2-bromo-1-azaazulene | 855396-53-1

• 分子结构分类: 有机化合物
• 英文名称: 2-bromo-1-azaazulene
• 英文别名: 2-Bromocyclohepta[b]pyrrole
• CAS: 855396-53-1
• 化学式: C₉H₆BrN
• 分子量: 208.057
• InChiKey: BINBOBVHXSKLTQ-UHFFFAOYSA-N

物化性质

• 沸点：
  346.0±34.0 °C(Predicted)
• 密度：
  1.51±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-bromo-1-azaazulene 在 bis-triphenylphosphine-palladium(II) chloride N-溴代丁二酰亚胺(NBS) 、 potassium carbonate 、 过氧化苯甲酰 作用下， 以 四氯化碳 、 甲苯 为溶剂， 反应 10.5h， 生成 3-bromo-2-phenyl-1-azaazulene
  参考文献：
  名称：

  Effective Methods for Introducing Some Aryl and Heteroaryl Substituent onto 1-Azaazulene Nuclei

  摘要：

  Introduction of aryl and heteroaryl groups onto 1-azaazulene ring was achieved by addition-elimination reaction and Suzuki coupling. Reaction of 2-chloro-1-azaazulenes with 2-aryllithium and 2-heteroaryllithium followed by dehydrogenation with o-chloranil gave 8-aryl- and 8-heteroaryl-2-chloro-1-azaazulene in good yields. Suzuki coupling of 3-iodo-1-azaazulenens with phenylboronic acid in the presence of Pd catalyst afforded 3-phenyl-1-azaazulenes in excellent yield. Suzuki coupling of 2-bromo-1-azaazulenes with phenylboronic acid gave 2-phenyl-1-azaazulenes. Suzuki coupling of 2,3-dibromo-1-azaazulene with phenylboronic acid preferentially occurred at C-2. Reaction of 3-iodo-1-azaazulene with bis(pinacolato)diboron produced 3,3'-bis(1-azaazulene) derivative.

  DOI：

  10.3987/com-05-s(k)10
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 三溴化磷 作用下， 生成 2-bromo-1-azaazulene
  参考文献：
  名称：

  Nozoe et al., Chemistry and industry, 1954, p. 1357

  摘要：

  DOI：

文献信息

• Syntheses and properties of linear π-conjugated molecules composed of 1-azaazulene and azulene
  作者：Keito Ohtsu、Ryohei Hayami、Takuya Sagawa、Satoru Tsukada、Kazuki Yamamoto、Takahiro Gunji

  DOI：10.1016/j.tet.2019.130658

  日期：2019.11

  Two compounds, 6-(1-azaazulen-2-yl)ethynylazulene (8) and 6-(2-azulenyl)ethynylazulene (10), were synthesized using the Sonogashira-Hagihara cross-coupling reaction followed by decarboxylation with concentrated phosphoric acid. Compounds 8 and 10 were characterized by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, ultraviolet–visible (UV–Vis) spectroscopy, cyclic voltammetry

  使用Sonogashira-Hagihara交叉偶联反应，然后用浓磷酸脱羧，合成了两种化合物6-（1-（氮杂氮烯-2-基）乙炔基氮杂烯（8）和6-（2-氮杂烯基）乙炔基氮杂烯（10）。化合物8和10的特征在于1 H和13 C核磁共振（NMR）光谱，质谱，紫外可见（UV-Vis）光谱，循环伏安法和密度泛函理论（DFT）计算。根据该结果，证实两种化合物在其整个分子结构中均具有π共轭。化合物8和10的酸响应度使用UV-Vis和1 H NMR光谱进行了评估。发现化合物8对三氟乙酸高度敏感，其1-氮杂氮烯基部分充当碱。当与过量的三氟乙酸混合时，化合物10产生z阳离子。
• Synthesis and properties of 2-(2-pyridyl)-1-azaazulene
  作者：Mitsunori Oda、Kazutaka Ogura、Nguyen Chung Thanh、Sayaka Kishi、Shigeyasu Kuroda、Kunihide Fujimori、Tomonori Noda、Noritaka Abe

