2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-bromo-5-iodobenzoate | 223774-17-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-bromo-5-iodobenzoate
• CAS: 223774-17-2
• 化学式: C₁₄H₁₈BrIO₅
• 分子量: 473.102
• InChiKey: QWFJVYHMXSOPNC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-bromo-5-iodobenzoate 在 三乙胺 copper(l) iodide 、 tris(dibenzylideneacetone)dipalladium (0) 、 四丁基氟化铵 、 溶剂黄146 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 2-(2-(2-methoxyethoxy)ethoxy)ethyl 3,5-diethynylbenzoate
  参考文献：
  名称：

  Arylene Ethynylene Macrocycles Prepared by Precipitation-Driven Alkyne Metathesis

  摘要：

  A convenient, multigram-scale synthesis of arylene ethynylene macrocycles near room temperature is described. Driven by the precipitation of a diarylacetylene byproduct, alkyne metathesis produces the desired macrocycles in one step from monomers in high yields.

  DOI：

  10.1021/ja046531v
• 作为产物：
  描述：

  三甘醇单甲醚 、 3-溴-5-碘苯甲酸 在 氯化亚砜 、 三乙胺 作用下， 以 甲苯 、 四氢呋喃 为溶剂， 反应 14.0h， 以78%的产率得到2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-bromo-5-iodobenzoate
  参考文献：
  名称：

  Photofoldamers 的变构控制以在阴离子调节和双到单螺旋转换之间进行选择

  摘要：

  蛋白质结构和功能的变构调节是生物学的一个标志。蛋白质样非生物折叠体的结构受到变构控制，然而，对其功能的调节很少见。在发现小阴离子和大阴离子分别在单螺旋结构和双螺旋结构之间进行选择之后，我们使用光敏折叠体报告了这种行为。相应地，这些阴离子激活了折叠器中的不同功能；小阴离子开启阴离子浓度的光调节，而大阴离子开启四级结构的手性转换。在这个演示中，我们使用了基于芳基三唑的光折叠体，其中偶氮苯的光驱动反顺式异构化改变了链内 π-π 接触，而三唑定义了变构阴离子结合位点。对与 11 个不断增大的阴离子的结合进行量化（Cl-、Br-、NO2-、I-、NO3-、SCN-、BF4-、ClO4-、ReO4-、PF6-、SbF6-）。与单螺旋会扩展以容纳越来越大的客体的预期相反，这种行为只发生在较小的阴离子（Cl- 到 NO3-；<45 Å3），超过此较大的阴离子形成双螺旋（SCN- 到 SbF6-；>45 Å

  DOI：

  10.1021/jacs.8b10538

文献信息

• Solid-Phase Synthesis of <i>m</i>-Phenylene Ethynylene Heterosequence Oligomers
  作者：Erin L. Elliott、Christian R. Ray、Stefan Kraft、Joseph R. Atkins、Jeffrey S. Moore

  DOI：10.1021/jo0607212

  日期：2006.7.1

  Both homo- and heterosequence m-phenylene ethynylene oligomers are synthesized using a conceptually simple iterative solid-phase strategy. Oligomers are attached to Merrifield's resin through a known triazene-type linkage. The phenylene ethynylene molecular backbone is constructed through a series of palladium-mediated cross-coupling reactions. The strategy employs two types of monomers that bear orthogonal reactivity, one being a monoprotected bisethynyl arene and the other being a 3-bromo-5-iodo arene. The catalyst conditions are tailored to the requirements of each monomer type. The monoprotected bisethynyl arene is coupled to the growing chain in 2 h at room temperature using a Pd(I) dimer precatalyst ((Bu3P)-Bu-t-(Pd(mu-Cl)(mu-2-methyl allyl) Pd)(PBu3)-Bu-t) in conjunction with ZnBr2 and diisopropylamine. In alternate steps, the resin is deprotected in situ with TBAF and coupled to the 3-bromo-5-iodo arene using the iodo selective Pd(tri-2-furylphosphine) 4 catalyst in conjunction with CuI and piperidine; this reaction is also completed in 2 h at room temperature. These cross-coupling events are alternated until an oligomer of the desired length is achieved. The oligomer is then cleaved from the resin using CH2I2/I-2 at 110 degrees C and purified using preparatory GPC. Using this method, a series of homo- and heterosequence oligomers up to 12 units in length in excellent yield and purity were synthesized on the 100 mg scale. Longer oligomers were attempted; however, deletion sequences were found in oligomers longer than 12 units.
• Supramolecular Chelation Based on Folding
  作者：Matthew T. Stone、Jeffrey S. Moore

