2-<3-<3-(5-t-butyl-2-hydroxyphenylthio)-5-t-butyl-2-hydroxyphenylthio>-5-t-butyl-2-hydroxyphenylthio>-4-t-butylphenol | 56857-30-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-<3-<3-(5-t-butyl-2-hydroxyphenylthio)-5-t-butyl-2-hydroxyphenylthio>-5-t-butyl-2-hydroxyphenylthio>-4-t-butylphenol
• 英文别名: 4-Tert-butyl-2-[5-tert-butyl-3-(5-tert-butyl-2-hydroxyphenyl)sulfanyl-2-hydroxyphenyl]sulfanyl-6-(5-tert-butyl-2-hydroxyphenyl)sulfanylphenol
• CAS: 56857-30-8
• 化学式: C₄₀H₅₀O₄S₃
• 分子量: 691.033
• InChiKey: MZIBEPKIPNUHKX-UHFFFAOYSA-N

物化性质

• 熔点：
  101.5-103 °C(Solv: hexane (110-54-3))
• 沸点：
  739.4±60.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13.4
• 重原子数：
  47
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  157
• 氢给体数：
  4
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-<3-<3-(5-t-butyl-2-hydroxyphenylthio)-5-t-butyl-2-hydroxyphenylthio>-5-t-butyl-2-hydroxyphenylthio>-4-t-butylphenol 在 二氯化硫 作用下， 以 二氯甲烷 为溶剂， 以4.1%的产率得到4-叔丁基硫杂杯[4]芳烃
  参考文献：
  名称：

  Synthesis and properties of sulfur-bridged analogs of p-tert-Butylcalix[4]arene

  摘要：

  p-tert-Butylcalix[4]arene analogs in which up to four methylene bridges were replaced by sulfur bridge(s) were synthesized. NMR studies indicated that the thiacalixarenes were conformationally much more flexible than the parent calixarene in CDCl3 solution; the flexibility was greater with increasing number of the sulfur bridge. The thiacalixarenes serve as inclusion hosts for some organic compounds, forming 2:1 (host:guest) crystalline complexes in many cases. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00700-x
• 作为产物：
  描述：

  2,2'-thiobis<4-t-butylphenol> 在 二氯化硫 作用下， 以 二氯甲烷 为溶剂， 以51.5%的产率得到2-<3-<3-(5-t-butyl-2-hydroxyphenylthio)-5-t-butyl-2-hydroxyphenylthio>-5-t-butyl-2-hydroxyphenylthio>-4-t-butylphenol
  参考文献：
  名称：

  无环苯酚-甲醛低聚物硫桥类似物的合成及包合物性质

  摘要：

  合成了一系列化合物，其中无环对甲基-和对-丁基苯酚-甲醛四聚体的部分或全部亚甲基桥被硫桥取代。发现虽然硫桥连四聚体与多种有机化合物形成结晶主客体复合物，但它们的包合行为与母体四聚体不同。硫桥的数量和位置，以及四聚体中苯酚的对位取代基，对包合性质有很大影响。硫桥连四聚体 (SSS-a,b) 与苯的复合物的热稳定性，根据它们的热解离速率估计，低于母体四聚体 (CCC-a,b) 的热稳定性。

  DOI：

  10.1246/bcsj.64.576

文献信息

• Breaking thiacalix[4]arene into pieces – a novel synthetic approach to higher calixarenes bearing mixed (–S–, –CH₂–) bridges
  作者：Lukáš Kaiser、Tomáš Landovský、Karolína Salvadori、Václav Eigner、Hana Dvořáková、Pavel Lhoták

  DOI：10.1039/d1ra07464d

  日期：——

  scalable, robust, and straightforward synthesis and enables the preparation of larger calixarenes on a gram scale. As shown by 1H NMR and UV-vis titration experiments, the mixed-bridge calix[7]arene is able to recognize fullerenes C60 and C70, thus showing possible applications of such systems. The structures of the mixed bridge systems were confirmed by single crystal X-ray analysis, and the behavior of novel

  一种在骨架内具有混合（S 和 CH2）桥的杯 [5-7] 芳烃的新方法是基于硫杯 [4] 芳烃单亚砜与 BuLi 的反应，从而以基本定量的收率生成线性酚类四聚体。然后用合适的结构单元将该关键中间体环化，得到大环杯芳烃类似物。与类似系统的传统逐步构建相比，这种基于噻杯芳烃裂解的过程代表了一种可扩展、稳健且直接的合成方法，并且能够以克级制备更大的杯芳烃。如1H NMR和UV-vis滴定实验所示，混合桥杯[7]芳烃能够识别富勒烯C60和C70，从而显示出此类系统的可能应用。
• Sulfonyl-bridged oligo(benzoic acid)s: synthesis, X-ray structures, and properties as metal extractants
  作者：Naoya Morohashi、Kazutoshi Nagata、Tomoko Hayashi、Tetsutaro Hattori

