(4S,14S)-(+)-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-17,20-diene-19-(21H)-one | 260967-77-9

• 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-dimethyl-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-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]henicosa-1(20),17-dien-19-one
• CAS: 260967-77-9
• 化学式: C₁₇H₂₇NO₆
• 分子量: 341.404
• InChiKey: XITCEJBBZHHUIZ-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 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-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-17,20-diene-19-(21H)-one 在 bis-triphenylphosphine-palladium(II) chloride 、 氟化铵 、 copper(l) iodide 、 copper(ll) sulfate pentahydrate 、 三氟甲磺酸酐 、 sodium ascorbate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 84.0h， 生成
  参考文献：
  名称：

  当冠醚最终点击时：新型的、点击组装的、荧光对映体纯吡啶基冠醚基化学传感器——以及含有一个的 N-2-芳基-1,2,3-三唑

  摘要：

  已经合成了三种新颖的、点击组装的荧光 pyridino-18-crown-6 醚用于对映体传感。我们还制备了新的叠氮化物和乙炔基取代的 pyridino-18-crown-6 醚作为它们的前体，这为使用点击化学进一步有趣的应用开辟了道路。还通过后三唑芳基化合成了含有N -2-芳基-1,2,3-三唑型荧光团单元的旋光性吡啶基-18-冠-6 醚。研究了这四种荧光传感器分子的光学特性以及它们对 1-苯乙胺、1-（1-萘基）乙胺、苯甘氨酸甲酯和苯丙氨酸甲酯在乙腈中的高氯酸氢盐的对映体识别能力。

  DOI：

  10.1039/d1nj04173h
• 作为产物：
  描述：

  (4S,14S)-19-tetrahydropyranyloxy-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-triene 在 溶剂黄146 作用下， 以 乙醇 为溶剂， 以27.4%的产率得到(4S,14S)-(+)-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-17,20-diene-19-(21H)-one
  参考文献：
  名称：

  Chromatographic enantioseparation of racemic α-(1-naphthyl)ethylammonium perchlorate by a Merrifield resin-bound enantiomerically pure chiral dimethylpyridino-18-crown-6 ligand

  摘要：

  Three novel chiral pyridino-18-crown-6 ligands (S,S)-1, (S,S)-2 and (S,S)-3 were prepared and (S,S)-1 was attached to a Merrifield resin. The resulting adsorbent (S,S)-5 was used as a chiral stationary phase in the chromatographic enantioseparation of racemic alpha-(1 -naphthyl)ethylammonium perchlorate. Also, a new chiral pyridono-18-crown-6 ligand (S,S)-6, used for the synthesis of (S,S)-1 and (S,S)-2, was prepared in two different ways. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00515-7

文献信息

• Synthesis and Enantiomeric Recognition Studies of Optically Active Pyridino-Crown Ethers Containing an Anthracene Fluorophore Unit
  作者：Balázs Szemenyei、Ildikó Móczár、Dávid Pál、Ivett Kocsis、Péter Baranyai、Péter Huszthy

  DOI：10.1002/chir.22614

  日期：2016.7

  Novel enantiopure pyridino‐18‐crown‐6 ether‐based sensor molecules containing an anthracene fluorophore unit were synthesized. Their enantiomeric recognition abilities toward the enantiomers of 1‐phenylethylamine hydrogen perchlorate (PhEt), 1‐(1‐naphthyl)ethylamine hydrogen perchlorate (NapEt), phenylglycine methyl ester hydrogen perchlorate (PhgOMe), and phenylalanine methyl ester hydrogen perchlorate

  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.
• Enantioseparation of protonated primary arylalkylamines and amino acids containing an aromatic moiety on a pyridino-crown ether based new chiral stationary phase
  作者：Viktor Farkas、Tünde Tóth、György Orosz、Péter Huszthy、Miklós Hollósi

  DOI：10.1016/j.tetasy.2006.06.034

  日期：2006.7

  preparation and testing of a new pyridino-18-crown-6 ether based chiral stationary phase (CSP). The chiral crown ether was covalently bound to silica gel. Circular dichroism (CD) spectroscopy was used for probing the complex formation of the chiral crown ether with the enantiomers of protonated primary arylalkylamines. The (S,S)-dimethylpyridino-18-crown-6 ether selector having a terminal double bond was first

  本文报道了一种新的吡啶基-18-冠-6醚基手性固定相（CSP）的制备和测试。手性冠醚共价结合到硅胶上。圆二色性（CD）光谱用于探测手性冠醚与质子化伯芳基烷基胺的对映异构体的复杂形成。（S，S首先通过区域选择性氢化硅烷化将具有末端双键的）-二甲基吡啶基-18-冠-6醚选择剂转化为三乙氧基甲硅烷基衍生物，然后用球形HPLC质量的硅胶加热以获得CSP。使用外消旋体α-（1-萘基）乙胺（1-NEA），α-（2-萘基）乙胺（2-NEA）的外消旋高氯酸氢盐测试填充上述CSP的HPLC柱的鉴别能力。芳香族α-氨基酸和含有不同芳香族侧链保护基团的α-氨基酸的盐酸盐。
• 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。
• Preparation of pyridino-crown ether-based new chiral stationary phases and preliminary studies on their enantiomer separating ability for chiral protonated primary aralkylamines
  作者：József Kupai、Sándor Lévai、Kata Antal、György Tibor Balogh、Tünde Tóth、Péter Huszthy

  DOI：10.1016/j.tetasy.2012.04.008

  日期：2012.4

  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.
• When crown ethers finally click: novel, click-assembled, fluorescent enantiopure pyridino-crown ether-based chemosensors <b>–</b> and an <i>N</i>-2-aryl-1,2,3-triazole containing one
  作者：Balázs Szemenyei、Mira Malmosi、Dávid Pál、Péter Baranyai、László Drahos、Ildikó Móczár、Péter Huszthy

  DOI：10.1039/d1nj04173h

  日期：——

  novel, click-assembled fluorescent pyridino-18-crown-6 ethers have been synthesized for enantiomeric sensing. We also prepared new azide- and ethynyl-substituted pyridino-18-crown-6 ethers as their precursors, which open the way for further interesting applications using click chemistry. An optically active pyridino-18-crown-6 ether containing an N-2-aryl-1,2,3-triazole type fluorophore unit was also

  已经合成了三种新颖的、点击组装的荧光 pyridino-18-crown-6 醚用于对映体传感。我们还制备了新的叠氮化物和乙炔基取代的 pyridino-18-crown-6 醚作为它们的前体，这为使用点击化学进一步有趣的应用开辟了道路。还通过后三唑芳基化合成了含有N -2-芳基-1,2,3-三唑型荧光团单元的旋光性吡啶基-18-冠-6 醚。研究了这四种荧光传感器分子的光学特性以及它们对 1-苯乙胺、1-（1-萘基）乙胺、苯甘氨酸甲酯和苯丙氨酸甲酯在乙腈中的高氯酸氢盐的对映体识别能力。