5,11,17,23-tetra-t-butyl-25,26,27,28-tetraethoxycalix<4>arene | 85694-21-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,11,17,23-tetra-t-butyl-25,26,27,28-tetraethoxycalix<4>arene
• 英文别名: 5,11,17,23-Tetratert-butyl-25,26,27,28-tetraethoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene
• CAS: 85694-21-9
• 化学式: C₅₂H₇₂O₄
• 分子量: 761.141
• InChiKey: GOPRRLLXIUKTHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.7
• 重原子数：
  56
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetraethoxycalix<4>arene 在 碘代三甲硅烷 作用下， 以 氯仿 为溶剂， 反应 3.0h， 生成 28-ethoxy-p-tert-butylcalix<4>arene
  参考文献：
  名称：

  杯[4]芳烃单烷基醚的一般合成

  摘要：

  通过用等量的碘代甲基甲基硅烷在CHCl 3中处理易得的-（2）或二烷基醚（3），已经开发了一种首先通用且高收率合成杯[4]芳烃单烷基醚（4）的方法。

  DOI：

  10.1016/s0040-4020(01)96132-0
• 作为产物：
  描述：

  25,27-anti-5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-diethoxy-26,28-bis(phenylmethoxy)pentacyclo<19.3.1.1^3,7.1^9,13.1^15,19>octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene 在 Me₂SiBr 、 potassium tert-butylate 作用下， 以 氯仿 为溶剂， 反应 4.5h， 生成 5,11,17,23-tetra-t-butyl-25,26,27,28-tetraethoxycalix<4>arene
  参考文献：
  名称：

  Groenen, Leo C.; Van Loon, Jan-Dirk; Verboom, Willem, Journal of the American Chemical Society, 1991, vol. 113, # 7, p. 2385 - 2392

  摘要：

  DOI：

文献信息

• An easy access to tetra-o-alkylated calix[4]arenes of cone conformation
  作者：István Bitter、Alajos Grün、Béla Ágai、László Tôke

  DOI：10.1016/0040-4020(95)00401-s

  日期：1995.7

  Fully O-alkylated calix[4]arenes have been synthesized by the alkylation of p-tertbutylcalix[4]arene and its 1,3-dialkylated derivatives in liquid-liquid phase-transfer catalytic process. 1H4 and 1H2R2 could effeciently be deprotonated by aqueous NaOH (50% w/w)-toluene system and alkylated with alkyl (aralkyl, allyl) halogens in good yields affording calix[4]arene tetraethers of cone conformation.

  通过对-叔丁基杯[4]芳烃及其1,3-二烷基化衍生物在液-液相转移催化过程中的烷基化反应，可以合成出完全O-烷基化的杯[4]芳烃。1H 4和1H 2 R 2可以用NaOH（50％w / w）甲苯水溶液有效地去质子化，并用烷基（芳烷基，烯丙基）卤素进行烷基化，收率很高，得到圆锥构象的杯[4]芳烃四醚。
• Calixarenes 9
  作者：C.David Gutsche、Balram Dhawan、Jeffrey A. Levine、Kwang Hyun No、Lorenz J. Bauer

  DOI：10.1016/s0040-4020(01)88541-0

  日期：1983.1

  Calix[4]arene (1A), p-t-butylcalix[4]arene (1B), and p-allylcalix[4]arene (1C) have been converted to various derivatives, including the methyl, ethyl, allyl, benzyl and trimethylsilyl ethers and the acetates. Although the parent calixarenes exist preferentially in the cone conformation, they are conformationally flexible and at room temperature interconvert at a rate of ca 100 sec−1. All but the methyl