  DOI：10.1007/s10847-012-0283-9

  日期：2014.4

  Sulfonyl-bridged oligo(benzoic acid)s 7 n (n = 2–4) are prepared from the corresponding triflate esters (8 n ) of sulfur-bridged oligophenols by palladium-catalyzed methoxycarbonylation of the triflate moieties, followed by hydrolysis of the resulting methyl esters, and subsequent oxidation of the sulfur bridges. X-ray analysis reveals that dimer 7 2 forms supramolecular zig-zag chains through intermolecular hydrogen bonds between the carboxy groups. As for the crystal of trimer 7 3 , two molecules are associated through two couples of intermolecular hydrogen bonds between terminal and central carboxy groups to form a cyclic dimer, which connects with two adjacent dimers with the remaining carboxy groups to construct an infinite columnar structure. Tetramer 7 4 adopts a monomolecular cyclic structure through intramolecular hydrogen bonds between the terminal carboxy groups, and a molecule connects with each of two adjacent molecules through two couples of intermolecular hydrogen bonds between inner carboxy and sulfonyl groups. Solvent extraction experiments reveal that the oligo(benzoic acid)s exhibit high extractability toward lanthanoid ions (Ln3+); the performance follows the order 7 4  ≈ 7 3  > 7 2 . Moderate extraction selectivity is observed for the extraction of Pr3+, Gd3+, and Yb3+ with 7 2 . X-ray crystallographic analysis of cluster [Tb4L4(H2O)6](Et3NH)4, which was prepared from 7 4 (H4L) and Tb(NO3)3·6H2O in the presence of Et3N, reveals that no sulfonyl oxygens coordinate to the metal centers. This indicates that the high extractability of 7 4 originates from the electron-withdrawing nature of the sulfonyl function, which increases the acidity of two adjacent carboxy groups.

  磺酰桥联的低聚（苯甲酸）7 n（n = 2–4）由相应的三氟甲磺酸酯（8 n ）通过钯催化甲氧基羰基化反应制备，三氟甲磺酸酯部分，然后水解所得的甲基酯，并随后氧化硫桥。X射线分析显示，二聚体7 2通过羧基之间的分子间氢键形成超分子之字形链。至于三聚体7 3的晶体，两个分子通过末端和中央羧基之间的两对分子间氢键结合形成环状二聚体，该二聚体与两个相邻二聚体中的剩余羧基连接，构成无限柱状结构。四聚体7 4通过末端羧基之间的分子内氢键采用单
• Synthesis of hybrid calix[6]arenes having both methylene and epithio bridging groups
  作者：Naoya Morohashi、Tomohiro Ishiwata、Kazuaki Ito、Yoshihiro Ohba

  DOI：10.1016/j.tetlet.2003.11.041

  日期：2004.1

  and tetra-thiacalix[6]arene were obtained by acid-catalyzed condensation of the corresponding tetramer and dimer derivatives of p-tert-butylphenol bridged by methylene or sulfur. Replacement of CH2 by sulfur has significant effect on the properties of calix[6]arene such as the strength of intramolecular hydrogen bonding, inclusion ability toward organic molecules, and conformation properties.

  单- ，三- ，和四-硫杂杯[6]芳烃，借助相应的四聚体酸催化缩合和二聚体衍生物获得p -叔丁基苯酚桥被亚甲基或硫。用硫代替CH 2对杯[6]芳烃的性能有重要影响，例如分子内氢键的强度，对有机分子的包容能力和构象特性。
• Sulfur-bridged Oligo(benzoic acid)s as a Novel Family of Metal Extractants
  作者：Naoya Morohashi、Kazutoshi Nagata、Shinya Tanaka、Yoshihiro Ohba、Tetsutaro Hattori

  DOI：10.1246/cl.2008.1228

  日期：2008.12.5

  Sulfur-bridged phenol dimer and tetramer were converted into corresponding oligo(benzoic acid)s, which have high complexation ability toward lanthanide ions as revealed by solvent extraction study.

  溶剂萃取研究表明，硫桥接酚二聚体和四聚体转化为相应的低聚（苯甲酸），它们对镧系元素离子具有很高的络合能力。
• Synthesis of novel dihydroxydiphosphines and dihydroxydicarboxylic acids having a tetra(thio-1,3-phenylene-2-yl) backbone
  作者：Yuki Akahira、Kazutoshi Nagata、Naoya Morohashi、Tetsutaro Hattori

  DOI：10.1080/10610278.2010.514913

  日期：2011.1.1

  Novel tetradentate PPh2-OH hybrid ligands 5 and CO2H-OH hybrid ligands 6 have been successfully synthesised from tetra(thio-5-tert-butyl-2-hydroxy-1,3-phenylene) (24) by replacing the hydroxy groups at both the 2-position and either the 2'-, 2''- or 2'''-position with diphenylphosphino or carboxy groups, after converting into bistriflates 8; the substitution positions of newly introduced substituents are denoted hereafter by superscript 1,n as 51,n. Bistriflates 81,3 and 81,4 can be readily prepared by the regioselective detriflation of tetrakistriflate 7 with tetrabutylammonium fluoride (TBAF), conducted under different conditions. On the other hand, the preparation of bistriflate 81,2 requires a four-step process through protection/deprotection. Thus, the silylation of tetraol 24 with an excess of 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane gives O,O'- and O'',O'''-disiloxane-1,3-diyl-capped derivative 9. One of the two disiloxane bridges is removed by the treatment with 0.5mol equiv. of TBAF to give diol 10. Triflation of diol 10, followed by the removal of the remaining disiloxane bridge, affords bistriflate 81,2. Bistriflates 8 are subjected to palladium-catalysed phosphorylation, followed by the reduction of the resulting phosphine oxide 121,n to give PPh2-OH hybrid ligands 51,n (n=2-4), while CO2H-OH hybrid ligands 61,n (n=3,4) are obtained from 8 via acetylation of the remaining hydroxy groups, followed by palladium-catalysed methoxycarbonylation of the TfO moieties, and subsequent hydrolysis of the resulting tetraesters 14. X-ray structural analyses of dicarboxylic acids 61,3 and 61,4 reveal that they form quite different 3D network structures to each other. Interestingly, 61,4 constructs a porous channel with a potential for serving as a supramolecular host, by the stacking of its cyclic dimer that is formed by intermolecular hydrogen bondings between the carboxy groups.