3,8,13-[D3]Trimethoxy-10,15-dihydro-5H-tribenzo[a,d,g]cyclonenene-2,7,12-triol | 347894-31-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3,8,13-[D3]Trimethoxy-10,15-dihydro-5H-tribenzo[a,d,g]cyclonenene-2,7,12-triol
• 英文别名: 6,13,20-Tris(trideuteriomethoxy)tetracyclo[15.4.0.03,8.010,15]henicosa-1(21),3,5,7,10,12,14,17,19-nonaene-5,12,19-triol；6,13,20-tris(trideuteriomethoxy)tetracyclo[15.4.0.03,8.010,15]henicosa-1(21),3,5,7,10,12,14,17,19-nonaene-5,12,19-triol
• CAS: 347894-31-9
• 化学式: C₂₄H₂₄O₆
• 分子量: 417.38
• InChiKey: WUBWRWRJJNRMPO-GQALSZNTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  88.4
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-[4-(2-[D4]Iodoethoxy)-3-[D3]methoxybenzyloxy]tetrahydropyran 、 3,8,13-[D3]Trimethoxy-10,15-dihydro-5H-tribenzo[a,d,g]cyclonenene-2,7,12-triol 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 以89%的产率得到2,7,12-[D3]Trimethoxy-3,8,13-tris-{2-[2-[D3]methoxy-4-(tetrahydropyran-2-yloxymethyl)phenoxy]-[D4]ethoxy}-10,15-dihydro-5H-tribenzo[a,d,g]cyclononene
  参考文献：
  名称：

  Synthesis of Deuterium-Labeled Cryptophane-A and Investigation of Xe@Cryptophane Complexation Dynamics by 1D-EXSY NMR Experiments

  摘要：

  We present the synthesis of a series of deuterated cryptophanes 2-6 by a slightly modified procedure used for cryptophane-A. We show that for [Xe@cryptophane] complexes the use of variable-temperature one-dimensional 129Xe magnetization transfer (1D-EX-SY) allows the measurement of exchange rates. From these data the decomplexation activation energy Ea has been estimated to be 37.5+/-2 kJ mol(-1). The decomplexation activation enthalpy, deltaH(++) = 35.5+/-2 kJ mol(-1), and entropy, deltaS(++) = -60+/-5 J mol(-1) K(-1), have also been calculated. The calculated negative activation entropy suggests that the activated complex associated with decomplexation is conformationally more strained than the complex in its ground state.

  DOI：

  10.1002/1521-3765(20010401)7:7<1561::aid-chem1561>3.0.co;2-9
• 作为产物：
  描述：

  2,7,12-Tris(allyloxy)-3,8,13-[D3]trimethoxy-10,15-dihydro-5H-tribenzo[a,d,g]cyclononene 在 palladium diacetate 、 二乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.0h， 以67%的产率得到3,8,13-[D3]Trimethoxy-10,15-dihydro-5H-tribenzo[a,d,g]cyclonenene-2,7,12-triol
  参考文献：
  名称：

  Synthesis of Deuterium-Labeled Cryptophane-A and Investigation of Xe@Cryptophane Complexation Dynamics by 1D-EXSY NMR Experiments

  摘要：

  We present the synthesis of a series of deuterated cryptophanes 2-6 by a slightly modified procedure used for cryptophane-A. We show that for [Xe@cryptophane] complexes the use of variable-temperature one-dimensional 129Xe magnetization transfer (1D-EX-SY) allows the measurement of exchange rates. From these data the decomplexation activation energy Ea has been estimated to be 37.5+/-2 kJ mol(-1). The decomplexation activation enthalpy, deltaH(++) = 35.5+/-2 kJ mol(-1), and entropy, deltaS(++) = -60+/-5 J mol(-1) K(-1), have also been calculated. The calculated negative activation entropy suggests that the activated complex associated with decomplexation is conformationally more strained than the complex in its ground state.

