1,21,23,25-tetrakis(2-phenylethyl)-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5',4'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin-7,11,15,28-tetrol | 121424-78-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 1,21,23,25-tetrakis(2-phenylethyl)-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5',4'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin-7,11,15,28-tetrol
• 英文别名: 5,11,17,23-tetrahydroxy-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetra-(2-phenylethyl)-resorc[4]arene；25,29,33,37-Tetrakis(2-phenylethyl)-2,4,8,10,14,16,20,22-octaoxanonacyclo[21.15.1.124,38.05,36.07,34.011,32.013,30.017,28.019,26]tetraconta-1(39),5,7(34),11,13(30),17(28),18,23,26,31,35,38(40)-dodecaene-6,12,18,39-tetrol
• CAS: 121424-78-0
• 化学式: C₆₄H₅₆O₁₂
• 分子量: 1017.14
• InChiKey: VZEGZBGOBNHOAX-UHFFFAOYSA-N

物化性质

• 密度：
  1.331±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  14.7
• 重原子数：
  76
• 可旋转键数：
  12
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  155
• 氢给体数：
  4
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  白消安 、 1,21,23,25-tetrakis(2-phenylethyl)-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5',4'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin-7,11,15,28-tetrol 在 caesium carbonate 作用下， 以 various solvent(s) 为溶剂， 反应 18.0h， 生成 8,9,10,11,39,40,41,42-octahydro-1,18,26,28,53,55,63,74-octaphenethyl-34,47-(epoxybutanoxy)-20,24:57,61-dimethano-2,52:3,51:16,30;17,29-tetrametheno-1H,18H,26H,28H,53H,55H-bis[1,3]benzodioxocino[9,8-d:9',8'-d']bis[1,3]benzodioxocino...
  参考文献：
  名称：

  Syntheses, Binding Properties, and Structures of Seven New Hemicarcerands Each Composed of Two Bowls Bridged by Three Tetramethylenedioxy Groups and a Fourth Unique Linkage^1,2

  摘要：

  Treatment of 2 mol of the bowl-shaped tetrol 1 (derived originally from resorcinol and dihydrocinnamaldehyde) with 3 mol of Ts(6)(CH2)(4)OTs gave diol 2. Eight compounds with different combinations of bridges were formed from 2 by treatment with Cs2CO3 and the following reagents in the presence of potential guests to give either free or complexed hemicarcerands as follows: ClCH2Br gave 4; TsO(CH2)(2)OTs gave 5; TsO(CH2)(3)OTs gave 6; MsO(CH2)(4)OMs gave 7, a known system; MsO(CH2)(5)OMs gave 8; 2,3-bis(bromomethyl)quinoxaline gave 9; 1,3-(ClCH2)(2)C6H4 gave 10; 2,6-bis(chloromethyl)pyridine gave 11. Thirty-six fully characterized new hemicarceplexes are reported which were prepared either directly from diol 2 by the ''sealing in'' of the guest during introduction of the fourth bridge, or by guest exchange driven by mass law at 25 to 160 degrees C. The guests ranged in size from CHCl3 to 1,2,3-(MeO)(3)C6H3. The incarcerated guests correlated with portal sizes of their hosts. Crystal structures of 8.4-MeC(6)H(4)OMe and 10.CHCl3 were determined. Changes in chemical shifts in H-1 NMR spectra of incarcerated and free guests are interpreted in terms of their locations in the hosts' inner phases. The length and nature of the unique host bridge affects the chemical shifts of the other bridges. Force field calculations of structural models for N-methylpyrrolidinone incarcerated in 4-7 were made. Approximate half-lives for decomplexation were determined for complexes involving the larger hosts and guests. Force-field calculations were made of binding energies and activation energies for decomplexations of models of 7.N-methylpyrrolidinone, 8.N-methylpyrrolidinone, and 10.N-methylpyrrolidinone. The activation energies for decomplexation were dissected into intrinsic and constrictive components.

  DOI：

  10.1021/jo9612786
• 作为产物：
  描述：

  7,11,15,28-tetrabromo-1,21,23,25-tetrakis(2-phenylethyl)-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5',4'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin 在 正丁基锂 、 硼酸三甲酯 、 双氧水 、 sodium hydroxide 作用下， 以 四氢呋喃 、 正己烷 、 水 为溶剂， 以45%的产率得到1,21,23,25-tetrakis(2-phenylethyl)-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5',4'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin-7,11,15,28-tetrol
  参考文献：
  名称：

  微波辅助合成一系列新的间苯二酚[4]芳烃空洞型卟啉胶囊†

  摘要：

  胶囊状分子受体对于生物宿主-客体相互作用（例如酶促过程的特征）建模的基础是至关重要的。半角质型宿主是更加通用和有效的合成受体。在此，我们报道了六种新型间苯二酚[4]芳烃cavitand-封端的合成卟啉胶囊，是一系列新的分子胶囊的模型，这些分子胶囊是由Cram及其同事最初报道的经典半癌的模型制成的。在第一个报道的其在超分子封端的制备中的利用的实例中卟啉在宿主分子中，使用微波（MW）辐射（结合Adler条件）以原位形成卟啉帽。另外，相对于迄今报道的传统回流方案，通过这些条件获得的产率显示出显着的提高。第20–25胶囊无限稳定，我们观察到22和25的胶体具有迄今报道的间苯二酚[4]芳烃空泡封端的最小刚性腔卟啉 宿主分子。

  DOI：

  10.1039/b907547j

文献信息

• A tetrathiol bowl-shaped cavitand and a derived carceplex
  作者：Roger C. Helgeson、Carolyn B. Knobler、Donald J. Cram

  DOI：10.1039/c39950000307

  日期：——

  The syntheses and characterization of tetrathiol bowl 4, its rearranged byproduct 6 and its derived carceplex 7⊙Me2NCOMe·4PhNO2 are reported, and the crystal structure of this carceplex is compared to that of its oxygen analogue, 8⊙Me2NCOMe·5CHCl3.

