1-allyloxy-2-bromo-4-methoxybenzene | 68223-99-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-allyloxy-2-bromo-4-methoxybenzene
• 英文别名: 4-allyloxy-3-bromoanisole；2-Bromo-4-methoxy-1-(2-propen-1-yloxy)benzene；2-bromo-4-methoxy-1-prop-2-enoxybenzene
• CAS: 68223-99-4
• 化学式: C₁₀H₁₁BrO₂
• 分子量: 243.1
• InChiKey: YQINZLWFQORNAL-UHFFFAOYSA-N

物化性质

• 沸点：
  90 °C(Press: 0.05 Torr)
• 密度：
  1.337±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-allyloxy-2-bromo-4-methoxybenzene 在 镍 偶氮二异丁腈 、 氨 、 氢气 、 三正丁基氢锡 、 三氟乙酸 、 三氟乙酸酐 、 zinc(II) iodide 作用下， 以 乙醇 、 二氯甲烷 、 苯 为溶剂， 20.0 ℃ 、413.68 kPa 条件下， 反应 63.0h， 生成 C-(5-methoxy-1,6,7,8,9,9a-hexahydro-2-oxabenzo[cd]azulen-6-yl)methylamine
  参考文献：
  名称：

  1-Aminomethylbenzocycloalkanes:  Conformationally Restricted Hallucinogenic Phenethylamine Analogues as Functionally Selective 5-HT_2A Receptor Agonists

  摘要：

  A series of conformationally restricted analogues of the hallucinogenic phenethylamine 1 (2,5-dimethoxy4-bromophenethylamine, 2C-B) was synthesized to test several hypotheses concerning the bioactive conformation of phenethylamine ligands upon binding to the 5-HT2A receptor. These benzocycloalkane analogues were assayed for their receptor binding affinity and ability to activate downstream signaling pathways, and one exceptional compound was selected for testing in an in vivo drug discrimination model of hallucinogenesis. All compounds were examined in silico by virtual docking into a homology model of the 5-HT2A receptor. On the basis of these docking experiments, it was predicted that the R enantiomer of benzocyclobutene analogue 2 would be the most potent. Subsequent chemical resolution and X-ray crystallography confirmed this prediction, as (R)-2 proved to be equipotent to LSD in rats trained to discriminate LSD from saline. Thus, we propose that the conformation of 2 mimics the active binding conformation of the more flexible phenethylamine type hallucinogens. In addition, (R)-2 is one of the most potent and selective compounds yet discovered in the in vivo drug discrimination assay. Further, 2 was found to be a functionally selective agonist at the 5-HT2A receptor, having 65-fold greater potency in stimulating phosphoinositide turnover than in producing arachidonic acid release. If hallucinogenic effects are correlated with arachidonic acid production, such functionally selective 5-HT2A receptor agonists may lack the intoxicating properties of hallucinogens such as LSD.

  DOI：

  10.1021/jm060656o
• 作为产物：
  描述：

  4-甲氧基苯酚 在 溴 、 potassium carbonate 作用下， 以 甲醇 、 丙酮 为溶剂， 生成 1-allyloxy-2-bromo-4-methoxybenzene
  参考文献：
  名称：

  1-Aminomethylbenzocycloalkanes:  Conformationally Restricted Hallucinogenic Phenethylamine Analogues as Functionally Selective 5-HT_2A Receptor Agonists

  摘要：

  A series of conformationally restricted analogues of the hallucinogenic phenethylamine 1 (2,5-dimethoxy4-bromophenethylamine, 2C-B) was synthesized to test several hypotheses concerning the bioactive conformation of phenethylamine ligands upon binding to the 5-HT2A receptor. These benzocycloalkane analogues were assayed for their receptor binding affinity and ability to activate downstream signaling pathways, and one exceptional compound was selected for testing in an in vivo drug discrimination model of hallucinogenesis. All compounds were examined in silico by virtual docking into a homology model of the 5-HT2A receptor. On the basis of these docking experiments, it was predicted that the R enantiomer of benzocyclobutene analogue 2 would be the most potent. Subsequent chemical resolution and X-ray crystallography confirmed this prediction, as (R)-2 proved to be equipotent to LSD in rats trained to discriminate LSD from saline. Thus, we propose that the conformation of 2 mimics the active binding conformation of the more flexible phenethylamine type hallucinogens. In addition, (R)-2 is one of the most potent and selective compounds yet discovered in the in vivo drug discrimination assay. Further, 2 was found to be a functionally selective agonist at the 5-HT2A receptor, having 65-fold greater potency in stimulating phosphoinositide turnover than in producing arachidonic acid release. If hallucinogenic effects are correlated with arachidonic acid production, such functionally selective 5-HT2A receptor agonists may lack the intoxicating properties of hallucinogens such as LSD.

