5,11,17,23,29,35-Hexa-tert-butyl-39,42-dihydroxy-37,38,40,41-tetrakis<(4-nitrobenzoyl)oxy>calix<6>arene | 140175-12-8

• 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: 5,11,17,23,29,35-Hexa-tert-butyl-39,42-dihydroxy-37,38,40,41-tetrakis<(4-nitrobenzoyl)oxy>calix<6>arene
• CAS: 140175-12-8
• 化学式: C₉₄H₉₆N₄O₁₈
• 分子量: 1569.81
• InChiKey: GPDUPOKISNCERJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  21.25
• 重原子数：
  116.0
• 可旋转键数：
  12.0
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  318.22
• 氢给体数：
  2.0
• 氢受体数：
  18.0

反应信息

• 作为反应物：
  描述：

  5,11,17,23,29,35-Hexa-tert-butyl-39,42-dihydroxy-37,38,40,41-tetrakis<(4-nitrobenzoyl)oxy>calix<6>arene 在 三氯化铝 、 苯酚 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以85%的产率得到11,17,29,35-Tetra-tert-butyl-39,42-dihydroxy-37,38,40,41-tetrakis<(4-nitrobenzoyl)oxy>calix<6>arene
  参考文献：
  名称：

  Calixarenes. 29. Aroylation and arylmethylation of calix[6]arenes

  摘要：

  Aroylations and arylmethylations of p-tert-butylcalix[6]arene have been carried out using a variety of parasubstituted aroyl chlorides and arylmethyl halides to determine the effect of para substituents on the structural and/or conformational outcome of the reactions. When an excess of derivatizing agent is used with NaH as the base the products in all cases are the 1,2,4,5-tetrasubstituted compounds in the 1,2,3-alternate conformation. However, with Me3SiOK as the base the products of arylmethylation are the 1,4-diethers. By varying the reaction conditions it is possible in some cases to prepare hexaethers as well as monoethers. By means of H-1 NMR spectral measurements it has been shown that any aroyl moiety or any para-substituted phenylmethyl moiety is large enough to prevent its rotation through the annulus of the calix[6]arene, thus partially, or in some cases completely, freezing the conformation. The unsubstituted benzyl moiety, however, is small enough to pass through the annulus fairly easily, thus allowing complete conformational interconversion to occur. The synthetic utility of these derivatives is adumbrated by the selective de-tert-butylation of a tetraester and the intramolecular bridging of a diether.

  DOI：

  10.1021/jo00037a037
• 作为产物：
  描述：

  4-叔丁基杯[6]芳烃 、 4-硝基苯甲酰氯 在 N-甲基咪唑 作用下， 以 乙腈 为溶剂， 反应 0.5h， 以85%的产率得到5,11,17,23,29,35-Hexa-tert-butyl-39,42-dihydroxy-37,38,40,41-tetrakis<(4-nitrobenzoyl)oxy>calix<6>arene
  参考文献：
  名称：

  Calixarenes. 28. Synthesis, structures, and conformations of aroylates of calix[6]arenes

  摘要：

  A study of the aroylation of calix[6]arenes under a variety of conditions has shown that the reaction often yields the 1,2,4,5-tetraester as a major product but that the outcome is dependent both on the aroylating agent and the calixarene. The best results have been obtained with p-nitrobenzoyl chloride which reacts with p-tert-butylcalix[6]arene (1a) to yield a separable mixture containing ca. 40% tetraester 2a and 30% pentaester 3 when NaH is used as the base or up to 85% of the tetraester when 1-methylimidazole is used as the base. In comparable fashion benzoyl chloride and p-nitrobenzoyl chloride react with la and lb, respectively, to yield the tetraesters 2b and 2c, whereas p-allylcalix[6]arene (1c) reacts under the same conditions to produce the hexaester 6. With limiting amounts of p-nitrobenzoylating agent the diesters 4 and 5 have been isolated in low yields. 3,5-Dinitrobenzoyl chloride gives less satisfactory results, producing mixtures containing six or more eaters from which only small amounts of the 1,2,4,5-tetraester 2d have been isolated. The structure and conformation of the products have been established by elemental analysis, mass spectral measurements, and H-1 NMR techniques. In the case of 2a this includes difference NOE and transient NOE determinations which show that the compound exists in a conformation in which two of the aroylated moieties are canted inward so that their p-tert-butyl groups occupy the two faces of the calix[6]arene cavity, thus self-complexing the compound and preventing intermolecular complexation.

  DOI：

  10.1021/jo00037a036