1,11-bis(3-iodophenoxy)-3,6,9-trioxaundecane | 550297-47-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1,11-bis(3-iodophenoxy)-3,6,9-trioxaundecane
• 英文别名: 1-iodo-3-[2-[2-[2-[2-(3-iodophenoxy)ethoxy]ethoxy]ethoxy]ethoxy]benzene
• CAS: 550297-47-7
• 化学式: C₂₀H₂₄I₂O₅
• 分子量: 598.217
• InChiKey: TXFOBFBEDUUHII-UHFFFAOYSA-N

物化性质

• 沸点：
  571.8±50.0 °C(Predicted)
• 密度：
  1.658±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  27.0
• 可旋转键数：
  14.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  1,11-bis(3-iodophenoxy)-3,6,9-trioxaundecane 在 copper(l) iodide 、 sodium azide 、 copper(II) sulfate 、 sodium ascorbate 、 N,N'-二甲基乙二胺 、 三[(1-苄基-1H-1,2,3-三唑-4-基)甲基]胺 作用下， 以 四氢呋喃 、 乙醇 、 水 、 叔丁醇 为溶剂， 反应 21.0h， 生成 8-Tert-butyl-20,23,26,29,32-pentaoxa-2,3,4,12,13,14-hexazahexacyclo[31.3.1.12,5.16,10.111,14.115,19]hentetraconta-1(37),3,5(41),6(40),7,9,11(39),12,15(38),16,18,33,35-tridecaene
  参考文献：
  名称：

  Electrostatic and Allosteric Cooperativity in Ion-Pair Binding: A Quantitative and Coupled Experiment–Theory Study with Aryl–Triazole–Ether Macrocycles

  摘要：

  Cooperative binding of ion pairs to receptors is crucial for the manipulation of salts, but a comprehensive understanding of cooperativity has been elusive. To this end, we combine experiment and theory to quantify ion-pair binding and to separate allostery from electrostatics to understand their relative contributions. We designed aryl-triazole-ether macrocycles (MC) to be semiflexible, which allows ion pairs (NaX; X = anion) to make contact, and to be monocyclic to simplify analyses. A multiequilibrium model allows us to quantify, for the first time, the experimental cooperativity, alpha, for the equilibrium MC center dot Na+ + MC center dot X- (sic) MC center dot NaX + MC, which is associated with contact ion-pair binding of NaI (alpha = 1300, Delta G(alpha) = -18 kJ mol(-1)) and NaClO4 (alpha = 400, Delta G(alpha) = -15 kJ mol(-1)) in 4:1 dichloromethane-acetonitrile. We used accurate energies from density functional theory to deconvolute how the electrostatic effects and the allosteric changes in receptor geometry individually contribute to cooperativity. Computations, using a continuum solvation model (dichloromethane), show that allostery contributes similar to 30% to overall positive cooperativity. The calculated trend of electrostatic cooperativity using pairs of spherical ions (NaCl > NaBr > NaI) correlates to experimental observations (NaI > NaClO4). We show that intrinsic ionic size, which dictates charge separation distance in contact ion pairs, controls electrostatic cooperativity. This finding supports the design principle that semiflexible receptors can facilitate optimal electrostatic cooperativity. While Coulombs law predicts the size-dependent trend, it overestimates electrostatic cooperativity; we suggest that binding of the individual anion and cation to their respective binding sites dilutes their effective charge. This comprehensive understanding is critical for rational designs of ion-pair receptors for the manipulation of salts.

  DOI：

  10.1021/jacs.5b05839
• 作为产物：
  描述：

  四乙二醇二对甲苯磺酸酯 、 3-碘苯酚 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 12.5h， 以83%的产率得到1,11-bis(3-iodophenoxy)-3,6,9-trioxaundecane
  参考文献：
  名称：

  Electrostatic and Allosteric Cooperativity in Ion-Pair Binding: A Quantitative and Coupled Experiment–Theory Study with Aryl–Triazole–Ether Macrocycles

  摘要：

  Cooperative binding of ion pairs to receptors is crucial for the manipulation of salts, but a comprehensive understanding of cooperativity has been elusive. To this end, we combine experiment and theory to quantify ion-pair binding and to separate allostery from electrostatics to understand their relative contributions. We designed aryl-triazole-ether macrocycles (MC) to be semiflexible, which allows ion pairs (NaX; X = anion) to make contact, and to be monocyclic to simplify analyses. A multiequilibrium model allows us to quantify, for the first time, the experimental cooperativity, alpha, for the equilibrium MC center dot Na+ + MC center dot X- (sic) MC center dot NaX + MC, which is associated with contact ion-pair binding of NaI (alpha = 1300, Delta G(alpha) = -18 kJ mol(-1)) and NaClO4 (alpha = 400, Delta G(alpha) = -15 kJ mol(-1)) in 4:1 dichloromethane-acetonitrile. We used accurate energies from density functional theory to deconvolute how the electrostatic effects and the allosteric changes in receptor geometry individually contribute to cooperativity. Computations, using a continuum solvation model (dichloromethane), show that allostery contributes similar to 30% to overall positive cooperativity. The calculated trend of electrostatic cooperativity using pairs of spherical ions (NaCl > NaBr > NaI) correlates to experimental observations (NaI > NaClO4). We show that intrinsic ionic size, which dictates charge separation distance in contact ion pairs, controls electrostatic cooperativity. This finding supports the design principle that semiflexible receptors can facilitate optimal electrostatic cooperativity. While Coulombs law predicts the size-dependent trend, it overestimates electrostatic cooperativity; we suggest that binding of the individual anion and cation to their respective binding sites dilutes their effective charge. This comprehensive understanding is critical for rational designs of ion-pair receptors for the manipulation of salts.

  DOI：

  10.1021/jacs.5b05839

文献信息

• Cyclization of Dinuclear Aryl- and Aroylpalladium Complexes with the Metal Centers Tethered by an Oligo(ethylene oxide) Chain. Intramolecular Transmetalation of the Cationic Dinuclear Arylpalladium Complexes
  作者：Yuji Suzaki、Kohtaro Osakada

  DOI：10.1021/om030035i

  日期：2003.5.1

  The reaction of the dinuclear palladium(II) complexes [(bpy)(I)PdC6H4(OCH2CH2)0.5n+0.5}]2O (n = 3, 5) and [(bpy)(I)PdCOC6H4(OCH2CH2)2}]2O with AgBF4 produces crown ethers including a biphenylene or diaryl ketone part via intramolecular transfer of the aryl ligand and subsequent reductive elimination of the macrocyclic products.

  双核钯（II）络合物[（bpy）（I）Pd C 6 H 4（OCH 2 CH 2）0.5 n +0.5 }] 2 O（n = 3，5）和[（bpy）（ I）Pd COC 6 H 4（OCH 2 CH 2）2 }] 2 O与AgBF 4通过芳基配体的分子内转移和随后的大环产物还原消除，产生包括联苯或二芳基酮部分的冠醚。