshiyuki Shimada、Masahiko Hayashi

  DOI：10.1055/s-0034-1379368

  日期：——

  Abstract A concise synthesis of asymmetrically 4,5-disubstituted 9,9-dimethyl-9H-xanthenes was developed. The monolithiation of 4,5-dibromo-9H-xanthene, subsequent zincation, and the Negishi coupling with diverse electrophiles afforded the corresponding 4-aryl- or 4-vinyl-9H-xanthenes in good yields and with high selectivity. The second substitution reactions were performed under mild reaction conditions

  摘要 开发了不对称的4,5-二取代的9,9-二甲基-9 H-黄嘌呤的简明合成方法。4,5-二溴-9 H-蒽的整体化，随后的锌化以及与不同亲电试剂的Negishi偶联以良好的产率和高选择性提供了相应的4-芳基-或4-乙烯基-9 H-黄嘌呤。第二取代反应在温和的反应条件下进行，从而为基于9 H- x吨骨架的官能化分子提供了方便的合成途径。 开发了不对称的4,5-二取代的9,9-二甲基-9 H-黄嘌呤的简明合成方法。4,5-二溴-9 H-蒽的整体化，随后的锌化以及与不同亲电试剂的Negishi偶联以良好的产率和高选择性提供了相应的4-芳基-或4-乙烯基-9 H-黄嘌呤。第二取代反应在温和的反应条件下进行，从而为基于9 H- x吨骨架的官能化分子提供了方便的合成途径。
• Hangman Salen Platforms Containing Two Xanthene Scaffolds
  作者：Jenny Y. Yang、Julien Bachmann、Daniel G. Nocera

  DOI：10.1021/jo0613075

  日期：2006.11.1

  A synthetic strategy for the construction of chiral salen ligands bearing two rigid xanthene spacers functionalized with carboxylic acid and ester groups is presented. Suzuki cross-coupling methodology is used to furnish the appropriately functionalized xanthene spacers to a salicyladehyde, which is subsequently condensed with (1R,2R)-(−)-1,2-diaminocyclohexane to produce salen ligands featuring an

  提出了一种合成策略，用于构建带有两个被羧酸和酯基官能化的刚性x吨间隔基的手性塞伦配体。铃木交叉偶联方法用于将适当官能化的x吨间隔基提供给水杨醛，然后将其与（1 R，2 R）-（-）-1,2-二氨基环己烷生成除具有金属硅铝氧化化学外还具有多种氢键相互作用的可扩展分子裂隙的Salen配体。这些“ Hangman”平台支持质子偶联电子转移（PCET）介导的多电子化学的能力是由它们的亲和性促进通过高价金属氧代催化过氧化氢分解为氧气和水的能力而建立的。在这个功能化的Hangman框架内，salen平台的环己基骨架的立体化学在金属氧代对1,2-二氢萘的环氧化反应中得以揭示。
• Synthesis and spectroscopic properties of modular platinum(II) terpyridine phosphorescent pockets
  作者：Wah-Leung Tong、Michael C. W. Chan、Nianyong Zhu、Sze-Kar Leung

  DOI：10.1039/b900030e

  日期：——

  A modular design approach has been utilized to develop molecular ‘pockets’ featuring three integrated components, namely a phosphorescent Pt(II)-π(organic) moiety, a suitable receptor group, and a rigid, conjugated connecting backbone, and the cavities therein are examined by NMR spectroscopy and an X-ray crystal structure. Their photophysical properties have been investigated; unusually for Pt-terpyridine derivatives, the complexes are luminescent (near-red 3MLCT emission) in solution at room temperature. It has been shown that their emissive characteristics are affected by the nature of the backbone component but not the receptor group.

  我们采用模块化设计方法开发出了分子 "口袋"，其中包含三个集成组件，即磷光铂（II）-π（有机）分子、合适的受体基团和刚性共轭连接骨架，并通过核磁共振光谱和 X 射线晶体结构对其中的空腔进行了研究。对它们的光物理特性进行了研究；与铂-叔吡啶衍生物不同的是，这些复合物在室温下的溶液中具有发光特性（近红色 3MLCT 发射）。研究表明，它们的发射特性受骨架成分性质的影响，而不受受体基团的影响。
• Catalase and Epoxidation Activity of Manganese Salen Complexes Bearing Two Xanthene Scaffolds
  作者：Jenny Y. Yang、Daniel G. Nocera

  DOI：10.1021/ja070358w

  日期：2007.7.1

  A series of manganese Hangman salen ligand platforms functionalized by tert-butyl groups in the 3 and 3' positions using the Suzuki cross-coupling methodology are presented. The Hangman platforms support multielectron chemistry mediated by proton-coupled electron transfer (PCET), as demonstrated by their ability to promote the catalytic disproportionation of hydrogen peroxide to oxygen and water via a high-valent metal oxo. The addition of the steric groups to the salen macrocycle leads to enhanced catalase activity by circumventing side reactions that sequester the catalyst off pathway. The stereochemistry imposed by the cyclohexanediamine backbone of the salen platform is revealed by the epoxidation of 1,2-dihydronapthalene by a variety of oxidants. Improved enantiomeric excess and catalase activity as compared to sterically unmodified counterparts establishes the efficacy of the tert-butyl groups in promoting PCET catalysis on the Hangman platform.
• Congested Cyclometalated Platinum(II) Ditopic Frameworks and Their Phosphorescent Responses to S-Containing Amino Acids
  作者：Wah-Leung Tong、Michael C. W. Chan、Shek-Man Yiu

  DOI：10.1021/om1007488

  日期：2010.12.13

  New phosphorescent platinum(II) molecular hosts featuring a tridentate N,C,N-coordinating ligand, a conformationally rigid organic linker, and a binding group have been prepared. The complexes have been fully characterized by various spectroscopic techniques, and the X-ray crystal structure of one derivative has been determined. Their photophysical properties have been studied, and intense green metal-perturbed (IL)-I-3 emission is observed in solution at room temperature. The luminescent responses of these Pt(II) hosts to amino acids have been investigated: emission quenching and UV-vis absorption changes in polar/aqueous media are detected for terminal thiols only, and unusual preferential binding is apparent for cysteine over homocysteine. The nature of the host guest interactions has been examined by quantitative and comparative binding studies, mass spectrometry, and DFT calculations, which indicate that these observations may be ascribed to the presence of rigidly positioned ditopic binding sites.