5,11,17,23,29-penta-tert-butyl-31-amino-32,33,34,35-tetrahydroxycalix<5>arene | 171668-16-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,11,17,23,29-penta-tert-butyl-31-amino-32,33,34,35-tetrahydroxycalix<5>arene
• 英文别名: 35-Amino-5,11,17,23,29-pentatert-butylhexacyclo[25.3.1.13,7.19,13.115,19.121,25]pentatriaconta-1(31),3,5,7(35),9(34),10,12,15(33),16,18,21,23,25(32),27,29-pentadecaene-31,32,33,34-tetrol
• CAS: 171668-16-9
• 化学式: C₅₅H₇₁NO₄
• 分子量: 810.173
• InChiKey: BEXXMHABMVZUGP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.9
• 重原子数：
  60
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  107
• 氢给体数：
  5
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5,11,17,23,29-penta-tert-butyl-31-amino-32,33,34,35-tetrahydroxycalix<5>arene 在 盐酸 、 亚硝酸异戊酯 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以71%的产率得到5,11,17,23,29-Pentatert-butyl-32,33,34,35-tetrahydroxyhexacyclo[25.3.1.13,7.19,13.115,19.121,25]pentatriaconta-1(30),3(35),4,6,9(34),10,12,15,17,19(33),21,23,25(32),27(31),28-pentadecaene-31-diazonium;chloride
  参考文献：
  名称：

  Preparation and Conformation of Monohalotetrahydroxycalix[5]arenes

  摘要：

  The intraannular introduction of a halogen into a calixarene skeleton is described. Monoaminotetrahydroxy-p-tert-butylcalix[5]arene (2b) was diazotized by treatment with isoamyl nitrite/HCl/EtOH. Thermal dediazoniation of the salt in chloroform yielded monochlorotetrahydroxy-p-tert-butylcalix [5]arene (5a) and the xanthenocalix[5]arene 6. These products result from the capture of an intermediate phenyl cation derivative by chloride ion or intramolecularly, by a neighboring phenol ring. The product ratio 6:5a was not affected by the addition of excess external chloride, suggesting that the reacting intermediate exists as an ion pair. The dediazoniation reaction in the presence of bromide and iodide ions afforded the corresponding halocalixarenes 5b and 5c, while in the presence of a fluoride ion the calixindazole 8 was obtained. X-ray diffraction indicates that 5b exists in a distorted cone conformation (cone-in) in which the extraannular edge of the halophenyl ring is tilted toward the cavity center. The halocalixarenes undergo a cone-to-cone inversion process with a barrier in the 11.3-12.5 kcal mol(-1) range in CDCl3. The barrier height is a function of the size of the halo substituent. Xanthenocalix[5]arene 6 crystallizes with three ethanol solvent molecules and exists in a cone-like conformation.

  DOI：

  10.1021/jo9611428
• 作为产物：
  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