2-bromo-N,N-dibutylaniline | 1334232-88-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-bromo-N,N-dibutylaniline
• CAS: 1334232-88-0
• 化学式: C₁₄H₂₂BrN
• 分子量: 284.239
• InChiKey: STHCVCPMNPXPRL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-bromo-N,N-dibutylaniline 在 copper(l) iodide 、 正丁基锂 、 bis(triphenylphosphine)palladium(II) chloride 、 sodium hydride 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 74.08h， 生成 N,N-dibutyl-2-[(E)-2-[4-[(E)-2-[2-(dibutylamino)phenyl]ethenyl]-2,5-bis(2-pyridin-2-ylethynyl)phenyl]ethenyl]aniline
  参考文献：
  名称：

  The Photophysics of Pyridine-Derivatizedortho-,meta-, andpara-Dibutylamino Cruciforms

  摘要：

  AbstractThe photophysical properties of a series of para‐substituted donor–acceptor cruciform fluorophores (p1–4) were investigated and compared with their meta and ortho isomers (m1–4 and o1–4). The structural variations were found to have a significant effect on the solvatochromism, fluorescence quantum yields (Φfl), fluorescence lifetimes (τfl), and response upon addition of trifluoroacetic acid. The observed spectral shifts in absorption and emission caused by protonation of the cruciforms make them promising candidates as chemosensors. Additional computational studies provided more insight into the electronic structure of the systems.

  DOI：

  10.1002/chem.201300211
• 作为产物：
  描述：

  二正丁胺 在 titanium(IV) isopropylate 、 N-氯代丁二酰亚胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.41h， 生成 2-bromo-N,N-dibutylaniline
  参考文献：
  名称：

  使用伯胺和仲胺进行钛介导的格氏试剂的胺化

  摘要：

  制作，然后破坏它：使用标题转化法，在苯胺衍生物的合成中使用N-氯代琥珀酰亚胺（NCS）作为氧化剂（参见方案）。胺和格氏试剂均具有良好的功能性。雄激素受体激动剂和几种类似物被合成以证明该方法的实用性。

  DOI：

  10.1002/anie.201103700

文献信息

• Unexpected Rearrangement of 2-Bromoaniline under Biphasic Alkylation Conditions
  作者：Scott Barraza、Scott Denmark

  DOI：10.1055/s-0036-1590882

  日期：2017.12

  benzyl bromide under ostensibly basic N-alkylation conditions resulted in migration of bromine from the 2- to the 4-aryl position. Herein we report our studies to elucidate the mechanism of this rearrangement with the objective of suppressing this unexpected outcome. We find that careful choice of reagents is critical, and that this behavior may be extrapolated to alkylation reactions of electron-rich

  在表面上呈碱性的 N-烷基化条件下，2-溴苯胺与苄基溴的烷基化导致溴从 2- 到 4-芳基位置的迁移。在此，我们报告了我们的研究，以阐明这种重排的机制，目的是抑制这种意想不到的结果。我们发现谨慎选择试剂是至关重要的，并且这种行为通常可以外推到富含电子的溴苯胺和碘苯胺的烷基化反应。
• Selective N-Alkylation of Arylamines with Alkyl Chloride in Ionic Liquids: Scope and Applications
  作者：Antonio Monopoli、Pietro Cotugno、Marina Cortese、Cosima Damiana Calvano、Francesco Ciminale、Angelo Nacci

  DOI：10.1002/ejoc.201200202

  日期：2012.6

  An efficient N-selective alkylation of primary aromatic amines in molten quaternary ammonium salts, as the solvent, under relatively mild and base-free conditions is presented. On the basis of the Kamlet–Taft parameters and the nucleophilicity of the IL (ionic liquid) anions, the influence of the ionic liquid was evaluated. This protocol was validated on a larger multigram scale and with the syntheses

  介绍了在相对温和和无碱的条件下，以熔融季铵盐作为溶剂，伯芳胺的有效 N 选择性烷基化。在 Kamlet-Taft 参数和 IL（离子液体）阴离子的亲核性的基础上，评估了离子液体的影响。该协议在更大的多克规模上进行了验证，并与生物活性杂环（例如，1,4-苯并噻嗪和喹喔啉）和新的高效 MALDI 基质的合成有关。
• Chemoselective synthesis of tertiary and secondary amines by reductive amination of aldehydes
  作者：Wan-Jin Xiong、Lei Li、Jiang-Tao Li、Shi-Qiang Zhang、Jun-Lei Tang、Taigang Zhou

  DOI：10.1016/j.tetlet.2023.154684

  日期：2023.9

  A simple and efficient catalyst-free chemoselective reductive amination of primary amines and aldehydes to synthesis of tertiary and secondary amines with borane complex was developed. Primary amines are converted into tertiary and secondary amines in one pot reaction under mild condition with good functional group compatibility and It does not require any catalyst to participate in this reaction.

  开发了一种简单高效的无催化剂化学选择性还原胺化伯胺和醛，以与硼烷配合物合成叔胺和仲胺。伯胺转化为叔胺和仲胺的一锅反应条件温和，官能团相容性好，并且不需要任何催化剂参与该反应。通过改变硼烷络合物的空间位阻来实现化学选择性控制。该策略成功应用于合成丁卡因（麻醉剂），并通过同位素标记实验验证了其潜在机制。
• The Photophysics of Pyridine-Derivatized<i>ortho</i>-,<i>meta</i>-, and<i>para</i>-Dibutylamino Cruciforms
  作者：Florian Hinderer、Uwe H. F. Bunz

  DOI：10.1002/chem.201300211

  日期：2013.6.24

  AbstractThe photophysical properties of a series of para‐substituted donor–acceptor cruciform fluorophores (p1–4) were investigated and compared with their meta and ortho isomers (m1–4 and o1–4). The structural variations were found to have a significant effect on the solvatochromism, fluorescence quantum yields (Φfl), fluorescence lifetimes (τfl), and response upon addition of trifluoroacetic acid. The observed spectral shifts in absorption and emission caused by protonation of the cruciforms make them promising candidates as chemosensors. Additional computational studies provided more insight into the electronic structure of the systems.
• Titanium-Mediated Amination of Grignard Reagents Using Primary and Secondary Amines
  作者：Timothy J. Barker、Elizabeth R. Jarvo

  DOI：10.1002/anie.201103700

  日期：2011.8.29

  N‐chlorosuccinimide (NCS) was employed as the oxidant in the synthesis of aniline derivatives using the title transformation (see scheme). Functionalization was well tolerated on both the amine and Grignard reagent. An androgen receptor agonist and several analogues were synthesized to demonstrate the utility of this method.

  制作，然后破坏它：使用标题转化法，在苯胺衍生物的合成中使用N-氯代琥珀酰亚胺（NCS）作为氧化剂（参见方案）。胺和格氏试剂均具有良好的功能性。雄激素受体激动剂和几种类似物被合成以证明该方法的实用性。