4-(2-bromo-5-methoxyphenyl)-2-butanone | 371114-86-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-(2-bromo-5-methoxyphenyl)-2-butanone
• 英文别名: 4-(2-Bromo-5-methoxyphenyl)butan-2-one
• CAS: 371114-86-2
• 化学式: C₁₁H₁₃BrO₂
• 分子量: 257.127
• InChiKey: HMJQAFGZRBYTFA-UHFFFAOYSA-N

物化性质

• 熔点：
  34.0-34.5 °C
• 沸点：
  324.3±27.0 °C(Predicted)
• 密度：
  1.335±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(2-bromo-5-methoxyphenyl)-2-butanone 在 盐酸 、 4-二甲氨基吡啶 、 叔丁基锂 、 2-mercaptopyridine-1-oxide sodium salt 、 对甲苯磺酸 、 magnesium 作用下， 以 四氢呋喃 、 乙醚 、 苯 为溶剂， 反应 62.5h， 生成 2-butyl-6-methoxy-2-methylselenochromane
  参考文献：
  名称：

  Intramolecular Homolytic Substitution at Selenium:  Synthesis of Novel Selenium-Containing Vitamin E Analogues

  摘要：

  Treatment of 1-(benzylselenenyl)-5-butyl-5-nonanoI (10) with oxalyl chloride followed by the sodium salt of N-hydroxypyridine-2-thione afforded the corresponding pyridine-2-thione-N-oxycarbonyI (PTOC) oxalate ester which was not isolated but immediately heated to provide 2,2-dibutylselenane (7). This transformation presumably involves a tertiary alkyl radical that undergoes intramolecular homolytic substitution at selenium with loss of the benzyl radical to provide the selenium-containing ring system (7). A similar protocol, when applied to 1-(2-benzylselenenyl-5-methoxyphenyl)-3-methyl3-heptanol (18) and 1-(2-benzylselenenyl-5-methoxyphenyl)-3,7,11,15-tetramethyl-3-hexadecanoI (19), followed by deprotection, afforded the selenium-containing alpha -tocopherol analogues 4 and 1f, respectively, in moderate yields. To the best of our knowledge, these transformations represent the first examples of tertiary radicals involved in homolytic substitution chemistry at selenium.td2

  DOI：

  10.1021/jo010274k
• 作为产物：
  描述：

  tert-butyl-2-(2-bromo-5-methoxybenzyl) acetoacetate 在 盐酸 作用下， 反应 51.0h， 以100%的产率得到4-(2-bromo-5-methoxyphenyl)-2-butanone
  参考文献：
  名称：

  Intramolecular Homolytic Substitution at Selenium:  Synthesis of Novel Selenium-Containing Vitamin E Analogues

  摘要：

  Treatment of 1-(benzylselenenyl)-5-butyl-5-nonanoI (10) with oxalyl chloride followed by the sodium salt of N-hydroxypyridine-2-thione afforded the corresponding pyridine-2-thione-N-oxycarbonyI (PTOC) oxalate ester which was not isolated but immediately heated to provide 2,2-dibutylselenane (7). This transformation presumably involves a tertiary alkyl radical that undergoes intramolecular homolytic substitution at selenium with loss of the benzyl radical to provide the selenium-containing ring system (7). A similar protocol, when applied to 1-(2-benzylselenenyl-5-methoxyphenyl)-3-methyl3-heptanol (18) and 1-(2-benzylselenenyl-5-methoxyphenyl)-3,7,11,15-tetramethyl-3-hexadecanoI (19), followed by deprotection, afforded the selenium-containing alpha -tocopherol analogues 4 and 1f, respectively, in moderate yields. To the best of our knowledge, these transformations represent the first examples of tertiary radicals involved in homolytic substitution chemistry at selenium.td2

  DOI：

  10.1021/jo010274k

文献信息

• Intramolecular Substitution Reaction of Lithium Alkylidene Carbenoids. Regioselective Synthesis of Indenes
  作者：Hideyuki Yanagisawa、Kasei Miura、Mitsuru Kitamura、Koichi Narasaka、Kaori Ando

  DOI：10.1246/bcsj.76.2009

  日期：2003.10

  intramolecular substitution reaction with alkoxide moiety occurs at the lithium alkylidene carbenoid center to give dihydrofurans. The reaction mechanism of this intramolecular substitution reaction is studied by B3LYP density functional calculations with the 6-31+G(d) basis set, and the substitution is found to proceed in a concerted manner. This substitution reaction is applied to the regioselective preparation