  DOI：10.1016/j.tetlet.2007.05.008

  日期：2007.6

  The title azaazulene 3 was synthesized either by reaction of tropone with N-(2-pyridyl)acetyl}pyridinium iodide in the presence of ammonium acetate or by palladium-catalyzed cross-coupling between 2-halo-1-azaazulene and 2-substituted pyridine. The compound shows relatively stronger basicity compared with 2,2′-bipyridyl. While 3 showed no emission from the S1 state but from the S2 state like azulene

  标题氮杂氮烯3是通过在乙酸铵存在下将托普酮与N -（2-吡啶基）乙酰基}碘化吡啶碘化物反应或通过钯催化的2-卤代-1-氮杂氮杂烯与2-取代的氮杂的偶合而合成的。吡啶。与2,2'-联吡啶基相比，该化合物显示出相对较强的碱性。虽然3没有显示出从S 1状态发射出而是从S 2状态发射出的类似azulene，但是3的质子化物质却显示出了从S 1状态发射出的。还研究了与络合有关的阳离子金属依赖性吸收和发射。
• Synthesis of 2-Arylamino-1-azaazulenes
  作者：Satoru Tsukada、Makoto Nakazawa、Yuya Okada、Keito Ohtsu、Noritaka Abe、Takahiro Gunji

  DOI：10.3987/com-16-s(s)48

  日期：——

  A series of 2-arylamino-l-azaazulenes were synthesized by the Buchwald-Hartwig cross coupling reaction. The resulting compounds were characterized by H-1 NMR, C-13 NMR, HRMS analyses, and elemental analysis. X-Ray crystallographic analysis revealed that 2-(1-naphthylamino)-1-azaazuleneexists in dimeric form with two intermolecular N-H center dot center dot center dot N hydrogen bonds in its crystal structure.
• Syntheses of 2-Formyl-, 2,3-Diformyl- and 8-Formyl-1-azaazulenes
  作者：Noritaka Abe、Kazuya Koizumi、Chikara Miyake、Tomoyuki Ariyoshi、Kenji Umeda、Noriko Yamauchi、Shoji Tagashira、Yoshiko Murakami、Hiroyuki Fujii

  DOI：10.3987/com-07-s(u)6

  日期：——
• Synthesis of [Poly(2-pyridyl)-Substituted]-1-azaazulenes
  作者：Noritaka Abe、Tomoyuki Ariyoshi、Satomi Watarai、Shoji Tagashira、Tomonori Noda、Yoshiko Murakami、Hiroyuki Fujii

  DOI：10.3987/com-08-s(f)8

  日期：——

  2-(2-Pyridyl)-1-azaazulenes were derived from 2-bromo- or 2-iodo-1-azaazulenes and 3-(2-pyridyl)-1-azaazulenes were derived from 3-iodo-1-azaazulenes by Suzuki coupling. Reaction of 3-iodo-1-azaazulenes with B(NPDEA) gave corresponding 3-(2-pyridyl)-1-azaazulenes together with 3-borylated-2-chloor-1-azaazulene (9a) or 3,3'-bi(2-methoxy-1-azaazulene) (10b). Reactions of 8-(2-pyridyl)-1-azaazulene with 2-pyridyllithium gave 4,8-di(2-pyridyl)- and 6,8-di(2-pyridyl)-1-azaazulenes. Reactions of 4,8-di(2-pyridyl)-1-azaazulene with 2-pyridyl lithium gave 4,6,8-tri(2-pyridyl)-1-azaazulene. The reactivity of the seven-menbered ring is C8 > C6 > C4. Reaction of 3-(2-pyridyl)-1-azaazulenes with 2-pyridyllithium gave 3,4-di(2-pyridyl)- and 3,8-di(2-pyridyl)-1-azaazulenes.