5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,54-pentahydroxy-53,55,56-trimethoxycalix<8>arene | 156119-00-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,54-pentahydroxy-53,55,56-trimethoxycalix<8>arene
• 英文别名: 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,54-pentahydroxy-53,55,56-trimethoxycalix[8]arene；5,11,17,23,29,35,41,47-Octatert-butyl-53,55,56-trimethoxynonacyclo[43.3.1.13,7.19,13.115,19.121,25.127,31.133,37.139,43]hexapentaconta-1(48),3(56),4,6,9,11,13(55),15,17,19(54),21,23,25(53),27,29,31(52),33,35,37(51),39(50),40,42,45(49),46-tetracosaene-49,50,51,52,54-pentol
• CAS: 156119-00-5
• 化学式: C₉₁H₁₁₈O₈
• 分子量: 1339.93
• InChiKey: NSPLIBAHZLKJFY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  26.9
• 重原子数：
  99
• 可旋转键数：
  11
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  129
• 氢给体数：
  5
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,54-pentahydroxy-53,55,56-trimethoxycalix<8>arene 生成 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52-tetrahydroxy-53,54,55,56-tetramethoxycalix[8]arene
  参考文献：
  名称：

  Neri Placido, Battocolo Enrico, Cunsolo Francesca, Geraci Corrada, Piatte+, J. Org. Chem, 59 (1994) N 14, S 3880-3889

  摘要：

  DOI：
• 作为产物：
  描述：

  4-叔丁基杯[8]芳烃 、 碘甲烷 在 potassium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 以68%的产率得到5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,54-pentahydroxy-53,55,56-trimethoxycalix<8>arene
  参考文献：
  名称：

  Study on the Alkylation of p-tert-Butylcalix[8]arene. Partially O-Alkylated Calix[8]arenes

  摘要：

  Reactions of p-tert-butylcalix[8]arene (1) with various alkylating agents, including para-substituted benzyl bromides, tert-butyl bromoacetate, and 2-chloro-N,N-dimethylacetamide, were carried out in THF-DMF in the presence of a base. With strong bases (Nail or BaO/Ba(OH)(2)) octasubstituted derivatives were obtained, usually in good yield, while in the presence of weak bases (K2CO3 or CsF) more or less complicated reaction mixtures were obtained, wherefrom 1,3,5,7-tetraethers with C-4 symmetry were isolated in yields up to 49%. The eight equivalent ArCH2Ar groups of these compounds give rise to a singlet in the H-1-NMR spectrum, indicating a conformational freedom of the macrocycle, as confirmed by VT-NMR studies. The origin of the 1,3,5,7-regioselectivity can be explained, assuming that alkylation proceeds via a sequence of alternating monodeprotonation and alkylation steps. In each individual monodeprotonation step, those phenoxide monoanions are formed preferentially which are stabilized by two flanking hydrogen bonds. However, this cannot be the whole explanation. In fact, when methyl iodide was used as the electrophile in the reaction with 1, the main products were the 1,2,4-trimethoxy and 1,2,3,4-tetramethoxy derivatives, whereas the 1,3,5,7-tetramethyl ether was not detected in the reaction mixture. This finding leads us to believe that in the reaction with Mel some factor other than stability of oxyanions prevails, possibly the molecular dimension of the electrophile. This seems to be confirmed by the observation that n-butyl iodide, of intermediate dimension between MeI and arylmethyl bromides, gives alkylation products typical of both reaction courses.

  DOI：

  10.1021/jo00093a020

文献信息

• Study on the Alkylation of p-tert-Butylcalix[8]arene. Partially O-Alkylated Calix[8]arenes
  作者：Placido Neri、Enrico Battocolo、Francesca Cunsolo、Corrada Geraci、Mario Piattelli

  DOI：10.1021/jo00093a020

  日期：1994.7

  Reactions of p-tert-butylcalix[8]arene (1) with various alkylating agents, including para-substituted benzyl bromides, tert-butyl bromoacetate, and 2-chloro-N,N-dimethylacetamide, were carried out in THF-DMF in the presence of a base. With strong bases (Nail or BaO/Ba(OH)(2)) octasubstituted derivatives were obtained, usually in good yield, while in the presence of weak bases (K2CO3 or CsF) more or less complicated reaction mixtures were obtained, wherefrom 1,3,5,7-tetraethers with C-4 symmetry were isolated in yields up to 49%. The eight equivalent ArCH2Ar groups of these compounds give rise to a singlet in the H-1-NMR spectrum, indicating a conformational freedom of the macrocycle, as confirmed by VT-NMR studies. The origin of the 1,3,5,7-regioselectivity can be explained, assuming that alkylation proceeds via a sequence of alternating monodeprotonation and alkylation steps. In each individual monodeprotonation step, those phenoxide monoanions are formed preferentially which are stabilized by two flanking hydrogen bonds. However, this cannot be the whole explanation. In fact, when methyl iodide was used as the electrophile in the reaction with 1, the main products were the 1,2,4-trimethoxy and 1,2,3,4-tetramethoxy derivatives, whereas the 1,3,5,7-tetramethyl ether was not detected in the reaction mixture. This finding leads us to believe that in the reaction with Mel some factor other than stability of oxyanions prevails, possibly the molecular dimension of the electrophile. This seems to be confirmed by the observation that n-butyl iodide, of intermediate dimension between MeI and arylmethyl bromides, gives alkylation products typical of both reaction courses.
• Neri Placido, Battocolo Enrico, Cunsolo Francesca, Geraci Corrada, Piatte+, J. Org. Chem, 59 (1994) N 14, S 3880-3889
  作者：Neri Placido, Battocolo Enrico, Cunsolo Francesca, Geraci Corrada, Piatte+

  DOI：——

  日期：——