1,3,5-tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)azulene | 1187945-64-7

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1,3,5-tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)azulene
• 英文别名: 2-[1,3-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)azulen-5-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；2-[1,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)azulen-5-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 1187945-64-7
• 化学式: C₂₈H₄₁B₃O₆
• 分子量: 506.063
• InChiKey: RPUWQBNVOQFIBU-UHFFFAOYSA-N

物化性质

• 沸点：
  613.4±40.0 °C(predicted)
• 密度：
  1.09±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.69
• 重原子数：
  37
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,3,5-tris(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 3.0h， 生成 1,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)azulen-5-ol
  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 、 奥苷菊环 在 4,4'-二甲基-2,2'-联吡啶 、 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 144.17h， 以38%的产率得到1,3,5,7-tetra(Bpin)azulene
  参考文献：
  名称：

  1,3,5,7-Tetra(Bpin)azulene by Exhaustive Direct Borylation of Azulene and 5,7-Di(Bpin)azulene by Selective Subsequent Deborylation

  摘要：

  Exhaustive borylation of azulene with excess bis(pinacolato)-diboron (B(2)pin(2)) under conditions that promote equilibration of the borylated azulenes provides a convenient one-step synthesis of 1,3,5,7-tetra(Bpin)azulene as the major product. The Bpin substituents at positions 1 and 3 can be conveniently removed from 1,3,5,7-tetra-(Bpin)azulene by treatment with trifluoroacetic acid at room temperature to give 5,7-di(Bpin)azulene. The utility of 5,7-di(Bpin)azulene as a synthetic precursor to 5,7-disubstituted azulenes that are otherwise difficult to access is demonstrated by Suzuki coupling to give the previously unknown 5,7-diphenylazulene.

  DOI：

  10.1055/s-0034-1380686

文献信息

• 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.
• 1,3,5,7-Tetra(Bpin)azulene by Exhaustive Direct Borylation of Azulene and 5,7-Di(Bpin)azulene by Selective Subsequent Deborylation
  作者：Lawrence Scott、Hidetaka Nishimura、Maria Eliseeva、Atsushi Wakamiya

  DOI：10.1055/s-0034-1380686

  日期：——

  Exhaustive borylation of azulene with excess bis(pinacolato)-diboron (B(2)pin(2)) under conditions that promote equilibration of the borylated azulenes provides a convenient one-step synthesis of 1,3,5,7-tetra(Bpin)azulene as the major product. The Bpin substituents at positions 1 and 3 can be conveniently removed from 1,3,5,7-tetra-(Bpin)azulene by treatment with trifluoroacetic acid at room temperature to give 5,7-di(Bpin)azulene. The utility of 5,7-di(Bpin)azulene as a synthetic precursor to 5,7-disubstituted azulenes that are otherwise difficult to access is demonstrated by Suzuki coupling to give the previously unknown 5,7-diphenylazulene.