2,6-bis[2',6'-bis(bromomethyl)-4'-methylphenoxymethyl]pyridine | 182692-03-1

• 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: 2,6-bis[2',6'-bis(bromomethyl)-4'-methylphenoxymethyl]pyridine
• 英文别名: 2,6-Bis[[2,6-bis(bromomethyl)-4-methylphenoxy]methyl]pyridine
• CAS: 182692-03-1
• 化学式: C₂₅H₂₅Br₄NO₂
• 分子量: 691.095
• InChiKey: QPLPERBQJXXCDK-UHFFFAOYSA-N

物化性质

• 沸点：
  643.7±50.0 °C(Predicted)
• 密度：
  1.716±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  31.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,6-bis[2',6'-bis(bromomethyl)-4'-methylphenoxymethyl]pyridine 、 二乙二醇 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以13%的产率得到13,27-dimethyl-3,6,9,17,20,23,30,38-octaoxa-40-azahexacyclo[23.3.1.9^29,39.3^11,15.1^11,15.1^32,36]tetraconta-1(29),11,13,15(39),25,27,32,34,36(40)-nonaene
  参考文献：
  名称：

  Chiral Pyridine-Based Macrobicyclic Clefts:  Synthesis and Enantiomeric Recognition of Ammonium Salts

  摘要：

  An achiral (3) and two chiral pyridine-based macrobicyclic clefts (4 and 5) have been prepared by treating 2,6-bis[[2',6'-bis(bromomethyl)-4'-methylphenoxy]pyridine (2) with the appropriate achiral and chiral glycols. Starting 2 was prepared by first treating 2,6-bis(hydroxymethyl)-4-methylphenol with 2,6-[(tosyloxy)methyl]pyridine followed by phosphorus tribromide. Achiral macrobicyclic cleft 3 formed a complex at 25 degrees C in 50% CH3OH/50% CHCl3 (v/v) with a primary ammonium salt (log K=3.15) as evidenced by a significant change in the (1)HNMR spectrum. Highly organized (S,S,S,S)4, prepared by treating 2 with (1S,5S)-3-oxapentane-1,5-diol, exhibited recognition at 25 degrees C in 20% C2H5OH/80% 1,2-C2H4Cl2 (v/v) for the (S)-enantiomer of alpha-(1-naphthyl)-ethylammonium perchlorate (NapEt) over its (R)-form (Delta log K=0.85). This high recognition factor probably reflects an increase in molecular rigidity by the introduction of a second macro ring on the monocyclic pyridinocrown ligand.

  DOI：

  10.1021/jo960890u
• 作为产物：
  描述：

  2,6-bis[2',6'-bis(hydroxymethyl)-4'-methylphenoxymethyl]pyridine 在 三溴化磷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.5h， 以65%的产率得到2,6-bis[2',6'-bis(bromomethyl)-4'-methylphenoxymethyl]pyridine
  参考文献：
  名称：

  带有氨基醇亚基的手性吡啶-大环化合物对手性有机铵盐的对映体识别

  摘要：

  通过用适当的手性氨基醇处理2,6-双[[2'6'-双（溴甲基）-4'-甲基苯氧基]甲基]吡啶3来制备基于吡啶的大环化合物。通过UV滴定评估手性有机铵盐对这些带有吡啶基冠型配体的氨基醇亚基的大环的对映体识别。在（S，S，S）-1，（S，S，S）-2和（S，S，S）的（R）-Am2和（S）-Am2的K a值中观察到重要差异。）-3个主机，分别为K S / K R  = 5.0，K S / K R  = 2.4和K S / K R  = 5.0。宿主似乎普遍识别Am1和Am2的（S）-对映异构体。

  DOI：

  10.1016/j.tetasy.2009.06.010

文献信息

• Chiral Pyridine-Based Macrobicyclic Clefts:  Synthesis and Enantiomeric Recognition of Ammonium Salts
  作者：Paul C. Hellier、Jerald S. Bradshaw、J. Jolene Young、Xian Xin Zhang、Reed M. Izatt

  DOI：10.1021/jo960890u

  日期：1996.1.1

  An achiral (3) and two chiral pyridine-based macrobicyclic clefts (4 and 5) have been prepared by treating 2,6-bis[[2',6'-bis(bromomethyl)-4'-methylphenoxy]pyridine (2) with the appropriate achiral and chiral glycols. Starting 2 was prepared by first treating 2,6-bis(hydroxymethyl)-4-methylphenol with 2,6-[(tosyloxy)methyl]pyridine followed by phosphorus tribromide. Achiral macrobicyclic cleft 3 formed a complex at 25 degrees C in 50% CH3OH/50% CHCl3 (v/v) with a primary ammonium salt (log K=3.15) as evidenced by a significant change in the (1)HNMR spectrum. Highly organized (S,S,S,S)4, prepared by treating 2 with (1S,5S)-3-oxapentane-1,5-diol, exhibited recognition at 25 degrees C in 20% C2H5OH/80% 1,2-C2H4Cl2 (v/v) for the (S)-enantiomer of alpha-(1-naphthyl)-ethylammonium perchlorate (NapEt) over its (R)-form (Delta log K=0.85). This high recognition factor probably reflects an increase in molecular rigidity by the introduction of a second macro ring on the monocyclic pyridinocrown ligand.
• The enantiomeric recognition of chiral organic ammonium salts by chiral pyridino-macrocycles bearing aminoalcohol subunits
  作者：Hayriye Ozer、Şafak Ozhan Kocakaya、Abuzer Akgun、Halil Hoşgören、Mahmut Togrul

  DOI：10.1016/j.tetasy.2009.06.010

  日期：2009.7

  were prepared by treating 2,6-bis[[2′6′-bis(bromomethyl)-4′-methylphenoxy]methyl]pyridine 3 with the appropriate chiral aminoalcohols. The enantiomeric recognition of these macrocycles bearing aminoalcohol subunits of the pyridinocrown type ligand was evaluated for chiral organic ammonium salts by UV titration. The important differences were observed in the Ka values of (R)-Am2 and (S)-Am2 for (S,S,S)-1

  通过用适当的手性氨基醇处理2,6-双[[2'6'-双（溴甲基）-4'-甲基苯氧基]甲基]吡啶3来制备基于吡啶的大环化合物。通过UV滴定评估手性有机铵盐对这些带有吡啶基冠型配体的氨基醇亚基的大环的对映体识别。在（S，S，S）-1，（S，S，S）-2和（S，S，S）的（R）-Am2和（S）-Am2的K a值中观察到重要差异。）-3个主机，分别为K S / K R  = 5.0，K S / K R  = 2.4和K S / K R  = 5.0。宿主似乎普遍识别Am1和Am2的（S）-对映异构体。