  DOI：

  10.1002/1521-3765(20010401)7:7<1561::aid-chem1561>3.0.co;2-9

文献信息

• Synthesis and application of cryptophanol hosts: 129Xe NMR spectroscopy of a deuterium-labeled (Xe)2@bis-cryptophane complex
  作者：Magali Darzac、Thierry Brotin、Laurence Rousset-Arzel、Denis Bouchu、Jean-Pierre Dutasta

  DOI：10.1039/b312979a

  日期：——

  The new bis-cryptophanes 7–9 were prepared from cryptophanols 1–3 and illustrate the synthetic possibilities offered by the latter for the design of new host systems featuring the preparation of large supramolecular receptors and new polycryptophane bio-sensors for NMR imaging. Hosts 1–3 were obtained from the monoprotected cryptophanes 4–6 following a multi-step strategy. The complexation of xenon by the dissymmetrical bis-cryptophane 8 was studied by 129Xe NMR spectroscopy. At low temperature, a strong discrimination (Δδ = 1.16 ppm) of the encapsulated xenon guests inside the two cryptophane cavities was observed. The kinetic parameters for the complexation process were determined from 1D-EXSY 129Xe NMR experiments. The activation energy Ea = 39.0 ± 3 kJ mol−1 and associated parameters ΔH≠ = 37.0 ± 3 kJ mol−1 and ΔS≠ = −46.0 ± 10 kJ mol−1 K−1 are in agreement with the values determined for cryptophane-A and [D27]-cryptophane-A.

  新的双隐酚 7-9 由隐酚 1-3 制备而成，说明后者为设计新的宿主系统提供了合成的可能性，该系统的特点是制备大型超分子受体和用于 NMR 成像的新型聚隐酚生物传感器。宿主 1-3 是通过多步骤策略从单保护的加密货币 4-6 中获得的。通过 129Xe NMR 光谱研究了不对称双隐烷 8 与氙的络合作用。在低温下，观察到两个隐光子空腔内封装的氙客体具有很强的辨别力（Δδ = 1.16 ppm）。络合过程的动力学参数由 1D-EXSY 129Xe NMR 实验确定。活化能 Ea = 39.0 ± 3 kJ mol−1 和相关参数 ΔH≠ = 37.0 ± 3 kJ mol−1 和 ΔS≠ = −46.0 ± 10 kJ mol−1 K−1 与 Cryptophane 确定的值一致A和[D27]-cryptophane-A。
• Cryptophanols, new versatile compounds for the synthesis of functionalized cryptophanes and polycryptophanesElectronic supplementary information (ESI) available: experimental details for compounds 4, 5, 6, 7, 8 and 14. See http://www.rsc.org/suppdata/cc/b1/b109301k/
  作者：Magali Darzac、Thierry Brotin、Denis Bouchu、Jean-Pierre Dutasta

  DOI：10.1039/b109301k

  日期：2002.1.14

  After deprotection with a palladium catalyst, mono-allylated cryptophane-A (1, 2) and cryptophane-E (3) gave the new cryptophanols 4, 5 and 6, respectively, which are important key compounds for the preparation of mono-functionalized cryptophanes as well as for the design of large supramolecular hosts such as the bis-cryptophanes 7 and 8.

  在钯催化剂的作用下进行脱保护处理后，单烯丙基化的隐烷-A（1、2）和隐烷-E（3）分别得到了新的隐烷醇 4、5 和 6，它们是制备单官能化隐烷以及设计双隐烷 7 和 8 等大型超分子宿主的重要关键化合物。
• Synthesis of Deuterium-Labeled Cryptophane-A and Investigation of Xe@Cryptophane Complexation Dynamics by 1D-EXSY NMR Experiments
  作者：Thierry Brotin、Thomas Devic、Anne Lesage、Lyndon Emsley、André Collet

  DOI：10.1002/1521-3765(20010401)7:7<1561::aid-chem1561>3.0.co;2-9

  日期：2001.4.1

  We present the synthesis of a series of deuterated cryptophanes 2-6 by a slightly modified procedure used for cryptophane-A. We show that for [Xe@cryptophane] complexes the use of variable-temperature one-dimensional 129Xe magnetization transfer (1D-EX-SY) allows the measurement of exchange rates. From these data the decomplexation activation energy Ea has been estimated to be 37.5+/-2 kJ mol(-1). The decomplexation activation enthalpy, deltaH(++) = 35.5+/-2 kJ mol(-1), and entropy, deltaS(++) = -60+/-5 J mol(-1) K(-1), have also been calculated. The calculated negative activation entropy suggests that the activated complex associated with decomplexation is conformationally more strained than the complex in its ground state.