25-propoxy-26,27,28-trihydroxycalix<4>arene | 150112-08-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 25-propoxy-26,27,28-trihydroxycalix<4>arene
• 英文别名: 25,26,27-trihydroxy-28-propoxycalix<4>arene；25,26,27-trishydroxy-28-propoxycalix[4]arene；25,26,27-trihydroxy-28-propoxycalix[4]arene；25,26,27,28-tetrahydroxycalix[4]arene；25,26,27,28-tetrahydroxycalix[4]arene monopropyl ether；25-propyloxy-26,27,28-trihydroxycalix[4]arene；25-propoxy-26,27,28-trihydroxycalix[4]arene；28-Propoxypentacyclo[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-dodecaene-25,26,27-triol
• CAS: 150112-08-6
• 化学式: C₃₁H₃₀O₄
• 分子量: 466.577
• InChiKey: XPVGULJTMAEKPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  35
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  69.9
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  25-propoxy-26,27,28-trihydroxycalix<4>arene 在 吡啶 、 sodium hydride 、 sodium hydroxide 作用下， 以 四氢呋喃 、 乙醇 、 乙腈 、 mineral oil 为溶剂， 反应 38.0h， 生成 25,27-dihydroxy-26,28-dipropoxycalix[4]arene
  参考文献：
  名称：

  25,26-二烷氧基杯[4]芳烃。第1部分：25-烷氧基-26,27-二乙酰氧基路线

  摘要：

  杯[4]亚芳基1，3-二烷基醚的乙酰化得到相应的单乙酸酯。的1 1 H NMR谱分析表明，该产品的烷氧基部分是‘限制旋转’。杯[4]亚芳基单烷基醚与乙酰氯的酰化在不同的反应条件下产生单乙酸酯和/或2,3-二乙酸酯。一个简单的重结晶过程能够以高收率分离出2,3-二乙酸酯。二乙酰化产物的1 H NMR谱表明，这些化合物还具有“旋转受限”的烷氧基部分。在K 2 CO 3存在下作为反应基础，2，3-二乙酸酯的烷基化产生了乙酰基迁移的1，3-二烷氧基衍生物。乙酰迁移化合物的基本水解产生已知的1,3-二烷氧基杯[4]芳烃。在NaH作为反应碱的存在下，在有和没有乙酰基迁移的情况下使2，3-二乙酸酯烷基化。对于高反应性的苄基溴和烯丙基溴，大部分烷基化反应在没有乙酰基迁移的情况下进行。在其他烷基卤化物中，产物是乙酰迁移的1，3-二烷氧基衍生物以及少于未迁移的1，2-二烷氧基衍生物量的四分之一。

  DOI：

  10.1016/j.tet.2011.03.010
• 作为产物：
  描述：

  25,27-dihydroxy-26,28-dipropoxycalix[4]arene 在 碘代三甲硅烷 作用下， 以 氯仿 为溶剂， 反应 18.0h， 生成 25-propoxy-26,27,28-trihydroxycalix<4>arene
  参考文献：
  名称：

  Syntheses and optical resolution of calix[4]arenes with molecular asymmetry. Systematic classification of all possible chiral isomers derivable from calix[4]arene

  摘要：

  All possible chiral isomers that can be derived from calix[4]arene by modification of the OH groups were systematically classified. Molecular asymmetry can be generated not only by different substituents but also by conformational isomerism. The numbers of chiral isomers are 24 for tetra-O-substituted calix[4]arenes, 10 for tri-O-substituted calix[4]arenes, 3 for di-O-substituted calix[4]arenes, and 0 for mono-O-substituted calix[4]arenes. This implies that calix[4]arene is a useful building block for the design of novel asymmetric ring structures. In order to demonstrate asymmetry in these chiral calix[4]arenes, we synthesized several tetra-, tri-, and di-O-substituted calix[4]arenes by using the metal template method, the stepwise synthesis method, the protection-deprotection method, etc., which were developed in efforts directed toward regioselective O-alkylation and control of conformational isomerism in calix[4]arenes. Finally, we succeeded in complete optical resolution of chiral calix[4]arenes by an HPLC method using a chiral-packed column or by the formation of diastereomers with the (-)-menthoxyacetyl group. This article thus contains all of the molecular design concepts, syntheses, and optical resolutions of chiral calix[4]arenes.

  DOI：

  10.1021/ja00063a020

文献信息

• Microwave-assisted synthesis of 1,3-dialkyl ethers of calix[4]arenes: application to the synthesis of cesium selective calix[4]crown-6 ionophores
  作者：Sandip K. Nayak、Manoj K. Choudhary

  DOI：10.1016/j.tetlet.2011.10.142

  日期：2012.1

  phenolic-OH groups of calix[4]arenes with various alkyl halides/tosylates and K2CO3 under microwave irradiation afforded 1,3-dialkoxycalix[4]arenes in their cone conformation only as predominant/sole product in good yields (71–85%). The protocol was found to be much superior to conventional heating both in terms of yield and reaction time. Some of the 1,3-dialkoxycalix[4]arenes were elaborated further

  微波辐射下杯[4]芳烃的苯酚-OH基与各种烷基卤化物/甲苯磺酸酯和K 2 CO 3的部分醚化，仅以主要/单一产物的形式提供1,3-二烷氧基杯[4]芳烃，其圆锥构象仅为高收率（71–85％）。发现该方案在产率和反应时间方面均比常规加热好得多。一些1,3-二烷氧基杯[4]芳烃被进一步精制为铯选择性杯[4]冠6离子载体的合成。
• Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups
  作者：Jonathan Gagnon、Martin Vézina、Marc Drouin、Pierre D Harvey

