3,3-diphenylquinuclidine | 67171-23-7

• 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: 3,3-diphenylquinuclidine
• 英文别名: 3,3-diphenyl-1-azabicyclo[2.2.2]octane
• CAS: 67171-23-7
• 化学式: C₁₉H₂₁N
• 分子量: 263.382
• InChiKey: DMOSQLXGQBDKLB-UHFFFAOYSA-N

物化性质

• 沸点：
  383.4±11.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  碘甲烷 、 3,3-diphenylquinuclidine 以 二甲基亚砜 为溶剂， 以70 %的产率得到1-methyl-3,3-diphenylquinuclidinium
  参考文献：
  名称：

  Stable Anion Exchange Membrane Bearing Quinuclidinium for High‐performance Water Electrolysis

  摘要：

  Anion exchange membranes (AEMs) are core components in anion exchange membrane water electrolyzers (AEM‐WEs). However, the stability of functional quaternary ammonium cations, especially under high temperatures and harsh alkaline conditions, seriously affects their performance and durability. Herein, we synthesized a 1‐methyl‐3,3‐diphenylquinuclidinium molecular building unit. Density functional theory (DFT) calculations and accelerated aging analysis indicated that the quinine ring structure was exceedingly stable, and the S_N2 degradation mechanism dominated. Through acid‐catalyzed Friedel–Crafts polymerization, a series of branched poly(aryl‐quinuclidinium) (PAQ‐x) AEMs with controllable molecular weight and adjustable ion exchange capacity (IEC) were prepared. The stable quinine structure in PAQ‐x was verified and retained in the ex situ alkaline stability. Furthermore, the branched polymer structure reduces the swelling rate and water uptake to achieve a tradeoff between dimensional stability and ionic conductivity, significantly improving the membrane's overall performance. Importantly, PAQ‐5 was used in non‐noble metal‐based AEM‐WE, achieving a high current density of 8 A cm⁻² at 2 V and excellent stability over 2446 h in a gradient constant current test. Based on the excellent alkaline stability of this diaryl‐quinuclidinium group, it can be further considered as a multifunctional building unit to create multi‐topological polymers for energy conversion devices used in alkaline environments.

  DOI：

  10.1002/anie.202400764
• 作为产物：
  描述：

  3-奎宁环酮盐酸盐 、 苯 在 三氯化铝 作用下， 以68%的产率得到3,3-diphenylquinuclidine
  参考文献：
  名称：

  6-氨基甲酰基-5-苯基-2,3,5,6-四氢-1 H -1,4-乙基苯并[ f ]喹啉的合成及反应活性。（4a R，5 S，6 R，10b R）-5-苯基-2,3,4a，5,6,10b-六氢-1 H -1,4-乙基苯并[ f ]喹啉的X射线分子结构乙酸-6-丁酯

  摘要：

  在硫酸存在下2-（2-氰基-1,2-二苯基乙基）奎宁环酮-3-酮1的环缩合得到分子内苯基化而不是内酰胺的形成。将该环状产物氢化，得到6-氨基甲酰基-5-苯基-2,3,4a，5,6,10b-六氢-1 H -1,4-乙基苯并-[ f ]喹啉。用LiAlH 4处理时，氨基甲酰基被立体定向​​地替换为羟基。将该醇乙酰化，并通过X射线晶体学确认结构。认为羟基化反应是通过甲腈中间体进行的。在空气存在下，腈可以转化为酮，然后将其还原为醇，并保持整体构型。

  DOI：

  10.1039/p19950000475

文献信息

• Synthesis and reactivity of 6-carbamoyl-5-phenyl-2,3,5,6-tetrahydro-1H-1,4-ethanobenzo[f]quinoline. X-Ray molecular structure of (4aR,5S,6R,10bR)-5-phenyl-2,3,4a,5,6,10b-hexahydro-1H-1,4-ethanobenzo[f]quinolin-6-yl acetate
  作者：Yevgeny Besidsky、Kristina Luthman、Alf Claesson、Ingeborg Csöregh、Uli Hacksell