  DOI：10.1021/ja050713n

  日期：2005.4.1

  Crystallographic analysis revealed that pyricline-palladium complexation is a good geometric match to the m-phenylene ethynylene (mPE) repeat unit and thus could serve as a reversible linking group to join oligomer segments together. A series of pyricline-terminated mPE oligomers were then synthesized and found to coordinate with palladium dichloride to give complexes effectively twice the length of the free oligomers. A quantitative analysis of these coordination equilibria by isothermal calorimetry found the ability of the pyricline end-group to form a coordination complex corresponded with their ability to fold. Oligomers that were able to form complexes of sufficient length to fold showed positive cooperativity based on experimental determination of their association constants with a palladium ion. We suggest that the additional free energy of complexation for the folded oligomers is analogous to chelation by multidentate ligands, but here the "multidentate ligand" is held together by supramolecular rather than covalent bonds.
• The Size-Selective Synthesis of Folded Oligomers by Dynamic Templation
  作者：Tohru Nishinaga、Aya Tanatani、Keunchan Oh、Jeffrey S. Moore

  DOI：10.1021/ja025698q

  日期：2002.5.1

  A dynamic pool of m-phenylene ethynylene oligomers generated by sequence ligation using the imine metathesis reaction was equilibrated under a variety of conditions, and the mixture of products was analyzed by HPLC. The equilibration was performed in the presence and absence of rodlike ligand 2b, which exhibits an affinity for the helical oligomers that is very length specific. Among the eight oligomers generated during metathesis equilibrium, the formation of 22-mer 6b was enhanced in acetonitrile in the presence of 2b. This particular oligomer has the highest binding affinity for 2b. Quantitative analysis by HPLC of the products indicated that 6b was produced in 66% yield in the presence of 2 equiv 2b while a 37% yield was produced in the absence of 2b. Judging from the binding affinities of oligomers 6 with 2b, the equilibrium shifting was driven by the selective binding of 6b with 2b.
• Helical Pitch of <i>m</i>-Phenylene Ethynylene Foldamers by Double Spin Labeling
  作者：Kenji Matsuda、Matthew T. Stone、Jeffrey S. Moore

  DOI：10.1021/ja027437m

  日期：2002.10.1

  To investigate the helical conformation of oligo(m-phenylene ethynylene)s, a pair of TEMPO spin labels were appended to the backbone. The two TEMPO radicals were separated by the four, five, and six repeating units. ESR spectra of the labeled oligomers were measured in chloroform and in ethyl acetate solvents in which the oligomers are disordered and folded, respectively. The measurement and analysis of ESR spectra revealed that six repeating units make one helical turn.
• Reversible Polymerization Driven by Folding
  作者：Dahui Zhao、Jeffrey S. Moore

  DOI：10.1021/ja026957e

  日期：2002.8.1

  Bisfunctionalized m-phenylene ethynylene imine oligomers were polymerized in the polar solvent acetonitrile, resulting in high-molecular weight poly(m-phenylene ethynylene imine)s. It is hypothesized that this polymerization, which proceeds through the reversible metathesis of imine bonds, is driven by the folding of the long m-phenylene ethynylene imine chains. Upon conducting the polymerization in a series of solvents in which the m-phenylene ethynylene oligomers exhibit different folding stabilities, it was possible to correlate the molecular weight of the resulting poly(m-phenylene ethynylene imine)s with the helical stability of the corresponding oligomers. The polymerization was also demonstrated to be reversible and responsive to solvent and temperature changes.