6,12,18,24,30,36-Hexatert-butyl-39,40,41,42-tetrahydroxy-2-oxaoctacyclo[32.3.1.11,4.110,14.116,20.122,26.128,32.03,8]tritetraconta-3(8),4,6,10,12,14(42),16,18,20(41),22(40),23,25,28(39),29,31,34,36-heptadecaen-38-one | 171668-14-7

• 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: 6,12,18,24,30,36-Hexatert-butyl-39,40,41,42-tetrahydroxy-2-oxaoctacyclo[32.3.1.11,4.110,14.116,20.122,26.128,32.03,8]tritetraconta-3(8),4,6,10,12,14(42),16,18,20(41),22(40),23,25,28(39),29,31,34,36-heptadecaen-38-one
• CAS: 171668-14-7
• 化学式: C₆₆H₈₂O₆
• 分子量: 971.373
• InChiKey: NGBGUIDVOUASJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.5
• 重原子数：
  72
• 可旋转键数：
  6
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  107
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6,12,18,24,30,36-Hexatert-butyl-39,40,41,42-tetrahydroxy-2-oxaoctacyclo[32.3.1.11,4.110,14.116,20.122,26.128,32.03,8]tritetraconta-3(8),4,6,10,12,14(42),16,18,20(41),22(40),23,25,28(39),29,31,34,36-heptadecaen-38-one 在 三乙基硅烷 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以35%的产率得到5,13,19,25,31,37-Hexatert-butyl-9-oxaoctacyclo[33.3.1.17,11.117,21.123,27.129,33.03,8.010,15]tritetraconta-1(38),3(8),4,6,10(15),11,13,17,19,21(42),23,25,27(41),29(40),30,32,35(39),36-octadecaene-39,40,41,42-tetrol
  参考文献：
  名称：

  在杯芳烃中形成分子内AR--O--AR键。

  摘要：

  通过轻柔地氧化杯芳烃，然后用离子氢化混合物处理所得的单螺二烯酮衍生物（9c），分两步完成对叔丁基杯[6]芳烃的两个邻位苯酚部分的正式脱水反应。 SiH / CF（3）COOH）。9c反应生成未取代的黄嘌呤并[6]亚芳基11d，同时用Et（3）SiH / CF（3）COOH处理球状杯芳烃（13）的单螺二烯酮衍生物，得到二苯并呋喃衍生物15。后一种产物表明，至少对于13，在产物中形成Ar-O-Ar键的环不是在起始材料中通过螺键连接的环。用对甲苯磺酸甲酯/ K（2）CO（3）或硫酸二甲酯/碱将11d的酚羟基甲基化，得到其二甲基和四甲基醚衍生物。母体蒽酮杯[6]芳烃衍生物17b的制备是通过苯酚基团的O-甲基化，然后是吨亚甲基的CrO（3）氧化和OH基团的脱保护。杯黄酮17a的McMurry偶联提供了二x吨18。杯状芳烃11d和15（分别具有x吨和二苯并呋喃基团）在结构上通过X射线晶体学表征。

  DOI：

  10.1021/jo0103468
• 作为产物：
  描述：

  4-叔丁基杯[6]芳烃 在 phenyltrimethylammonium tribromide 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以52%的产率得到6,12,18,24,30,36-Hexatert-butyl-39,40,41,42-tetrahydroxy-2-oxaoctacyclo[32.3.1.11,4.110,14.116,20.122,26.128,32.03,8]tritetraconta-3(8),4,6,10,12,14(42),16,18,20(41),22(40),23,25,28(39),29,31,34,36-heptadecaen-38-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

文献信息

• Selective hydroxyl replacement in calixarenes: amino-, azo-, and xanthenocalixarene derivatives.
  作者：Oleg Aleksiuk、Shmuel Cohen、Silvio E. Biali

  DOI：10.1021/ja00143a005

  日期：1995.9

  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.
• Intramolecular Ar−O−Ar Bond Formation in Calixarenes
  作者：Kasim Agbaria、Silvio E. Biali

  DOI：10.1021/jo0103468

  日期：2001.8.1

  are not those connected by the spiro bond in the starting material. Methylation of the phenolic hydroxyl groups of 11d with methyl p-toluenesulfonate/K(2)CO(3) or dimethyl sulfate/base afforded its dimethyl and tetramethyl ether derivatives. The parent xanthone calix[6]arene derivative 17b was prepared by O-methylation of the phenol groups followed by CrO(3) oxidation of the xanthene methylene group

  通过轻柔地氧化杯芳烃，然后用离子氢化混合物处理所得的单螺二烯酮衍生物（9c），分两步完成对叔丁基杯[6]芳烃的两个邻位苯酚部分的正式脱水反应。 SiH / CF（3）COOH）。9c反应生成未取代的黄嘌呤并[6]亚芳基11d，同时用Et（3）SiH / CF（3）COOH处理球状杯芳烃（13）的单螺二烯酮衍生物，得到二苯并呋喃衍生物15。后一种产物表明，至少对于13，在产物中形成Ar-O-Ar键的环不是在起始材料中通过螺键连接的环。用对甲苯磺酸甲酯/ K（2）CO（3）或硫酸二甲酯/碱将11d的酚羟基甲基化，得到其二甲基和四甲基醚衍生物。母体蒽酮杯[6]芳烃衍生物17b的制备是通过苯酚基团的O-甲基化，然后是吨亚甲基的CrO（3）氧化和OH基团的脱保护。杯黄酮17a的McMurry偶联提供了二x吨18。杯状芳烃11d和15（分别具有x吨和二苯并呋喃基团）在结构上通过X射线晶体学表征。