  DOI：10.1139/v01-161

  日期：2001.10.1

  The regioselective upper-rim functionalization of calix[4]arene have been performed to prepare all the multisubstituted diphenylphosphine derivatives. In addition, the X-ray structures of 5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene and 5,11,17,23-tetrakis(diphenylphosphino)-25,26,27,28-tetra-i-propoxy-calix[4]arene have been determined. Regioselective functionalizations have been achieved using methods that involve appropriate choices of bases, alkyllithium-solvent systems, stoichiometry, and reaction times. A new and convenient method for selectively preparing derivitized calix[4]arenes at proximal positions in relative large scale quantity has been developed and involves a transesterification of the distal diester derivative into the proximal isomer.Key words: calix[4]arenes, phosphine, upper-rim, X-ray structure, transesterification.

  对calix[4]arene的上缘选择性官能化已经进行，以制备所有多取代二苯基膦衍生物。此外，已确定了5,17-二溴-11,23-双(二苯基膦基)-25,26,27,28-四-n-丙氧基calix[4]arene和5,11,17,23-四(二苯基膦基)-25,26,27,28-四异丙氧基calix[4]arene的X射线结构。通过适当选择碱、烷基锂-溶剂系统、化学计量、反应时间等方法实现了选择性官能化。开发了一种新的便捷方法，可在相对较大规模上选择性地制备calix[4]arenes的衍生物，涉及将远端二酯衍生物转酯化为近端异构体。关键词：calix[4]arenes、膦、上缘、X射线结构、转酯化。
• 25‐Propyloxy‐26,27‐dibenzoyloxy‐calix[4]arene as Precursor for the Synthesis of Inherently Chiral Calixarenes
  作者：Oleksandr O. Trybrat、Oleksandr A. Yesypenko、Svitlana V. Shishkina、Eduard B. Rusanov、Yevgen A. Karpichev、Vitaly I. Kalchenko

  DOI：10.1002/ejoc.202100624

  日期：2021.7.26

  25-Propyloxy-26,27-dibenzoyloxy-calix[4]is a convenient precursor for the formation of inherently chiral configuration on the calixarene platform. The synthesis of inherently chiral calixarenes with one, two and three different functional groups on the upper rim was described.

  25-Propyloxy-26,27-dibenzoyloxy-calix[4] 是在杯芳烃平台上形成固有手性构型的方便前体。描述了在上缘具有一个、两个和三个不同官能团的固有手性杯芳烃的合成。
• Synthesis of Lower Rim Polyhydroxylated Calix[4]arenes
  作者：Margarita Segura、Francesco Sansone、Alessandro Casnati、Rocco Ungaro

  DOI：10.1055/s-2001-18065

  日期：——

  Synthesis of Lower Rim Polyhydroxylated Calix[4]arenes Ma g rita Segura,a Francesco Sansone,b Alessandro Casnati,b Rocco Ungaro*b a Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049, Madrid, Spain b Dipartimento di Chimica Organica e Industriale dell’Università, Parco Area delle Scienze 17/A, 43100, Parma, Italy Fax [phone]; E-mail: ungaro@unipr

  下缘多羟基化杯[4]芳烃的合成 Mag rita Segura,a Francesco Sansone,b Alessandro Casnati,b Rocco Ungaro*ba Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049, 马德里, 西班牙 b Dipartimento di Chimica Organica e Industriale dell'Università, Parco Area delle Scienze 17/A, 43100, Parma, Italy 传真 [phone]；电子邮件：[e-mail] 2001 年 6 月 25 日收到；2001 年 8 月 6 日修订
• Design, synthesis and structure determination of new inherently chiral <i>para</i>-bromoalkoxycalix[4]arenes
  作者：Oleksandr A. Yesypenko、Marija A. Klyachina、Maksym V. Dekhtyarenko、Vladimir V. Pirozhenko、Svitlana V. Shishkina、Vyacheslav I. Boyko、Zoia V. Voitenko、Vitaly I. Kalchenko

  DOI：10.1080/10610278.2016.1167210

  日期：2017.1.2

  Abstract The preparative method for the synthesis of inherently chiral para-bromoalkoxycalix[4]arenes based on para-bromination, stepwise regioselective debenzoylation and the following alkylation of the readily available 25-propoxy-26,27-dibenzoyloxycalix[4]arene with propyl bromide or (R)-N-(1-phenylethyl)bromoacetamide has been developed. Three types of the inherently chiral calix[4]arenes in cone

  摘要 基于对溴化、逐步区域选择性脱苯甲酰化和易得的 25-丙氧基-26,27-二苯甲酰氧基杯[4]芳烃与溴化丙烷的后续烷基化，合成固有手性对溴烷氧基杯[4]芳烃的制备方法或 (R)-N-(1-苯乙基) 溴乙酰胺已开发。已经以外消旋、非对映体纯或对映体纯形式获得了三种类型的固有手性杯 [4] 芳烃，它们具有锥形或部分锥形构象，具有不对称（AHHHHBHH、AAHHHBHH、AHBHHCHH）取代上下边缘。它们的结构和绝对构型已通过 NMR 和 X 射线确定。