  杯[4]芳烃（1A），对叔丁基杯[4]芳烃（1B）和对-烯丙基[4]芳烃（1C）已转化为各种衍生物，包括甲基，乙基，烯丙基，苄基和三甲基甲硅烷基醚和乙酸酯。尽管亲本杯芳烃优先存在于圆锥构象中，但它们构象灵活，并且在室温下以约100 sec -1的速率相互转化。另一方面，除甲基醚外，所有醚在室温下均呈构象刚性。在大多数情况下，优选的构型是视锥和部分视锥，这取决于形成的衍生物（即甲基和乙基醚偏爱部分视锥；苄基和三甲基甲硅烷基醚偏爱视锥）。在烯丙基醚和乙酸酯的情况下，对位取代基似乎会影响构象结果（即1A和1B分别形成部分圆锥和圆锥构象的烯丙基醚；1A和1B分别形成1,3-交替和部分圆锥构象的乙酸盐）。圆锥和部分圆锥构象中的构象刚性杯芳烃衍生物属于一小组合成化合物，这些化合物包含一个永久性空腔（“不变杯”），该空腔的大小足以包封其他分子。
• Conformations and structures of tetra-O-alkyl-p-tert-butylcalix[4]arenes. How is the conformation of calix[4]arenes immobilized?
  作者：Koji Iwamoto、Koji Araki、Seiji Shinkai

  DOI：10.1021/jo00016a027

  日期：1991.8

  p-tert-Butylcalix[4]arene (1H4) was tetra-O-alkylated with alkyl halogens (RX: R = Me, Et, n-Pr, and n-Bu) in the presence of NaH as base, and the products (1R4) were analyzed by HPLC and H-1 NMR spectroscopy. It was found that (i) ring inversion is suppressed by R greater Et, (ii) the final conformer distribution in 1Pr4 and 1Bu4 is governed by the kinetic control, the main products being ''cone'' and ''partial cone'' (approximately in a 1:1 ratio), (iii) 1 Me4 mostly exists as a thermodynamically stable partial-cone conformer, and (iv) 1Et4 shows an intermediary behavior between 1Me4 and 1Pr4: it mostly exists as a partial-cone conformer but slowly isomerizes to a ''1,2-alternate'' conformer at high temperature. The X-ray crystallographic analysis of partial-cone-1Et4 was investigated. To clarify where and how the conformation of 1R4 is immobilized, we alkylated 1H4 in a stepwise manner. It was shown that when NaH is used as base, the conformation of 1Et4 is determined at the fourth ethylation step (1HEt3 --> 1Et4), whereas the conformation of 1Pr4 is determined at the third propylation step (1H2Pr2 --> 1HPr3). The conformer distribution was significantly affected by alkali and alkaline earth metal cations used as base; in particular, it is worthy of mentioning that (i) when Cs2CO3 is used as base, 1,2-alternate-1Pr4 is formed in addition to partial-cone-1Pr4 and (ii) when Ba(OH)2 is used as base, cone-1Pr4 is yielded in 100% selectivity. On the basis of these studies, we discuss how the conformation of calix[4]arenes is immobilized.
• Araki, Koji; Iwamoto, Koji; Shinkai, Seiji, Chemistry Letters, 1989, p. 1747 - 1750
  作者：Araki, Koji、Iwamoto, Koji、Shinkai, Seiji、Matsuda, Tsutomu

  DOI：——

  日期：——
• syn-1,2-dialkylated calix[4]arenes : general intermediates in the NaH/DMF tetraalkylation of calix[4]arenes
  作者：Leo C. Groenen、Bianca H.M. Ruël、Alessandro Casnati、Peter Timmerman、Willem Verboom、Sybolt Harkema、Andrea Pochini、Rocco Ungaro、David N. Reinhoudt

  DOI：10.1016/s0040-4039(00)78816-2

  日期：1991.6

  In DMF or acetonitrile with NaH as a base at room temperature the tetraalkylation of calix[4]arenes 1a and 1b proceeds via the syn-1,2-disubstituted products to the tetraalkylated calix[4]arenes in the cone conformation. With KH as a base the tetraalkylated calix[4]arenes are predominantly formed in the partial cone conformation, and the reaction proceeds via both the syn-1,3-di and the syn-1,2-disubstituted products. Also the solvent influences the pathway via which tetraalkylation takes place. The syn-1,2-disubstituted calix[4]arenes 2-6 can be isolated in 15-55 % from the NaH/DMF or MeCN reactions when only 2.2 equiv of the electrophile are used.