25-O-ethyl-27-O-(diethoxyphosphoryl)calix[4]arene | 212612-16-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 25-O-ethyl-27-O-(diethoxyphosphoryl)calix[4]arene
• 英文别名: (27-Ethoxy-26,28-dihydroxy-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaenyl) diethyl phosphate
• CAS: 212612-16-3
• 化学式: C₃₄H₃₇O₇P
• 分子量: 588.637
• InChiKey: AYAKMQZSWFERNT-UHFFFAOYSA-N

物化性质

• 熔点：
  172-175°C
• 稳定性/保质期：

  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  42
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  94.4
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  25-O-ethyl-27-O-(diethoxyphosphoryl)calix[4]arene 在 盐酸 、 lithium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 作用下， 以 丙酮 为溶剂， 反应 96.0h， 生成 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：

  氯磷酸二乙酯 、 25-乙氧基杯[4]芳香烃 在 三乙胺 作用下， 以 氯仿 为溶剂， 反应 6.0h， 以72%的产率得到25-O-ethyl-27-O-(diethoxyphosphoryl)calix[4]arene
  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

• Inherently Chiral Phosphoruscontaining Calix[4]Arenes
  作者：Leonid N. Markovsky、Miroslav A. Vysotsky、Maxim A. Tairov、Vitaly I. Kalchenko

  DOI：10.1080/10426509908546189

  日期：1999.1.1

  Inherently chiral phosphoruscontaining calix[4]arenes with asymmetrical placement of substituents at the macrocyclic lower rim (phenolic oxygen atoms) as well as with asymmetrical superposition of substituents at the upper rim (para-positions of benzene rings) and at the lower rim have been synthesized. The key steps of the synthesis are O,O-phosphorotropic rearrangements of 1,3-distally disubstituted

  固有的手性含磷杯[4]芳烃在大环下缘（酚氧原子）的取代基不对称放置以及上缘（苯环的对位）和下缘的取代基不对称叠加已被发现合成的。合成的关键步骤是由强碱诱导的 1,3- 远端双取代杯 [4] 芳烃的 O,O-磷向重排成 1,2- 近端异构体。
• 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。