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... | 161264-20-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 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...
• CAS: 161264-20-6
• 化学式: C₁₄₀H₁₃₀O₂₄
• 分子量: 2196.56
• InChiKey: BKFQXGXPBXFESY-MODZMNTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  29.01
• 重原子数：
  164.0
• 可旋转键数：
  24.0
• 环数：
  28.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  243.52
• 氢给体数：
  2.0
• 氢受体数：
  24.0

反应信息

• 作为反应物：
  描述：

  1,3-丙二醇-二-间-甲苯磺酸盐 、 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... 在 caesium carbonate 作用下， 反应 48.0h， 以46%的产率得到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-2,52:17,29-dimetheno-3,51,16,30-(methynoxypropanoxymetino)-1H,18H,26H,28H,53H,55H-bis[1,3]benzodioxocino[9,8-d:9',8'-d']bis[1,3]
  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：

  在 甲基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 8.0h， 以65%的产率得到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：

  壳内烷基锂的添加和硼烷的还原。

  摘要：

  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

  DOI：

  10.1021/jo026649z

文献信息

• Inner-Phase Reaction Dynamics: The Influence of Hemicarcerand Polarizability and Shape on the Potential Energy Surface of an Inner-Phase Reaction
  作者：Sigifredo Sánchez Carrera、Jean-Luc Kerdelhué、Kevin J. Langenwalter、Neil Brown、Ralf Warmuth

  DOI：10.1002/ejoc.200400578

  日期：2005.6

  absorption spectra. From the red shifts and from plots of the n-π*-excitation energy of the free diazirines against the solvent polarizability P, the inner-phase polarizability was estimated. P ranges from 0.39 to 0.58 and is larger than the polarizabilities of common organic solvents. A comparison of the activation parameters ΔH , TΔS , and ΔG for the diazirine decomposition in the inner phase with those in

  六种苯基二氮丙啶 (2) hemicarceplexes 的热分解和这些 hemicarceplexes 的光谱特性，以及一种螺[环丁苯-1(2H),3'-二氮丙啶] (1) 和一种 p-tolyldiazirine (3) hemicarceplex , 已被研究以确定 hemicarcerand 对内相反应的势能表面的影响。这些半纤维素复合物具有戊基或苯乙基脚基团、三个四亚甲基连接基团，并且一个连接基团X的性质不同如下：1：X=(CH 2 ) 5 ；2: X = (CH 2 ) n (n = 2, 3, 4), (S,S)-CH 2 CH[OC(CH 3 ) O]CHCH 2 和邻-CH 2 C 6 H 4 CH 2 ；3：X = (CH 2 ) 4 。通过MM2力场计算分析了连接基团X对苯基二氮丙啶半复合物结构的影响，并导致内相弯曲的变化，其增加顺序为 (S,S)-CH 2 CH[OC(CH
• Mapping the Potential Energy Surface of the Tolylcarbene Rearrangement in the Inner Phase of a Hemicarcerand
  作者：Jean-Luc Kerdelhué,、Kevin J. Langenwalter、Ralf Warmuth

  DOI：10.1021/ja027831k

  日期：2003.1.1

  Chem. 2002, 67, 2532-2540). The slightly higher inner phase activation free energy of the 3b to 18 rearrangement is explained through steric constraints imposed by the surrounding hemicarcerand on the transition state. The enthalpy-entropy compensation observed for the 3b to 18 rearrangement is discussed and interpreted as a result of a hemicarcerand and solvent reorganization along the reaction coordinate

  在 77 K 下，在 C(6)D(5)CD(3) 中具有四个丁烷-1,4-二氧基连接基团 (5) 的 hemicarcerand 内相中的 p-tolyldiazirine (6) 光解产生 5-methylcycloheptatetraene hemicarceplex 5 环 3b 占 41%，以及由瞬时对甲苯基卡宾 (1b) 插入缩醛 CH 或连接体 CO 键 5 和将 1b 添加到 5 芳基单元产生的内分子反应产物。如果 6 在具有氘化扳手和丁烷-1,4-二氧基连接基团 (d(48)-5) 的 hemicarcerand 内光解，则嵌入的 3b 增加至 67%。如果在 CDCl(3) 中进行光解，则不会形成 Hemicarceplex 5 圆 3b。Incarcated 3b 在无氧的情况下在室温下是稳定的，并通过 1D 和 2D NMR 光谱进行表征。在氧气存在的情况下，3b 定量反应生成甲苯和
• The Room-Temperature Stabilization of Bicyclo[2.2.2]oct-1-ene and Bicyclo[3.2.1]oct-1-ene
  作者：Paul Roach、Ralf Warmuth

  DOI：10.1002/anie.200351120

  日期：2003.7.7