2-{[16-(2-hydroxy-5-methylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecan-7-yl]methyl}-4-methylphenol | 168280-24-8

• 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: 2-{[16-(2-hydroxy-5-methylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecan-7-yl]methyl}-4-methylphenol
• 英文别名: 7,16-bis(2-hydroxy-5-methylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane；7,16-bis(2-hydroxy-5-methylbenzyl)1,4,10,13-tetraoxa-7,16-diazacyclooctadecane；2-[[16-[(2-Hydroxy-5-methylphenyl)methyl]-1,4,10,13-tetraoxa-7,16-diazacyclooctadec-7-yl]methyl]-4-methylphenol
• CAS: 168280-24-8
• 化学式: C₂₈H₄₂N₂O₆
• 分子量: 502.651
• InChiKey: RWXVVJBXVNMDFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  36
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  83.9
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  N,N-双(甲氧基甲基)二氮-18-冠-6 、 2-{[16-(2-hydroxy-5-methylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecan-7-yl]methyl}-4-methylphenol 以 xylene 为溶剂， 反应 24.0h， 以16%的产率得到51,52-dihydroxy-5,22-dimethyl-12,15,29,32,37,40,45,48-octaoxa-1,9,18,26-tetraazapentacyclo<24.8.8.8.1^3,7.1^20,24>dipentaconta-3,5,7(51),20,22,24(52)-hexaene
  参考文献：
  名称：

  A New Approach to the Synthesis of Phenol-Containing Macroheterocycles

  摘要：

  A one-step method for the synthesis of new phenol-containing cryptands and cryptohemispherands by treating N,N'-bis(methoxymethyl)diazacrowns with the appropriate bis- and trisphenols is reported. This method, based on a special Mannich reaction, gives cyclized products without-the need for protecting groups and high dilution conditions. Unusually high yields of cryptohemisherands were realized using a relatively high concentration of the starting materials (50 mmol/L) and in the absence of metal cations as template agents in the reaction mixture. These excellent yields can be explained by intramolecular hydrogen bonding which prevents polycondensation. This new method also allowed preparation of new phenol-containing cylindrical tricyclic ligands by first forming bisphenol-substituted diaza-18-crown-6 at 80 degrees C followed by its reaction with a second bis(methoxymethyl)-substituted diaza-18-crown-6 at 144 degrees C. Crystal structures of two cryptohemispherands are reported herein. A shorter internal distance between N and O atoms in 27 as compared to 6 (R = NO2, n = m = 2) indicates intramolecular hydrogen bonding in phenol-containing macrocycle 27.

  DOI：

  10.1021/jo00120a040
• 作为产物：
  描述：

  对甲酚 、 N,N-双(甲氧基甲基)二氮-18-冠-6 以 四氯化碳 为溶剂， 以84%的产率得到2-{[16-(2-hydroxy-5-methylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecan-7-yl]methyl}-4-methylphenol
  参考文献：
  名称：

  A New Approach to the Synthesis of Phenol-Containing Macroheterocycles

  摘要：

  A one-step method for the synthesis of new phenol-containing cryptands and cryptohemispherands by treating N,N'-bis(methoxymethyl)diazacrowns with the appropriate bis- and trisphenols is reported. This method, based on a special Mannich reaction, gives cyclized products without-the need for protecting groups and high dilution conditions. Unusually high yields of cryptohemisherands were realized using a relatively high concentration of the starting materials (50 mmol/L) and in the absence of metal cations as template agents in the reaction mixture. These excellent yields can be explained by intramolecular hydrogen bonding which prevents polycondensation. This new method also allowed preparation of new phenol-containing cylindrical tricyclic ligands by first forming bisphenol-substituted diaza-18-crown-6 at 80 degrees C followed by its reaction with a second bis(methoxymethyl)-substituted diaza-18-crown-6 at 144 degrees C. Crystal structures of two cryptohemispherands are reported herein. A shorter internal distance between N and O atoms in 27 as compared to 6 (R = NO2, n = m = 2) indicates intramolecular hydrogen bonding in phenol-containing macrocycle 27.