  DOI：10.1039/p19950000475

  日期：——

  phenylation instead of lactam formation. The cyclic product was hydrogenated to give 6-carbamoyl-5-phenyl-2,3,4a,5,6,10b-hexahydro-1H-1,4-ethanobenzo-[f]quinoline. On treatment with LiAlH4 the carbamoyl group was stereospecifically replaced by a hydroxy group. The alcohol was acetylated and the structure was confirmed by X-ray crystallography. The hydroxylation reaction is believed to proceed via a

  在硫酸存在下2-（2-氰基-1,2-二苯基乙基）奎宁环酮-3-酮1的环缩合得到分子内苯基化而不是内酰胺的形成。将该环状产物氢化，得到6-氨基甲酰基-5-苯基-2,3,4a，5,6,10b-六氢-1 H -1,4-乙基苯并-[ f ]喹啉。用LiAlH 4处理时，氨基甲酰基被立体定向​​地替换为羟基。将该醇乙酰化，并通过X射线晶体学确认结构。认为羟基化反应是通过甲腈中间体进行的。在空气存在下，腈可以转化为酮，然后将其还原为醇，并保持整体构型。
• Synthesis of Aryl-Substituted Piperidines by Superacid Activation of Piperidones
  作者：Douglas A. Klumpp、Manuel Garza、Andre Jones、Saray Mendoza

  DOI：10.1021/jo990454i

  日期：1999.9.1

  (80-99%) by the reaction of piperidones (3d-h) with benzene and the Bronsted superacid, trifluoromethanesulfonic acid (CF(3)SO(3)H, TfOH). Tropinone (6) and quinuclidone (7) also react in good yields with benzene in TfOH to give the condensation products (13 and 14). Ketal and acetal derivatives also give condensation products (8 and 24) upon reaction with C(6)H(6) in TfOH. The conversion of 3g to 11 is

  通过使哌啶酮（3d-h）与苯和布朗斯台德超强酸三氟甲磺酸（CF（3）SO（3）H）反应，可以制备出高至优异收率（80-99％）的二芳基哌啶（8-12）， TfOH）。Tropinone（6）和quinuclidone（7）也可以与苯在TfOH中反应，得到缩合产物（13和14）。与C（6）H（6）在TfOH中反应时，缩酮和缩醛衍生物还会产生缩合产物（8和24）。3g转化为11对酸量和酸强度均敏感。提出了一种用于转换的调用机制的机制。
• Stable Anion Exchange Membrane Bearing Quinuclidinium for High‐performance Water Electrolysis
  作者：Liqiang Yin、Rong Ren、Lanlan He、Wentao Zheng、Yu Guo、Linqin Wang、Husileng Lee、Jian Du、Zhiheng Li、Tang Tang、Guoheng Ding、Licheng Sun

  DOI：10.1002/anie.202400764

  日期：2024.5.6

  Anion exchange membranes (AEMs) are core components in anion exchange membrane water electrolyzers (AEM‐WEs). However, the stability of functional quaternary ammonium cations, especially under high temperatures and harsh alkaline conditions, seriously affects their performance and durability. Herein, we synthesized a 1‐methyl‐3,3‐diphenylquinuclidinium molecular building unit. Density functional theory (DFT) calculations and accelerated aging analysis indicated that the quinine ring structure was exceedingly stable, and the S_N2 degradation mechanism dominated. Through acid‐catalyzed Friedel–Crafts polymerization, a series of branched poly(aryl‐quinuclidinium) (PAQ‐x) AEMs with controllable molecular weight and adjustable ion exchange capacity (IEC) were prepared. The stable quinine structure in PAQ‐x was verified and retained in the ex situ alkaline stability. Furthermore, the branched polymer structure reduces the swelling rate and water uptake to achieve a tradeoff between dimensional stability and ionic conductivity, significantly improving the membrane's overall performance. Importantly, PAQ‐5 was used in non‐noble metal‐based AEM‐WE, achieving a high current density of 8 A cm⁻² at 2 V and excellent stability over 2446 h in a gradient constant current test. Based on the excellent alkaline stability of this diaryl‐quinuclidinium group, it can be further considered as a multifunctional building unit to create multi‐topological polymers for energy conversion devices used in alkaline environments.