6-溴-2,3,5-三甲基-1-苯并噻吩 | 14207-25-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻吩类
• 中文名称: 6-溴-2,3,5-三甲基-1-苯并噻吩
• 英文名称: 6-bromo-2,3,5-trimethylbenzo[b]thiophene
• 英文别名: Benzo[b]thiophene, 6-bromo-2,3,5-trimethyl-；6-bromo-2,3,5-trimethyl-1-benzothiophene
• CAS: 14207-25-1
• 化学式: C₁₁H₁₁BrS
• 分子量: 255.178
• InChiKey: WWQLVACPBPTTNJ-UHFFFAOYSA-N

物化性质

• 熔点：
  79 °C
• 沸点：
  339.2±37.0 °C(Predicted)
• 密度：
  1.433±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 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-溴-2,3,5-三甲基-1-苯并噻吩 在 aluminum oxide 、 正丁基锂 作用下， 以 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 4.83h， 生成 2,3,5-trimethyl-7,7-bis(4-methoxyphenyl)-[7H]-chromene[5,6-b]thiophene
  参考文献：
  名称：

  Synthesis and photochromic behaviour of new methyl induced linear and angular thieno-2H-chromenes

  摘要：

  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.

  DOI：

  10.1016/s0040-4020(03)00262-x
• 作为产物：
  描述：

  2,3,5-Trimethyl-benzothiophen 在 溴 作用下， 以 乙醚 为溶剂， 生成 6-溴-2,3,5-三甲基-1-苯并噻吩
  参考文献：
  名称：

  Screening of antimicrobial activity of diarylamines in the 2,3,5-trimethylbenzo[b]thiophene series: a structure–activity evaluation study

  摘要：

  Gram positive (Bacillus cereus, B. subtilis), Gram negative (Pseudomonas aeruginosa, Escherichia coli) bacteria, and Candida albicans as a representative of fungi were used for screening the in vitro antimicrobial activity of diarylamines in the 2,3,5-trimethylbenzo[b]thiophene series bearing different substituents, synthesized by us using the palladium-catalyzed C-N coupling methodology. The minimal inhibitory concentration (MIC) and structure-activity relationships (SARs) were evaluated. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2004.09.038

文献信息

• Synthesis of β-Benzo[b]thienyldehydrophenylalanine Derivatives by One-Pot Palladium-Catalyzed Borylation and Suzuki Coupling (BSC) and Metal-Assisted Intramolecular Cyclization - Studies of Fluorescence and Antimicrobial Activity
  作者：Ana S. Abreu、Paula M. T. Ferreira、Maria-João R. P. Queiroz、Isabel C. F. R. Ferreira、Ricardo C. Calhelha、Letícia M. Estevinho

  DOI：10.1002/ejoc.200500040

  日期：2005.7

  (Z)-N-(tert-butoxycarbonyl)-p-(2,3,5-trimethylbenzo[b]thien-6-yl)dehydrophenylalanine with Pd(OAc) 2 and Cu(OAc) 2 in DMF at 160 °C gave two indole derivatives (1:3), the major product resulting from isomerization and cyclization and the minor product resulting from direct cyclization (thienoindole). Carrying out the reaction at 100 °C gave the same products in similar amounts. Use of the methyl ester of (Z)-N-

  钯催化硼化和铃木偶联（BSC）在一锅法中成功应用于苯并[b]噻吩系列中几种β-取代的脱氢苯丙氨酸的合成，同时保持了起始材料的立体化学。带有邻位 EDG（OMe 或 Me）的溴苯并 [b] 噻吩用作要与频哪醇硼烷硼化的组分，而 β-溴代氢苯丙氨酸的纯立体异构体用作其他 Suzuki 偶联组分。用Pd(OAc) 2 和Cu(OAc)处理获得的(Z)-N-(叔丁氧基羰基)-对-(2,3,5-三甲基苯并[b]噻吩-6-基)脱氢苯丙氨酸甲酯2 在 DMF 中于 160 °C 得到两种吲哚衍生物 (1:3)，主要是异构化和环化产生的产物，而直接环化产生的次要产物（噻吩并吲哚）。在 100 °C 下进行反应得到相似量的相同产物。使用 (Z)-N-(叔丁氧基羰基)-β-(2,3,7-三甲基苯并[b]噻吩-6-基)脱氢苯丙氨酸的甲酯作为起始原料仅得到一种产物，其由异构化和在 100 °C 下环化。对两种环化
• 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。
• Novel synthetic routes to thienocarbazoles via palladium or copper catalyzed amination or amidation of arylhalides and intramolecular cyclization
  作者：Isabel C.F.R Ferreira、Maria-João R.P Queiroz、Gilbert Kirsch

  DOI：10.1016/s0040-4020(02)00904-3

  日期：2002.9

  thienocarbazoles. Other method of intramolecular cyclization of diarylamines based on the reoxidation of the Pd(0) formed by Cu(OAc)2, avoiding the use of stoichiometric amounts of Pd(OAc)2, gave thienocarbazoles in a moderate yield, including a ring A methoxylated compound. An attempt to combine palladium and copper catalyses in a ‘one pot’ reaction of amination and intramolecular cyclization gave as major product

  进行钯或铜催化的胺化或酰胺化反应以获得噻吩并咔唑的二芳基胺和二芳基乙酰胺前体。在已知邻位卤代二苯胺的咔唑条件下，邻溴二芳基胺未环化为相应的噻吩并咔唑的事实使我们获得了一种钯催化的分子内环化反应的高效方法，其中邻卤代二芳基乙酰胺N脱保护为噻吩并咔唑。基于由Cu（OAc）2形成的Pd（0）的再氧化避免二芳基胺分子内环化的其他方法，避免使用化学计量的Pd（OAc）2得到适量产率的噻吩并咔唑，包括环A甲氧基化化合物。尝试在胺化和分子内环化的“一锅法”反应中结合钯和铜催化剂，以低收率得到N-苯并[ b ]噻吩取代的咔唑和所需的噻吩并咔唑作为主要产物。
• Palladium-catalyzed amination and cyclization to heteroannellated indoles and carbazoles
  作者：Isabel C.F.R Ferreira、Maria-João R.P Queiroz、Gilbert Kirsch

  DOI：10.1016/s0040-4020(03)00552-0

  日期：2003.5

  New ortho-bromodiarylamines in the benzo[b]thiophene series were prepared by palladium-catalyzed amination, either in the benzene or in the thiophene ring. These were submitted to palladium-catalyzed cyclization, under different required conditions, to give several differently substituted thieno[3,2-c] or [2,3-b]carbazoles and indolo[3,2-b]benzo[b]thiophenes. This constitutes a novel synthetic route

  通过钯催化的胺化反应，可以在苯或噻吩环中制备苯并[ b ]噻吩系列的新邻溴二芳基胺。将它们在不同的条件下进行钯催化的环化反应，得到几种不同取代的噻吩并[3,2- c ]或[2,3- b ]咔唑和吲哚并[3,2- b ]苯并[ b ]噻吩。这构成了通往两个四环系统的新颖合成途径。
• 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.