  DOI：

  10.1021/jo00120a040

文献信息

• Reaction on a solid surface — A simple, economical, and efficient Mannich reaction of azacrown ethers over graphite
  作者：Hashem Sharghi、Reza Khalifeh

  DOI：10.1139/v08-026

  日期：2008.5.1

  Graphite brings about a rapid Mannich reaction with a range of activated and unactivated phenolic compounds such as p-cresol and p-nitrophenol. The reactions are carried out with azacrown ether and paraformaldehyde in solvent-free conditions at 100 °C for 20–30 min. The graphite powder can be reused up to three times after simple washing with acetone.Key words: azacrown ether, lariat ether, graphite

  石墨与一系列活化和未活化的酚类化合物（如对甲酚和对硝基苯酚）发生快速曼尼希反应。用氮杂冠醚和多聚甲醛在无溶剂条件下在 100°C 下进行反应 20-30 分钟。石墨粉经丙酮简单洗涤后，最多可重复使用3次。关键词：氮杂冠醚，套索醚，石墨，无溶剂，曼尼希反应。
• Synthesis and crystal structure of copper complex of 7,16-bis(2-hydroxy-5-methyl-3-nitrobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane
  作者：Shu-lan Ma、Wen-xiang Zhu

  DOI：10.1016/s0022-2860(02)00441-6

  日期：2002.12

  been determined by X-ray diffraction. Both crystal structure analysis and spectroscopy study indicated that the side-arm phenols of lariat crown ether are nitrated while complexing with Cu(NO 3 ) 2 . Structure shows that the copper(II) ion is coordinated to two nitrogen and four oxygen atoms, two from the crown ether and other two from the deprotonated phenolate groups. The coordination polyhedron is

  通过一锅曼尼希反应制备了套索冠醚化合物 7,16-双(2-羟基-5-甲基苄基)-1,4,10,13-四氧杂-7,16-二氮杂环十八烷。与配体 7,16-bis(2-hydroxy-5-methyl-3-nitrobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane 配体的铜 (II) 配合物意外合成，并以元素为特征分析、红外和紫外光谱。该配合物的晶体结构已通过 X 射线衍射确定。晶体结构分析和光谱研究表明套索冠醚的侧臂酚在与Cu(NO 3 ) 2 络合时被硝化。结构显示铜 (II) 离子与两个氮原子和四个氧原子配位，其中两个来自冠醚，另外两个来自去质子化酚盐基团。配位多面体是扭曲的八面体。
• The syntheses of phenol-containing azamacrocycles and liquid membrane transports of alkali cations
  作者：Shu-Lan Ma、Chuan-Min Qi、Wen-Xiang Zhu、Qian-Ling Guo、Ying-Chun Liu、Jing Zhang

  DOI：10.1016/j.molstruc.2004.08.002

  日期：2005.1

  synthesized via one-pot Mannich reaction. The compound 1 is structurally characterized. The liquid membrane transports of alkali metal cations using these two new diazamacrocycles and the other previously prepared diazamacrocyclic derivative 7,16-bis(3-hydroxy-6-methyl-2-pyridylmethyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (3) as ion-carriers are also studied. The results show that the rates of cation

  摘要 两种新的含双酚二氮杂冠醚衍生物，7,16-双(2-羟基-5-乙基苯甲酸苄基)-1,4,10,13-四氧杂-7,16-二氮杂环十八烷 (1) 和 7,16-双( 2-羟基-3,4-二甲基苄基)-1,4,10,13-四氧杂-7,16-二氮杂环十八烷 (2)，已通过一锅曼尼希反应合成。化合物1的结构特征。使用这两种新的二氮杂大环和另一种先前制备的二氮杂大环衍生物 7,16-双(3-羟基-6-甲基-2-吡啶基甲基)-1,4,10,13-四氧杂-7 进行碱金属阳离子的液膜传输还研究了 ,16-二氮杂环十八烷 (3) 作为离子载体。结果表明，阳离子传输速率与氮供体数量和取代基团的空间效应密切相关。与其他大环化合物相比，
• Syntheses and aggregate study of bisphenol-containing diaza-18-crown-6 ligands
  作者：Ning Su、Jerald S. Bradshaw、Paul B. Savage、Krzysztof E. Krakowiak、Reed M. Izatt、Stephen L. De Wall、George W. Gokel

  DOI：10.1016/s0040-4020(99)00555-4

  日期：1999.8

  Bisphenol-containing diaza-18-crown-6 ligands (1-16) were synthesized as potential membrane-forming amphiphiles via the one-pot Mannich reaction. Sonication of the crude products in a small amount of MeOH followed by filtration and drying proved to be an efficient method of purifying nearly all compounds. Compounds 8 and 9 were selected for assay as amphiphiles. Compared to simple, alkylated diazacrown ethers, the stability of the amphisomes formed from these monomers is lower possibly because intramolecular hydrogen bonding prevents formation of intermolecular hydrogen bonds. (C) 1999 Elsevier Science Ltd. All rights reserved.
• A New One-Pot Synthesis of Double-Armed Ionizable Crown Ethers Using the Mannich Reaction
  作者：Ki-Whan Chi、Han-Chao Wei、Thomas Kottke、Richard J. Lagow

  DOI：10.1021/jo960332f

  日期：1996.1.1