5,11,17,23,29,35-Hexa-tert-butyl-38,39,40,41,42-pentahydroxy-37-[(4-methoxybenzyl)oxy]calix[6]arene | 140659-21-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23,29,35-Hexa-tert-butyl-38,39,40,41,42-pentahydroxy-37-[(4-methoxybenzyl)oxy]calix[6]arene
• 英文别名: 5,11,17,23,29,35-Hexatert-butyl-42-[(4-methoxyphenyl)methoxy]heptacyclo[31.3.1.13,7.19,13.115,19.121,25.127,31]dotetraconta-1(36),3,5,7(42),9,11,13(41),15,17,19(40),21(39),22,24,27(38),28,30,33(37),34-octadecaene-37,38,39,40,41-pentol
• CAS: 140659-21-8
• 化学式: C₇₄H₉₂O₇
• 分子量: 1093.54
• InChiKey: CHJRFIVAYRYINN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  21.2
• 重原子数：
  81
• 可旋转键数：
  10
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  120
• 氢给体数：
  5
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  4-叔丁基杯[6]芳烃 、 4-甲氧基氯苄 在 sodium hydride 作用下， 生成 5,11,17,23,29,35-Hexa-tert-butyl-38,39,40,41,42-pentahydroxy-37-[(4-methoxybenzyl)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

文献信息

• Calixarenes. 29. Aroylation and arylmethylation of calix[6]arenes
  作者：Suseela Kanamathareddy、C. David Gutsche

  DOI：10.1021/jo00037a037

  日期：1992.5

  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.
• Interplay of Steric Hindrance and Hydrogen Bonding To Restrict Mono-<i>O</i>-substituted <i>p</i>-<i>tert</i>-Butylcalix[6]arenes in Cone Conformation
  作者：J. Oriol Magrans、Ana M. Rincón、Félix Cuevas、Javier López-Prados、Pedro M. Nieto、Miquel Pons、Pilar Prados、Javier de Mendoza

  DOI：10.1021/jo971443x

  日期：1998.2.1

  The simple mono-O-benzyl-p-tert-butylcalix[6]arene (2a) has been reported to display a cone conformation with a slow inversion rate at room temperature. Here, a series of mono-O-substituted p-tert-butylcalix[6]arenes (2a-g, 3-9) has been studied by 2D and variable-temperature NMR spectroscopies. Cone conformations with slow macrocyclic inversion were found for calix[6]arenes whose O-substituent was larger than butyl, whereas freezing of the conformation was observed for substituents larger than benzyl. Steric effects and preservation of the cyclic array of hydrogen bonds are suggested as the main cause for the high inversion barriers.