(5,11-dibromo-26-ethoxy-27,28-dihydroxy-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3(28),4,6,9,11,13(27),15,17,19(26),21(25),22-dodecaenyl) diethyl phosphate | 212612-18-5

• 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-dibromo-26-ethoxy-27,28-dihydroxy-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3(28),4,6,9,11,13(27),15,17,19(26),21(25),22-dodecaenyl) diethyl phosphate
• CAS: 212612-18-5
• 化学式: C₃₄H₃₅Br₂O₇P
• 分子量: 746.429
• InChiKey: ZZTGICKHUDZKQQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.26
• 重原子数：
  44.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  94.45
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (5,11-dibromo-26-ethoxy-27,28-dihydroxy-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3(28),4,6,9,11,13(27),15,17,19(26),21(25),22-dodecaenyl) diethyl phosphate 在 盐酸 、 lithium hydroxide 作用下， 以60%的产率得到11,17-Dibromo-28-ethoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene-25,26,27-triol
  参考文献：
  名称：

  Inherently chiral calix[4]arenes with asymmetrical superposition of substituents at the lower and the upper rims of macrocycle

  摘要：

  Three types of inherently chiral calix[4]arenes (AAHH(BHBH), AHHH(HBBH) , AAHH(HHBH)) with asymmetrical superposition of ethyl, diethoxyphosphoryl groups at the lower rim of the macrocycle and bromine atoms at the upper rim, have been synthesized. The key steps of the synthesis are O,O'-phosphorotropic rearrangements of 1,3-distally disubstituted calix[4]arenes into 1,2-proximal isomers, regioselective bromination of the upper rim and hydrolytic removing of phosphoryl or benzoyl group from the lower rim. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01246-5
• 作为产物：
  描述：

  25-O-ethyl-26-O-(diethoxyphosphoryl)calix[4]arene 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 丙酮 为溶剂， 反应 12.0h， 以75%的产率得到(5,11-dibromo-26-ethoxy-27,28-dihydroxy-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3(28),4,6,9,11,13(27),15,17,19(26),21(25),22-dodecaenyl) diethyl phosphate
  参考文献：
  名称：

  Inherently chiral calix[4]arenes with asymmetrical superposition of substituents at the lower and the upper rims of macrocycle

  摘要：

  Three types of inherently chiral calix[4]arenes (AAHH(BHBH), AHHH(HBBH) , AAHH(HHBH)) with asymmetrical superposition of ethyl, diethoxyphosphoryl groups at the lower rim of the macrocycle and bromine atoms at the upper rim, have been synthesized. The key steps of the synthesis are O,O'-phosphorotropic rearrangements of 1,3-distally disubstituted calix[4]arenes into 1,2-proximal isomers, regioselective bromination of the upper rim and hydrolytic removing of phosphoryl or benzoyl group from the lower rim. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01246-5

文献信息

• Symmetrical and inherently chiral water-soluble calix[4]arenes bearing dihydroxyphosphoryl groups
  作者：Maxim A. Tairov、Myroslav O. Vysotsky、Olga I. Kalchenko、Vladimir V. Pirozhenko、Vitaly I. Kalchenko

  DOI：10.1039/b110691k

  日期：2002.5.23

  A series of symmetrical and inherently chiral water-soluble calix[4]arenes bearing one, two or four proton-ionisable dihydroxyphosphoryl groups at the narrow rim of the macrocycle has been synthesised by consecutive treatment of appropriate diethoxyphosphoryl derivatives with bromotrimethylsilane and methanol. The calix[4]arene phosphoric acids synthesised possess pKa-values 2.85–3.10 (CH3OH–H2O 70 : 30) and form salts with L-(−)-α-phenylethylamine or (1S,2R)-(+)-ephedrine in methanol solution. The salts of the inherently chiral calixarene phosphoric acids with chiral amines are easily separated into diastereomeric forms by the RP HPLC method on Separon SGX C18 or Partisil 5 ODS 3 achiral columns.

  通过用溴化三甲基硅烷和甲醇连续处理适当的二乙氧基磷衍生物，合成了一系列对称的、固有手性的水溶性钙[4]烯，这些钙[4]烯在大环的窄边上带有一个、两个或四个可质子离子化的二羟基磷基。合成的钙[4]炔磷酸的 pKa 值为 2.85-3.10（CH3OH-H2O 70：30），并在甲醇溶液中与 L-(-)-α-苯乙胺或 (1S,2R)-(+)-麻黄碱形成盐。在 Separon SGX C18 或 Partisil 5 ODS 3 非手性色谱柱上采用 RP HPLC 方法，可以轻松地将固有手性的钙烯烃磷酸盐与手性胺分离成非对映异构体。