  当 4,4-dibromo-3-alkenols 用丁基锂处理时，在锂亚烷基卡宾中心发生与醇盐部分的分子内取代反应，得到二氢呋喃。用6-31+G(d)基组通过B3LYP密度泛函计算研究了这种分子内取代反应的反应机理，发现取代以协同方式进行。该取代反应适用于茚衍生物的区域选择性制备。也就是说，用丁基锂处理 3-(o-溴苯基)-1,1-二溴丙烯衍生物 23 会导致形成分子内取代中间体，3-茚基锂 D，其被亲电试剂捕获以区域选择性地提供取代的茚。
• Olefination via Cu-Mediated Dehydroacylation of Unstrained Ketones
  作者：Xukai Zhou、Yan Xu、Guangbin Dong

  DOI：10.1021/jacs.1c09587

  日期：2021.12.8

  unique reaction pathway involving aromatization-driven C–C cleavage to remove the acyl moiety, followed by Cu-mediated oxidative elimination to form an alkene between the α and β carbons. The newly adopted N′-methylpicolinohydrazonamide (MPHA) reagent is key to enable efficient cleavage of ketone C–C bonds at room temperature. Diverse alkyl- and aryl-substituted olefins, dienes, and special alkenes

  酮脱氢酰化为烯烃是在温和条件下实现的，它表现出独特的反应途径，包括芳构化驱动的 C-C 裂解以去除酰基部分，然后通过 Cu 介导的氧化消除在 α 和 β 碳之间形成烯烃。新采用的N'-甲基吡啶甲酰肼 (MPHA) 试剂是在室温下有效裂解酮 C-C 键的关键。生成具有广泛官能团耐受性的多种烷基和芳基取代的烯烃、二烯和特殊烯烃。还展示了该方法的战略应用。
• Site-Specific and Degree-Controlled Alkyl Deuteration via Cu-Catalyzed Redox-Neutral Deacylation
  作者：Xukai Zhou、Tingting Yu、Guangbin Dong

  DOI：10.1021/jacs.2c04382

  日期：2022.6.8

  Deuterated organic compounds have become increasingly important in many areas; however, it remains challenging to install deuterium site-selectively to unactivated aliphatic positions with control of the degree of deuteration. Here, we report a Cu-catalyzed degree-controlled deacylative deuteration of diverse alkyl groups with the methylketone (acetyl) moiety as a traceless activating group. The use

  氘代有机化合物在许多领域变得越来越重要；然而，通过控制氘化程度将氘选择性地安装到未激活的脂肪族位置仍然具有挑战性。在这里，我们报告了铜催化的不同烷基的度控制脱酰氘化，甲基酮（乙酰基）部分作为无痕活化基团。的使用-methylpicolino-hydrazonamide (MPHA) 促进有效的芳构化驱动的 C-C 裂解。可以选择性地实现特定站点的单、双和三氘化。该反应是氧化还原中性的，具有广泛的官能团耐受性。该方法的实用性已在形成一套完整的氘代乙基、与 Diels-Alder 反应合并、净脱乙烯基氘化以及合成 d 2 -Austedo 类似物方面得到证明。
• Deacylative Thiolation by Redox‐Neutral Aromatization‐Driven C−C Fragmentation of Ketones
  作者：Xukai Zhou、Daniel Pyle、Zining Zhang、Guangbin Dong

  DOI：10.1002/anie.202213691

  日期：2023.4.3

  A redox-neutral, heavy-metal-free approach has been developed to realize deacylative thiolation of common ketones, which provides a unique method to introduce thioether groups site-specifically to unactivated aliphatic positions. Experimental and computational mechanistic studies suggest the involvement of a radical chain pathway.

  开发了一种氧化还原中性、无重金属的方法来实现常见酮的脱酰硫醇化，这提供了一种将硫醚基团位点特异性引入到未活化的脂肪族位置的独特方法。实验和计算机制研究表明自由基链途径的参与。
• Intramolecular Homolytic Substitution at Selenium:  Synthesis of Novel Selenium-Containing Vitamin E Analogues
  作者：Nawaf Al-Maharik、Lars Engman、Jonas Malmström、Carl H. Schiesser

  DOI：10.1021/jo010274k

  日期：2001.9.1

  Treatment of 1-(benzylselenenyl)-5-butyl-5-nonanoI (10) with oxalyl chloride followed by the sodium salt of N-hydroxypyridine-2-thione afforded the corresponding pyridine-2-thione-N-oxycarbonyI (PTOC) oxalate ester which was not isolated but immediately heated to provide 2,2-dibutylselenane (7). This transformation presumably involves a tertiary alkyl radical that undergoes intramolecular homolytic substitution at selenium with loss of the benzyl radical to provide the selenium-containing ring system (7). A similar protocol, when applied to 1-(2-benzylselenenyl-5-methoxyphenyl)-3-methyl3-heptanol (18) and 1-(2-benzylselenenyl-5-methoxyphenyl)-3,7,11,15-tetramethyl-3-hexadecanoI (19), followed by deprotection, afforded the selenium-containing alpha -tocopherol analogues 4 and 1f, respectively, in moderate yields. To the best of our knowledge, these transformations represent the first examples of tertiary radicals involved in homolytic substitution chemistry at selenium.td2