di-(4-fluorophenyl)methyl ether | 1332707-99-9

• 物质功能分类: 有机原料 - 杂环化合物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: di-(4-fluorophenyl)methyl ether
• 英文别名: bis(4,4'-difluorodiphenylmethyl) ether；(bis(4-fluorophenyl)methoxy)bis(4-fluorophenyl)methane；Bis[bis[4-fluorophenyl]methyl]ether；1-[bis(4-fluorophenyl)methoxy-(4-fluorophenyl)methyl]-4-fluorobenzene
• CAS: 1332707-99-9
• 化学式: C₂₆H₁₈F₄O
• 分子量: 422.422
• InChiKey: WNEUDTAHYHQWKQ-UHFFFAOYSA-N

物化性质

• 熔点：
  78-79 °C
• 沸点：
  468.9±40.0 °C(Predicted)
• 密度：
  1.265±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  di-(4-fluorophenyl)methyl ether 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 为溶剂， 反应 60.0h， 生成
  参考文献：
  名称：

  Breslow 中间体的激进 [1,3] 重排

  摘要：

  带有自由基稳定N取代基（例如苄基、肉桂基和二芳基甲基）的Breslow中间体在温和条件下容易发生C - N键均裂，得到正式的[1,3]重排产物而不是安息香缩合产物。EPR 实验和计算分析支持基于激进的机制。讨论了硫胺素酶的影响。

  DOI：

  10.1002/anie.201508368
• 作为产物：
  描述：

  4,4'-二氟二苯甲醇 在 sodium hydrogensulfite 作用下， 反应 1.0h， 以95%的产率得到di-(4-fluorophenyl)methyl ether
  参考文献：
  名称：

  亚硫酸氢钠：一种通过芳香/脂肪醇脱水形成醚的有效催化剂

  摘要：

  亚硫酸氢钠在无溶剂条件下可通过分子间脱水直接催化苄醇（1）的醚化反应。在存在0.3mol％或0.6mol％量的亚硫酸氢钠的情况下，由相应的醇以高产率（高达95％）制备对称和不对称醚。还讨论了苯甲醇的醚化。

  DOI：

  10.1002/cjoc.201190220

文献信息

• Reversible Generation of Labile Secondary Carbocations from Alcohols in the Nanospace of H-Mordenite and Their Long-Lasting Preservation at Ambient Temperature
  作者：Yoichi Masui、Taiki Hattori、Makoto Onaka

  DOI：10.1021/jacs.7b03336

  日期：2017.6.28

  side reactions prevailed in TfOH and formation of 2 was not observed. Preservation of other secondary carbocations from benzhydrol, 4,4′-dichlorobenzhydrol, and 9-fluorenol was also realized in H-Mor. It was confirmed that the generation of 2 from 1 was controlled by thermodynamic equilibrium rather than kinetic regulations. The equilibrium between 2 and 1 was accompanied by reversible chromism, which

  由于不稳定，因此在环境温度下很难长时间观察到次级碳正离子。在这项研究中，当4,4'-二氟苯甲酸（1）与H-丝光沸石（H-Mor）混合时，产生了4,4'-二氟二苯甲基阳离子（2）作为主要产物，通过UV-vis和13 C-MAS NMR光谱学分析，在室温下保存1周以上。令人惊讶地，1的聚合和歧化在H-Mor的微孔中几乎没有进行。但是，这些副反应主要存在于TfOH和2的形成中。没有被观察到。在H-Mor中，还实现了从苯甲醇，4,4'-二氯苯甲醇和9-芴醇中保留其他次级碳正离子的作用。可以确定，从1生成2是受热力学平衡而不是动力学规则控制的。2和1之间的平衡伴随着可逆的色度，通过改变H-Mor中的水分含量可以很容易地控制色度。此外，本文描述了在微孔内表面上密集地填充有酸位的沸石中的特定酸催化的新见解。
• An expedient, efficient and solvent-free synthesis of T3P®-mediated amidation of benzhydrols with poorly reactive N-nucleophiles under MW irradiation
  作者：Srinivas Cheruku、Sandhya C. Nagarakere、Makanahalli P. Sunilkumar、Yatheesh Narayana、Kumara N. Manikyanally、Kanchugarakoppal S. Rangappa、Kempegowda Mantelingu

  DOI：10.1039/d1nj04502d

  日期：——

  An expedient, efficient, economical, environmentally benign, and solvent free amidation protocol of benzhydrols with less reactive nitrogen nucleophiles assisted by propylphosphonic anhydride (T3P®) under microwave irradiation has been developed. The methodology has been deployed for a wide range of heterocycles and electron-withdrawing & electron-donating groups. The protocol resulted in good to excellent

  已经开发了一种方便、高效、经济、环境友好且无溶剂的苯甲醇与低活性氮亲核试剂的酰胺化方案，该方案在微波辐射下由丙基膦酸酐 (T3P®) 辅助。该方法已应用于广泛的杂环和吸电子和给电子基团。该协议在给定条件下产生了良好的产量（26 个示例，68-93% 的产量）。
• Process Development and Optimization for Production of a Potassium Ion Channel Blocker, ICA-17043
  作者：Bingidimi I. Mobele、Sripathy Venkatraman、Grant McNaughton-Smith、Cameron Gibb、Luckner G. Ulysse、Carl A. Lindmark、Stephen Shaw、Brian Marron、Kerry Spear、Mark J. Suto

  DOI：10.1021/op3000916

  日期：2012.8.17

  A scalable process for the manufacture of a potassium ion channel blocker was developed and optimized. Key features of the process include an optimized Grignard reaction, a direct cyanation of the intermediate trityl alcohol derivative, and an improved nitrile hydrolysis protocol, relative to the original acidic hydrolysis conditions, to generate the crude active pharmaceutical ingredient (API) with >95% HPLC purity. The Grignard and the cyanation reactions could be telescoped, resulting in an improved throughput compared to the original four-step process. An effective recrystallization of the API was also developed and the process scaled up to manufacture multiple batches at the pilot scale.
• Synthesis of 4-Fluoro-β-(4-fluorophenyl)-<scp>l</scp>-phenylalanine by an Asymmetric Phase-Transfer Catalyzed Alkylation:  Synthesis on Scale and Catalyst Stability
  作者：Daniel E. Patterson、Shiping Xie、Lynda A. Jones、Martin H. Osterhout、Christopher G. Henry、Thomas D. Roper

  DOI：10.1021/op060190j

  日期：2007.5.1

  4-Fluoro-beta-(4-fluorophenyl)-L-phenylalanine 1 was synthesized by the asymmetric phase- transfer catalyzed alkylation of tertbutyl glycinate-benzophenone Schiff base using the cinchona alkaloid derived catalyst 6. Upon scaling, it was observed that to achieve high levels of enantioselectivity, it was necessary to add the catalyst or base last. From these studies, insight into the stability of the catalyst 6 under the reaction conditions was gained.