(4S,14S)-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-17,20-diene-19(21H)-one | 307556-45-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (4S,14S)-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-17,20-diene-19(21H)-one
• 英文别名: (4S,14S)-4,14-bis(2-methylpropyl)-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]henicosa-1(20),17-dien-19-one
• CAS: 307556-45-2
• 化学式: C₂₃H₃₉NO₆
• 分子量: 425.566
• InChiKey: NPZWMDWHYDBSKA-GOTSBHOMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  75.2
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (4S,14S)-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-17,20-diene-19(21H)-one 在 氯化亚砜 、 N,N-二甲基甲酰胺 作用下， 以 氯仿 为溶剂， 反应 193.5h， 生成 (4S,14S)-(-)-N-n-butyl-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21)-17,19-trien-19-amine
  参考文献：
  名称：

  Preparation of pyridino-crown ether-based new chiral stationary phases and preliminary studies on their enantiomer separating ability for chiral protonated primary aralkylamines

  摘要：

  This paper reports the preparation and testing of three new pyridino-18-crown-6 ether-based chiral stationary phases (S,S)-CSP-12, (S,S)-CSP-17 and (S,S)-CSP-20. Secondary amine (S,S)-7 was first transformed to triethoxysilyl derivative (S,S)-11, which contains a urea unit by treating the former with 3-(triethoxysilyl)propyl isocyanate. Next, (S,S)-11 was heated with spherical HPLC quality silica gel in toluene to obtain (S,S)-CSP-12. In order to acetylate the 3-aminopropylsilyl groups bonded to the silica gel during immobilization of the triethoxysilyl derivative (S,S)-11, we pumped acetic anhydride and triethylamine in DMF through the column to give the modified chiral stationary phase (S,S)-CSP-20.Triflate (S,S)-13 was first transformed to a pyridino-18-crown-6 ether derivative (S,S)-15, which contains a 4-(methoxycarbonyl)phenyl substituent at the 4-position of the pyridine ring by a Suzuki carbon-carbon coupling reaction. The hydrolysis of ester (S,S)-15 gave carboxylic acid (S,S)-21. Carboxylic acid (S,S)-21 was reacted with an excess of thionyl chloride to form the appropriate acyl chloride, which was treated with 3-(triethoxysilyl)propylamine in the presence of triethylamine in THF to furnish triethoxysilyl derivative (S,S)-16 containing an amide unit. Triethoxysilyl derivative (S,S)-16 was heated with spherical HPLC quality silica gel in toluene to give the chiral stationary phase (S,S)-CSP-17.The enantiomer separating ability of chiral stationary phases (S,S)-CSP-12, (S,S)-CSP-17 and (S,S)-CSP-20 were tested by using mixtures of enantiomers of 1-(1-naphthyl)ethylamine hydrogen perchlorate (1-NEA), 1-(2-naphthyl)ethylamine (2-NEA), 1-(4-bromophenyl)ethylamine (Br-PEA) and 1-(4-nitrophenyl)ethylamine hydrogen chloride (NO2-PEA). Chiral stationary phase (S,S)-CSP-17 showed the best enantiomer separating ability for the mixtures of enantiomers of amine compounds amongst the pyridino-crown ether-based CSPs ever synthesized. The high enantioselectivity is probably due to the strong pi-pi interaction of the extended pi system of the aryl-substituted pyridine unit. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.04.008
• 作为产物：
  描述：

  (4S,14S)-(-)-2,16-dimethyl-6,9,12-trioxaheptadecane-4,14-diol 在 palladium 10% on activated carbon 、 氢气 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醇 、 mineral oil 为溶剂， 反应 99.67h， 生成 (4S,14S)-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-17,20-diene-19(21H)-one
  参考文献：
  名称：

  含蒽荧光团单元的旋光吡啶并冠醚的合成和对映体识别研究。

  摘要：

  合成了含有蒽荧光团的新型对映体纯的吡啶基-18-冠-6醚基传感器分子。它们对1-苯乙胺高氯酸氢盐（PhEt），1-（1-萘基）乙胺高氯酸氢盐（NapEt），苯甘氨酸甲酯高氯酸氢盐（PhgOMe）和苯丙氨酸甲酯高氯酸氢盐（PheOMe）的对映体识别能力为。使用荧光光谱法在乙腈中检测。传感器分子对NapEt，PhEt和PhgOMe的对映异构体显示出可观的对映异构体识别。发现在大环上含有异丁基的冠醚和NapEt的对映异构体中，对映选择性最高。手性28：562–568，2016。©2016 Wiley Periodicals，Inc.

  DOI：

  10.1002/chir.22614

文献信息

• Synthesis of new enantiopure dimethyl- and diisobutyl -substituted pyridino-18-crown-6 ethers containing a halogen atom or a methoxy group at position 4 of the pyridine ring for enantiomeric recognition studies
  作者：József Kupai、Péter Huszthy、Kata Székely、Tünde Tóth、László Párkányi

  DOI：10.3998/ark.5550190.0012.906

  日期：——

  New enantiomerically pure dimethyl- and diisobutyl-substituted pyridino-18-crown-6 ethers containing a halogen atom or a methoxy group at position 4 of the pyridine ring [(S,S)-1, (S,S)-2, (S,S)-3, (S,S)-4] have been synthesized. A new synthetic route and the solid state structure of the reported enantiopure dimethyl-substituted pyridino-18-crown-6 ether [(S,S)-5] containing a chlorine atom at position

  新的对映体纯二甲基和二异丁基取代的 pyridino-18-crown-6 醚在吡啶环 [(S,S)-1, (S,S)-2, (S,S)-2, (S,S)-2, ( S,S)-3, (S,S)-4] 已合成。还描述了一种新的合成路线和报道的对映纯二甲基取代的 pyridino-18-crown-6 醚 [(S,S)-5] 在吡啶环的 4 位含有一个氯原子的固态结构。这些配体是质子化伯胺、氨基酸及其衍生物的对映体识别研究的良好候选者。