6,12,18,24,30-Pentatert-butyl-33,34,35-trihydroxy-2-oxaheptacyclo[26.3.1.11,4.110,14.116,20.122,26.03,8]hexatriaconta-3(8),4,6,10,12,14(35),16(34),17,19,22(33),23,25,28,30-tetradecaen-32-one | 171668-13-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 英文名称: 6,12,18,24,30-Pentatert-butyl-33,34,35-trihydroxy-2-oxaheptacyclo[26.3.1.11,4.110,14.116,20.122,26.03,8]hexatriaconta-3(8),4,6,10,12,14(35),16(34),17,19,22(33),23,25,28,30-tetradecaen-32-one
• CAS: 171668-13-6
• 化学式: C₅₅H₆₈O₅
• 分子量: 809.142
• InChiKey: NFWYQPMIWSUBFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.3
• 重原子数：
  60
• 可旋转键数：
  5
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  87
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6,12,18,24,30-Pentatert-butyl-33,34,35-trihydroxy-2-oxaheptacyclo[26.3.1.11,4.110,14.116,20.122,26.03,8]hexatriaconta-3(8),4,6,10,12,14(35),16(34),17,19,22(33),23,25,28,30-tetradecaen-32-one 在 硫酸 、 氢碘酸 作用下， 以 甲醇 、 Petroleum ether 为溶剂， 反应 3.0h， 生成 5,11,17,23,29-penta-tert-butyl-31-amino-32,33,34,35-tetrahydroxycalix<5>arene
  参考文献：
  名称：

  Selective hydroxyl replacement in calixarenes: amino-, azo-, and xanthenocalixarene derivatives.

  摘要：

  The synthesis of monoamino-, azo-, and xanthenocalixarenes and dehydroxylated calixarenes via condensation, reduction, or rearrangement of monospirodienone calixarene derivatives is described. Mild oxidation of p-tert-butylcalix[5]arene and p-tert-butylcalix[6]arene yielded their corresponding monospirodienone derivatives 4b and 4c. Monospirodienone 4b was characterized by X-ray crystallography. Reaction of 4b with (2,4-dinitrophenyl)hydrazine gave a (dinitrophenyl)azo derivative (8), which by reaction with HI gave the monoaminotetrahydroxycalix[5]arene 10. Reaction of 4b with hydrazine/base yielded in a Wolff-Kishner-type reaction, the monodehydroxylated calix[5]arene 8. Reaction of 4b with a methanolic solution of hydrazine at room temperature yielded a derivative characterized by X-ray crystallography as a system with an azo bridge (15). Spirodienone 4b rearranges in MeOH/H+, yielding the xanthene derivative 16 as the main product, together with the linear pentamer 17. The larger spirodienone 4c rearranges by treatment with MeOH/H+, yielding the xanthenocalix[6]arene 18. X-ray diffraction of a crystal of 18 grown in MeCN shows that in the crystal the molecules form intermolecular hydrogen-bonded dimers in which the two molecules mutually include each other; i.e., one of the protuberances of each molecule is located in the V-shaped cavity of its neighboring molecule. Molecules 16 and 18 represent the first examples of calixarene systems incorporating a xanthene moiety.

  DOI：

  10.1021/ja00143a005
• 作为产物：
  描述：

  4-叔丁基杯[5]芳烃 在 phenyltrimethylammonium tribromide 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以63%的产率得到6,12,18,24,30-Pentatert-butyl-33,34,35-trihydroxy-2-oxaheptacyclo[26.3.1.11,4.110,14.116,20.122,26.03,8]hexatriaconta-3(8),4,6,10,12,14(35),16(34),17,19,22(33),23,25,28,30-tetradecaen-32-one
  参考文献：
  名称：

  Selective hydroxyl replacement in calixarenes: amino-, azo-, and xanthenocalixarene derivatives.

  摘要：

  The synthesis of monoamino-, azo-, and xanthenocalixarenes and dehydroxylated calixarenes via condensation, reduction, or rearrangement of monospirodienone calixarene derivatives is described. Mild oxidation of p-tert-butylcalix[5]arene and p-tert-butylcalix[6]arene yielded their corresponding monospirodienone derivatives 4b and 4c. Monospirodienone 4b was characterized by X-ray crystallography. Reaction of 4b with (2,4-dinitrophenyl)hydrazine gave a (dinitrophenyl)azo derivative (8), which by reaction with HI gave the monoaminotetrahydroxycalix[5]arene 10. Reaction of 4b with hydrazine/base yielded in a Wolff-Kishner-type reaction, the monodehydroxylated calix[5]arene 8. Reaction of 4b with a methanolic solution of hydrazine at room temperature yielded a derivative characterized by X-ray crystallography as a system with an azo bridge (15). Spirodienone 4b rearranges in MeOH/H+, yielding the xanthene derivative 16 as the main product, together with the linear pentamer 17. The larger spirodienone 4c rearranges by treatment with MeOH/H+, yielding the xanthenocalix[6]arene 18. X-ray diffraction of a crystal of 18 grown in MeCN shows that in the crystal the molecules form intermolecular hydrogen-bonded dimers in which the two molecules mutually include each other; i.e., one of the protuberances of each molecule is located in the V-shaped cavity of its neighboring molecule. Molecules 16 and 18 represent the first examples of calixarene systems incorporating a xanthene moiety.

  DOI：

  10.1021/ja00143a005