  DOI：

  10.1021/jm060656o

文献信息

• Photo-induced Carboiodination: A Simple Way to Synthesize Functionalized Dihydrobenzofurans and Indolines
  作者：Xiaobo Yang、Wenbo Liu、Lu Li、Wei Wei、Chao-Jun Li

  DOI：10.1002/chem.201603608

  日期：2016.10.17

  readily available and cheap aryl bromides and sodium iodide as the starting materials to synthesize valuable functionalized dihydrobenzofurans and indolines in good to excellent yields with broad functional‐group compatibility. As examples to demonstrate the utility of this protocol, gram‐scale reactions and further transformations of the products were accomplished towards the synthesis of bioactive

  在此，我们报告了在非常温和的条件下发生的简单的氧化还原中性和pH中性光诱导的碳碘化反应。该方案采用容易获得且便宜的芳基溴化物和碘化钠作为起始原料，以良好的产率和优异的产率以及广泛的官能团相容性来合成有价值的官能化二氢苯并呋喃和二氢吲哚。作为证明该方案实用性的实例，完成了克级反应和产物的进一步转化，以合成生物活性药物候选物。最重要的是，据我们所知，该反应是级联原子-自由基转移加成反应的第一个例子，涉及芳族C-Br键的裂解。
• Electron transfer promoted photochemical reductive radical cyclization reactions of allyl 2-bromoaryl ethers
  作者：Yasuharu Yoshimi、Hirotomo Kanai、Keisuke Nishikawa、Yasushi Ohta、Yoshiki Okita、Kousuke Maeda、Toshio Morita

  DOI：10.1016/j.tetlet.2013.02.103

  日期：2013.5

  Tin-free, photoinduced electron transfer promoted reductive radical cyclization reactions of allyl 2-bromoaryl ethers in the presence of NaOH in 2-PrOH were found to take place efficiently to give 3-methyl-2,3-dihydrobenzofurans. In contrast to conventional radical cyclization reactions that employ AIBN/Bu3SnH in benzene, the new method utilizes NaOH and 2-PrOH that are both readily available and benign

  发现在2-PrOH中的NaOH存在下，无锡，光诱导的电子转移促进的烯丙基2-溴芳基醚的还原自由基环化反应有效地产生了3-甲基-2,3-二氢苯并呋喃。与在苯中使用AIBN / Bu 3 SnH的常规自由基环化反应相反，该新方法利用了既容易获得又良性的NaOH和2-PrOH。因此，新开发的光化学方法是进行芳基自由基环化反应的一种通用且环保的方法。
• 一种卡利呫吨霉素A糖基配体及其中间体和 制备方法
  申请人：华东师范大学

  公开号：CN108558899B

  公开（公告）日：2021-02-26

  本发明公开了一种卡利呫吨霉素A糖基配体及其中间体和制备方法，所述卡利呫吨霉素A糖基配体具有式1所示化学结构：该卡利呫吨霉素A糖基配体的制备，包括如下合成路线中的步骤(2)或步骤(1)～(2)：本发明同时还公开了卡利呫吨霉素A糖基配体中间体，所述中间体分别具有式2、4、5、7所示化学结构：本发明首次实现了卡利呫吨霉素A糖基配体的化学合成，制得的卡利呫吨霉素A糖基配体经过简单的糖苷化反应即可制得卡利呫吨霉素A，对实现卡利呫吨霉素A的化学合成具有极强的实用价值。
• Cathodic Radical Cyclisation of Aryl Halides Using a Strongly‐Reducing Catalytic Mediator in Flow
  作者：Ana A. Folgueiras‐Amador、Alexander E. Teuten、Mateo Salam‐Perez、James E. Pearce、Guy Denuault、Derek Pletcher、Philip J. Parsons、David C. Harrowven、Richard C. D. Brown

  DOI：10.1002/anie.202203694

  日期：2022.8.26

  Cathodic radical cyclisations of aryl halides have been achieved in an undivided flow electrolysis cell, using phenanthrene as mediator in loadings down to 0.05 equiv, and without the requirement for a sacrificial anode. It is proposed that mediated homogeneous electron transfer proceeds in a reaction layer detached from the cathode, accounting for the observed selectivity.

  芳基卤化物的阴极自由基环化已在不分流电解池中实现，使用菲作为介体，负载量低至 0.05 当量，且无需牺牲阳极。据推测，介导的均匀电子转移在与阴极分离的反应层中进行，从而解释了观察到的选择性。
• Green, Ivan R.; De Koning, Charles B.; Hugo, Victor I., South African Journal of Chemistry, 1999, vol. 52, # 4, p. 112 - 119
  作者：Green, Ivan R.、De Koning, Charles B.、Hugo, Victor I.

  DOI：——

  日期：——