2-(4,4-二氟戊基)异吲哚-1,3-二酮 | 1017241-13-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 中文名称: 2-(4,4-二氟戊基)异吲哚-1,3-二酮
• 英文名称: 2-(4,4-difluoropentyl)isoindoline-1,3-dione
• 英文别名: 2-(4,4-Difluoropentyl)isoindole-1,3-dione；2-(4,4-difluoropentyl)isoindole-1,3-dione
• CAS: 1017241-13-2
• 化学式: C₁₃H₁₃F₂NO₂
• 分子量: 253.249
• InChiKey: ZIFKUGJLWQNBMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  N-(4-戊炔基)酞酰亚胺 在 Potassium;sulfuric acid;fluoride 、 C₆H₁₂N₂O*12FH 作用下， 以 neat (no solvent) 为溶剂， 反应 3.0h， 以65%的产率得到2-(4,4-二氟戊基)异吲哚-1,3-二酮
  参考文献：
  名称：

  功能化炔烃和丙二烯的无溶剂和无金属区域选择性氢氟化：合成宝石二氟化物的有效方案

  摘要：

  两种易于处理的高酸性液体 HF 络合物试剂 DMPU-12HF 和 KHSO 4 -13HF 的组合产生了高酸性氟化系统，该系统促进 HF 与广泛官能化的炔烃（包括炔烃系留药物或丙二烯）进行排他性马尔可夫尼科夫加成，以生产宝石二氟化物具有高原子经济性，并且易于后处理。

  DOI：

  10.1039/c8gc03876g

文献信息

• Solventless and metal-free regioselective hydrofluorination of functionalized alkynes and allenes: an efficient protocol for the synthesis of <i>gem</i>-difluorides
  作者：Zhichao Lu、Bhvandip S. Bajwa、Shiwen Liu、Sheye Lee、Gerald B. Hammond、Bo Xu

  DOI：10.1039/c8gc03876g

  日期：——

  The combination of two easily handled, highly acidic liquid HF complex reagents, DMPU-12HF and KHSO4-13HF, generated a highly acidic fluorination system that facilitated exclusive Markovnikov addition of HF to widely functionalized alkynes, including alkyne tethered drugs, or allenes to produce gem-difluorides with high atom economy, and with an easy workup.

  两种易于处理的高酸性液体 HF 络合物试剂 DMPU-12HF 和 KHSO 4 -13HF 的组合产生了高酸性氟化系统，该系统促进 HF 与广泛官能化的炔烃（包括炔烃系留药物或丙二烯）进行排他性马尔可夫尼科夫加成，以生产宝石二氟化物具有高原子经济性，并且易于后处理。
• <i>gem</i>-Difluorination of Aminoalkynes via Highly Reactive Dicationic Species in Superacid HF−SbF₅:  Application to the Efficient Synthesis of Difluorinated Cinchona Alkaloid Derivatives
  作者：Anne-Céline Cantet、Hélène Carreyre、Jean-Pierre Gesson、Marie-Paule Jouannetaud、Brigitte Renoux

  DOI：10.1021/jo702441p

  日期：2008.4.1

  reacted in the superacid system HF−SbF5 to give regioselectively new β-gem-difluoroamines. The reaction, which is not observed in pure HF, is consistent with the formation of a dicationic intermediate (i.e., both vinylic and adjacent protonated N-ammonium cations). Application to the regioselective and efficient synthesis of difluorinated cinchona alkaloid derivatives is described.

  各种烷基化的胺，酰胺和酰亚胺在超酸体系HF-SbF 5中反应，生成区域选择性的新β-锗-二氟胺。在纯HF中未观察到的反应与双官能中间体（即乙烯基和相邻的质子化N-铵阳离子）的形成是一致的。描述了在区域选择性和有效合成二氟化金鸡纳生物碱衍生物中的应用。
• Designer HF-Based Fluorination Reagent: Highly Regioselective Synthesis of Fluoroalkenes and <i>gem</i>-Difluoromethylene Compounds from Alkynes
  作者：Otome E. Okoromoba、Junbin Han、Gerald B. Hammond、Bo Xu

