2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)azulene | 1187945-46-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)azulene
• 英文别名: 2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)azulenyl；2,6-bis(4′,4′,5′,5′-tetramethyl-[1′,3′,2′]dioxaborolan-2′-yl)azulene；4,4,5,5-Tetramethyl-2-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)azulen-6-yl]-1,3,2-dioxaborolane；4,4,5,5-tetramethyl-2-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)azulen-6-yl]-1,3,2-dioxaborolane
• CAS: 1187945-46-5
• 化学式: C₂₂H₃₀B₂O₄
• 分子量: 380.1
• InChiKey: MLVDENZIGFUHCH-UHFFFAOYSA-N

物化性质

• 沸点：
  503.3±23.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.39
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)azulene 在 双氧水 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 5.0h， 以50%的产率得到2,6-dihydroxyazulene
  参考文献：
  名称：

  Polyborylation of azulenes

  摘要：

  In the presence of an active Ir-based catalyst, azulene underwent stepwise borylation with bis(pinacolato)diboron to produce polyborylated products. The reactivity of the ring atoms toward borylation was found to decrease in the following order: 2-position>1,3-positiotls>6-position>5,7-positions. Extension of the borylation to some azulenes Substituted at the five-membered ring was also examined. Furthermore, the reaction of 2,6-bis(4,4,5.5-tetramethyl-1,3,2-dioxaborolanyl)azulene (3a) with an equivalent of hydrogen peroxide revealed that the oxidation proceeds preferentially at the 6-position. This indicates that the reactivity of the boryl group is governed by the pi-polarization of the azulenyl skeleton. (C) 2009 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2009.06.053
• 作为产物：
  描述：

  联硼酸频那醇酯 在 2,2'-联吡啶 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 作用下， 以 环己烷 为溶剂， 生成 2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)azulene
  参考文献：
  名称：

  将电子给体基团引入甘菊环结构：在可见光区域出现强烈的吸收和发射

  摘要：

  在这项工作中，通过高产率的Suzuki-Miyaura交叉偶联反应，合成了在甘菊环的2位和6位上含有二苯基苯胺基团的新型π-共轭甘菊环化合物。所获得的二苯基苯胺-甘菊环具有强烈的可见光吸收和发射（波长范围为400至600 nm）特性。研究表明，这种独特的光学性质，特别是蓝色和绿色光致发光区域的荧光发射（495 和 525 nm 处的 λem），是原始甘菊环中不存在的，是二苯基苯胺基团的电子供体效应的结果，这显着改变了甘菊环的电子结构，并导致允许的 HOMO → LUMO 电子跃迁。

  DOI：

  10.3390/molecules29143354

文献信息

• Synthesis of 2-Iodoazulenes by the Iododeboronation of Azulen-2-ylboronic Acid Pinacol Esters with Copper(I) Iodide
  作者：Masahiro Narita、Toshihiro Murafuji、Saki Yamashita、Masayuki Fujinaga、Kumiko Hiyama、Yurie Oka、Fumito Tani、Shin Kamijo、Katsuya Ishiguro

  DOI：10.1021/acs.joc.7b02820

  日期：2018.2.2

  Azulen-2-ylboronic acid pinacol ester, prepared by iridium-catalyzed C–H borylation of azulene, efficiently underwent iododeboronation with a stoichiometric amount of copper(I) iodide. This reaction allowed the synthesis of 2-iodoazulene in only two steps starting from azulene. This methodology was successfully applied to analogous azulenes.

  通过铱催化的z唑的CH硼氢化，制备的Azulen-2-基硼酸频哪醇酯与化学计量的碘化铜（I）有效地进行了碘脱硼作用。该反应允许从a烯开始仅两步合成2-碘io烯。该方法已成功地应用于类似的天青石。
• Trimethylsilanolate-Promoted Activation of Alkynyl Trimethylsilanes: Hiyama-Type Sonogashira Cross-Coupling for the Synthesis of Arylene–Ethynylene-Linked Porphyrin Arrays
  作者：Mitsuhiko Morisue、Nanase Ohno、Genki Saito、Miho Kawanishi

  DOI：10.1021/acs.joc.1c02879

  日期：2022.3.4

  such as the Glaser homocoupling. The rate-determining oxidative addition step results in the unexpected kinetic competition with the Glaser homocoupling, which is desired to be circumvented. We here propose two sets of improved strategies for the synthesis of arylene–ethynylene-linked porphyrin arrays from the meso-brominated porphyrin and alkynes. First, we explored the solvent-modulated approach employing

  为了合成内消旋-亚乙炔-共轭卟啉阵列，Sonogashira 交叉偶联反应可以直接构建 C(sp)–C(sp 2 ) 键，但该反应通常伴随着副反应，例如 Glaser 同源偶联。决定速率的氧化加成步骤导致与 Glaser 同源偶联的意外动力学竞争，这是需要规避的。我们在这里提出了两组改进的策略，用于从中间体合成亚芳基 - 亚乙炔基连接的卟啉阵列-溴化卟啉和炔烃。首先，我们探索了采用二氯甲烷作为反应溶剂的溶剂调节方法，以最大限度地减少作为格拉泽同偶联中间体的乙炔铜二聚体的形成，但该方法的范围有限。随后，我们开发了三甲基硅烷醇促进的 Hiyama 型方法，该方法通过在无胺条件下使用三甲基硅烷醇钾激活炔基三甲基硅烷 (TMS)。后一种方法不仅有利于跳过 TMS 组的预脱甲硅烷基化，而且有利于实现出色的分离产率。
• Intense absorption of azulene realized by molecular orbital inversion
  作者：Takahiro Tsuchiya、Tomohiro Hamano、Masahiro Inoue、Tomoya Nakamura、Atsushi Wakamiya、Yasuhiro Mazaki

  DOI：10.1039/d3cc02311g

  日期：——

  The introduction of diarylamino groups at the 2- and 6-positions of azulene was found to invert the order of the orbital energy levels and allowed the HOMO−LUMO transition, resulting in a substantial increase in absorbance in the visible region.

  在偶氮烯的 2 位和 6 位引入二芳基氨基后，发现轨道能级的顺序发生了逆转，实现了 HOMO-LUMO 转换，从而大幅提高了可见光区域的吸光度。
• JP5854436
  申请人：——

  公开号：——

  公开（公告）日：——
• Polyborylation of azulenes
  作者：Masayuki Fujinaga、Toshihiro Murafuji、Kei Kurotobi、Yoshikazu Sugihara

  DOI：10.1016/j.tet.2009.06.053

  日期：2009.8

  In the presence of an active Ir-based catalyst, azulene underwent stepwise borylation with bis(pinacolato)diboron to produce polyborylated products. The reactivity of the ring atoms toward borylation was found to decrease in the following order: 2-position>1,3-positiotls>6-position>5,7-positions. Extension of the borylation to some azulenes Substituted at the five-membered ring was also examined. Furthermore, the reaction of 2,6-bis(4,4,5.5-tetramethyl-1,3,2-dioxaborolanyl)azulene (3a) with an equivalent of hydrogen peroxide revealed that the oxidation proceeds preferentially at the 6-position. This indicates that the reactivity of the boryl group is governed by the pi-polarization of the azulenyl skeleton. (C) 2009 Published by Elsevier Ltd.