6-bromo-2,3,4,7-tetramethylbenzo[b]thiophene | 14207-28-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻吩类
• 英文名称: 6-bromo-2,3,4,7-tetramethylbenzo[b]thiophene
• 英文别名: 6-Bromo-2,3,4,7-tetramethyl-1-benzothiophene
• CAS: 14207-28-4
• 化学式: C₁₂H₁₃BrS
• 分子量: 269.205
• InChiKey: FTCWVBPROJOLBU-UHFFFAOYSA-N

物化性质

• 熔点：
  73 °C
• 沸点：
  360.3±37.0 °C(Predicted)
• 密度：
  1.385±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6-bromo-2,3,4,7-tetramethylbenzo[b]thiophene 在 正丁基锂 、 亚磷酸三乙酯 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 8.5h， 生成 2,3,4,10-tetramethyl-5H-thieno[3,2-b]carbazole
  参考文献：
  名称：

  钯催化交叉偶联伊莎贝尔合成的6-（2'-硝基苯基）苯并[ b ]噻吩的还原环化反应合成新的甲基化噻吩并[2,3- a ]和[3,2- b ]咔唑

  摘要：

  新的甲基化噻吩并[2,3-a]和[3,2-b]咔唑（5）（R = H）的合成是通过钯催化的交叉偶联，分子内还原环化反应来实现的。通过将6-硼代甲基苯并[ b ]噻吩中间体（2）与2-溴或碘硝基苯进行Suzuki交叉偶联，得到环化前体6-（（2'-硝基苯基）苯并[b]噻吩（3）。硼化中间体（2）的制备是通过溴-锂交换，然后进行硼金属转移，并使用Pd（OAc）2原位偶联，从而从6-溴苯并[ b ]硫代苯（ 1）到环化前体（3）。在还原环化步骤中，还获得了N-乙基噻吩并咔唑（5）（R ＝ Et）。为了避免形成亚磷酸三乙酯的量和反应时间，已经进行了一些实验。

  DOI：

  10.1002/jhet.5570380334

文献信息

• Synthesis and photochromic behaviour of new methyl induced linear and angular thieno-2H-chromenes
  作者：Maria-João R.P. Queiroz、Paula M.S. Plasencia、Roger Dubest、Jean Aubard、Robert Guglielmetti

  DOI：10.1016/s0040-4020(03)00262-x

  日期：2003.3

  New methyl induced linear and angular thieno-2H-chromenes 4, 5 and 6 were prepared by reaction of new methylated 6-hydroxybenzo[b]thiophenes 2 (a, b and c) and propargylic alcohols 3a and 3b, using acidic Alumina Brockmann I as catalyst and drying agent. Compounds 2 were prepared in good to excellent yields in a 'one pot' three step reaction from the corresponding bromo compounds 1. The photochromic behaviour of compounds 4, 5 and 6b was evaluated with the aid of a classical set of spectrokinetic parameters, and compared to reference compounds that are benzoannellated in the 5,6 and 6,7 positions of the chromene (naphthopyrans) and also to thieno-2H-chromenes 7 and 8, previously prepared, which are analogues of 5a. The resistance to fatigue (photodegradation) under continuous irradiation was also evaluated. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Tandem palladium-catalyzed borylation and Suzuki coupling (BSC) to thienocarbazole precursors
  作者：Isabel C.F.R. Ferreira、Maria-João R.P. Queiroz、Gilbert Kirsch

  DOI：10.1016/s0040-4039(03)00952-3

  日期：2003.6

  Substituted 2-methyl-2'-nitro diaryl compounds in the benzo[h]thiophene series were prepared by palladium-catalyzed, two-step. one-pot borylation/Suzuki coupling (BSC) reaction in good to high yields. The borylation reaction was performed on methylated 6-bromobenzo[b]thiophenes using pinacolborane and was followed by in situ Suzuki coupling with substituted (CF3, OMe) 2-bromonitrobenzenes. The compounds obtained were cyclized to the corresponding ring A substituted thienocarbazoles which can have biological activity or/and be used as biomarkers due to their fluorescence properties and possible DNA intercalation. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Synthesis of diarylamines in the benzo[b]thiophene series bearing electron donating or withdrawing groups by Buchwald–Hartwig C–N coupling
  作者：Isabel C.F.R Ferreira、Maria-João R.P Queiroz、Gilbert Kirsch

  DOI：10.1016/s0040-4020(02)01656-3

  日期：2003.2

  Diarylamines in the benzo[b]thiophene series bearing electron donating or withdrawing groups, were prepared by Buchwald-Hartwig C-N coupling in moderate to high yields. The conditions used were Pd(OAc)(2) (3 mol%), BINAP as ligand (4 mol%) and Cs2Co3 as base (1.4 equiv.), in toluene at 100degreesC, being 6-bromo or amino benzo[b]thiophenes coupled, respectively, with substituted anilines or phenylbromides. The 6-aminobenzo[b]thiophene derivatives were also prepared by palladium catalyzed C-N coupling of the corresponding 6-bromo compounds with benzophenone imine, followed by acidic hydrolysis of the imino derivatives. When 4-nitrobromobenzene and 4-bromobenzonitrile were used as coupling components, triarylamines were also isolated in small amounts. The presence of a fluorine atom on the phenylbromide highly increases the diarylamine yields. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Peixoto, Fernanda M.C.; Queiroz, Maria-Joao R.P.; Kirsch, Gilbert, Journal of Chemical Research, Miniprint, 1998, # 4, p. 801 - 812
  作者：Peixoto, Fernanda M.C.、Queiroz, Maria-Joao R.P.、Kirsch, Gilbert

  DOI：——

  日期：——
• Synthesis of new methylated thieno[2,3-<i>a</i>] and [3,2-<i>b</i>]carbazoles by reductive cyclization of 6-(2′-Nitrophenyl)benzo[<i>b</i>]thiophenes obtained by palladium-catalyzed cross-coupling isabel
  作者：C. F. R. Ferreira、Maria-João R. P. Queiroz、Gilbert Kirsch

  DOI：10.1002/jhet.5570380334

  日期：2001.5

  [3,2-b]carbazoles (5) (R=H) was achieved by a palladium-catalyzed cross-coupling, intramolecular reductive cyclization sequence of reactions. The cyclization precursors 6-(2′-nitrophenyl)benzo[b]thiophenes (3) were obtained by Suzuki cross-coupling of 6-boronated methylbenzo[b]thiophenes intermediates (2) with 2-bromo or iodonitrobenzene. The boronated intermediates (2) were prepared via bromine-lithium

  新的甲基化噻吩并[2,3-a]和[3,2-b]咔唑（5）（R = H）的合成是通过钯催化的交叉偶联，分子内还原环化反应来实现的。通过将6-硼代甲基苯并[ b ]噻吩中间体（2）与2-溴或碘硝基苯进行Suzuki交叉偶联，得到环化前体6-（（2'-硝基苯基）苯并[b]噻吩（3）。硼化中间体（2）的制备是通过溴-锂交换，然后进行硼金属转移，并使用Pd（OAc）2原位偶联，从而从6-溴苯并[ b ]硫代苯（ 1）到环化前体（3）。在还原环化步骤中，还获得了N-乙基噻吩并咔唑（5）（R ＝ Et）。为了避免形成亚磷酸三乙酯的量和反应时间，已经进行了一些实验。