  DOI：10.1021/ja508369z

  日期：2014.10.15

  hydrogen-bond acceptors (e.g., DMPU) can form stable complexes through hydrogen bonding. The DMPU/HF complex is a new nucleophilic fluorination reagent that has high acidity and is compatible with cationic metal catalysts. The gold-catalyzed mono- and dihydrofluorination of alkynes using the DMPU/HF complex yields synthetically important fluoroalkenes and gem-difluoromethlylene compounds regioselectively

  氟化氢 (HF) 和选定的非碱性和弱配位（对阳离子金属）氢键受体（例如，DMPU）可以通过氢键形成稳定的配合物。DMPU/HF配合物是一种新型的亲核氟化试剂，具有高酸性，与阳离子金属催化剂相容。使用 DMPU/HF 配合物对炔烃进行金催化的单和二氟化氢反应，可区域选择性地产生合成上重要的氟烯烃和墒二氟亚甲基化合物。
• Straightforward Synthesis of Alkyl Fluorides via Visible-Light-Induced Hydromono- and Difluoroalkylations of Alkenes with α-Fluoro Carboxylic Acids
  作者：Chunfang Guo、Xuliang Han、Yu Feng、Zhaolong Liu、Yueyun Li、Hui Liu、Lizhi Zhang、Yunhui Dong、Xinjin Li

  DOI：10.1021/acs.joc.2c00965

  日期：2022.7.15

  We herein report the first visible-light-induced hydromono- and difluoroalkylations of alkenes with inexpensive and easily accessible α-fluoro carboxylic acids. This metal-free protocol exhibits mild conditions, high efficiency, and excellent functional-group tolerance, providing a straightforward approach to mono- and difluoroalkylated alkanes. Moreover, the fluorine effect on the hydrofluoroalkylation

  我们在此报告了第一个可见光诱导的烯烃与廉价且易于获得的 α-氟代羧酸的氢单和二氟烷基化反应。这种无金属协议表现出温和的条件、高效率和出色的官能团耐受性，为单氟烷基化烷烃和二氟烷基化烷烃提供了一种直接的方法。此外，详细讨论了氟对氢氟烷基化反应的影响。
• Catalytic HF Shuttling between Fluoroalkanes and Alkynes**
  作者：Shannon E. S. Farley、Daniel Mulryan、Feriel Rekhroukh、Andreas Phanopoulos、Mark R. Crimmin

  DOI：10.1002/anie.202317550

  日期：2024.1.25

  In this paper, we report BF₃ ⋅ OEt₂ as a catalyst to shuttle equivalents of HF from a fluoroalkane to an alkyne. Reactions of terminal and internal aliphatic alkynes led to formation of difluoroalkane products, while diarylalkynes can be selectively converted into fluoroalkenes. The method tolerates numerous sensitive functional groups including halogen, protected amine, ester and thiophene substituents. Mechanistic studies (DFT, probe experiments) suggest the catalyst is involved in both the defluorination and fluorination steps, with BF₃ acting as a Lewis acid and OEt₂ a weak Lewis base that mediates proton transfer. In certain cases, the interconversion of fluoroalkene and difluoroalkane products was found to be reversible. The new catalytic system was applied to demonstrate proof‐of‐concept recycling of poly(vinylidene difluoride).

  摘要 在本文中，我们报告了 BF3 ⋅ OEt2 作为催化剂将等当量的 HF 从氟烷烃穿梭到炔烃的情况。末端和内部脂肪族炔烃的反应可形成二氟烷烃产物，而二芳基炔烃则可选择性地转化为氟烯烃。该方法可容忍多种敏感官能团，包括卤素、受保护的胺、酯和噻吩取代基。机理研究（DFT、探针实验）表明，催化剂参与了脱氟和氟化两个步骤，其中 BF3 起着路易斯酸的作用，而 OEt2 则是介导质子转移的弱路易斯碱。在某些情况下，氟烯烃和二氟烷烃产物的相互转化是可逆的。新催化系统被用于演示聚偏二氟乙烯的概念验证回收。