  报道了四硫醇碗4、其重排副产物6及其衍生卡塞plex 7⊙Me2NCOMe·4PhNO2的合成与表征，并将该卡塞plex的晶体结构与氧类似物8⊊Me2NCOMe·5CHCl3进行了比较。
• Guest-Assisted and Guest-Inhibited Shell Closures Provide Differently Shaped Carceplexes and Hemicarceplexes¹^,²
  作者：Roger C. Helgeson、Kyungsoo Paek、Carolyn B. Knobler、Emily F. Maverick、Donald J. Cram

  DOI：10.1021/ja9602152

  日期：1996.1.1

  The syntheses are reported of ten new carceplexes, hemicarceplexes, or their free hosts by coupling different or similar pairs of cavitands at their rims with four O(CH2)nO or four m-(OCH2)2C6H4 br...

  通过在其边缘与四个 O(CH2)nO 或四个 m-(OCH2)2C6H4 br 偶联不同或相似的空腔对，报告了十个新的 carceplexes、hemicarceplexes 或它们的自由宿主的合成。
• Molecular Engineering. 8.¹ Kinetic and Conformational Studies of Resorcin[4]arene-Based <i>C</i>₄ Tetraoxatetrathiahemicarceplexes:  Carceroisomerism and Twistomerism
  作者：Kyungsoo Paek、Hyejae Ihm、Sunggoo Yun、Hee Cheon Lee、Kyoung Tai No

  DOI：10.1021/jo015594i

  日期：2001.8.1

  kinetic properties, carceroisomerism, and twistomerism were studied by VT, 2D COSY, NOESY, and ROESY (1)H NMR experiments. The decomplexation rates of DMF or DMA were very slow with high activation energy barriers (73 and 104 kJ mol(-1), respectively) and the complexed guests feel more constriction than their free liquid state. The largest isomerization energy barrier of carceroisomers was 15.4 kcal mol(-1)

  合成并表征了新的C（4v）四氧杂四环硫杂半芳香族化合物及其六个包含DMF，DMA，DMSO或NMP的半融合体。通过VT，2D COSY，NOESY和ROESY（1）H NMR实验研究了它们的构象，动力学性质，油溶异构体和扭转异构体。具有高活化能垒（分别为73和104 kJ mol（-1））的DMF或DMA的分解速度非常慢，并且被络合的宾客比自由液体感觉到更多的收缩。异构体的最大异构化能垒为15.4 kcal mol（-1），而异构体的异构化能垒显着大于异构体。
• Synthesis, binding properties and crystal structure of a hemicarcerand containing four pentamethylenedioxy groups spanning two bowls
  作者：Young-Seok Byun、Timothy A. Robbins、Carolyn B. Knobler、Donald J. Cram

  DOI：10.1039/c39950001947

  日期：——

  Hemicarcerand 1, whose synthesis from two tetrol bowls and four pentamethylene ditosylate molecules was templated by veratrole, was found to bind in solution (one-to-one) eighteen different guests; the crystal structure of 1⊙4MeCN is centrosymmetric; hemicarcerand 2, containing four hexamethylenedioxy groups, is also discussed.

  发现Hemicarcerand 1是由Veratrole模板化的，它由两个四醇钵和四个五亚甲基二甲苯磺酸酯分子合成，并在溶液中（一对一）结合18个不同的客人。1⊙4MeCN的晶体结构为中心对称。还讨论了含有四个六亚甲基二氧基的半芳族化合物2。
• Through-Shell Alkyllithium Additions and Borane Reductions
  作者：Ralf Warmuth、Emily F. Maverick、Carolyn B. Knobler、Donald J. Cram

  DOI：10.1021/jo026649z

  日期：2003.3.1

  resonances. In the methyllithium and n-butyllithium addition to 4[symbol: see text]1 and 4[symbol: see text]3 at elevated temperatures, selective cleavage of a host's spanner or tetramethylenedioxy bridge, respectively, was observed. The cleavage of one spanner also took place in the methyllithium addition to the 1-methyl-2-pyrrolidinone hemicarceplex. These scission reactions are initiated by the initially

  据报道，通过苯甲醛（1），苯并环丁烯酮（2）和苯并环丁烯二酮（3）的壳层硼烷还原和甲基锂被嵌在具有四个四亚甲基二氧基桥的半芳烃（4）内。所有客人都可以减少和甲基化。观察到3的选择性单还原和单甲基化。在4 [符号：参见文本] 3的甲基锂中，最初形成的醇锂进行了摩尔重排。被包埋的客体对甲基锂的反应性增加的顺序为1 <2 << 3，对硼烷的反应性的增加顺序为1 << 2大约相等。3在优选的情况下，客体反应性与反应的羰基的内相位置相关客体内相取向。后者是根据4 [符号：参见文字] 1的X射线结构确定的，4 [符号：参见文本] 2和4 [符号：参见文本] 3，是从分子力学计算以及客体质子共振的半癌和高场位移引起的。在升高的温度下，在甲基锂和正丁基锂中除4 [符号：参见文本] 1和4 [符号：参见文本] 3外，分别观察到主体的扳手或四亚甲基二氧基桥的选择性裂解。除1-甲基-2-吡咯烷酮半血纤体外，在甲