(4S,14S)-(-)-19-chloro-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-triene | 1314884-17-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S,14S)-(-)-19-chloro-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-triene
• 英文别名: (4S,14S)-(-)-4,14-diisobutyl-19-chloro-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21)-17,19-triene
• CAS: 1314884-17-7
• 化学式: C₂₃H₃₈ClNO₅
• 分子量: 444.011
• InChiKey: FSHVDHMCWNBZCV-GOTSBHOMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.66
• 重原子数：
  30.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  59.04
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (4S,14S)-(-)-19-chloro-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-triene 、 苄胺 反应 192.0h， 以69%的产率得到(4S,14S)-(-)-N-benzyl-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：

  二甲基4-羰基-1,4-二氢-2,6-吡啶二羧酸酯 在 sodium tetrahydroborate 、 氯化亚砜 、 sodium hydride 、 N,N-二甲基甲酰胺 、 potassium hydroxide 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 氯仿 、 水 、 mineral oil 为溶剂， 反应 126.67h， 生成 (4S,14S)-(-)-19-chloro-4,14-diisobutyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-triene
  参考文献：
  名称：

  合成新的对映体纯二甲基和二异丁基取代的 pyridino-18-crown-6 醚，在吡啶环的 4 位含有卤素原子或甲氧基，用于对映体识别研究

  摘要：

  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。

  DOI：

  10.3998/ark.5550190.0012.906