2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-1,1,1,3,3,3-hexafluoropropan-2-ol | 1309060-96-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-1,1,1,3,3,3-hexafluoropropan-2-ol
• 英文别名: 1,1-Bis(trifluoromethyl)-2-(1,4,7,10-tetraoxa-13-azacyclopentadecane-13-yl)ethanol；1,1,1,3,3,3-hexafluoro-2-(1,4,7,10-tetraoxa-13-azacyclopentadec-13-ylmethyl)propan-2-ol
• CAS: 1309060-96-5
• 化学式: C₁₄H₂₃F₆NO₅
• 分子量: 399.331
• InChiKey: RGFAUQQTMHVBNV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  60.4
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-1,1,1,3,3,3-hexafluoropropan-2-ol 以 乙醚 为溶剂， 以83%的产率得到
  参考文献：
  名称：

  Potassium and Well-Defined Neutral and Cationic Calcium Fluoroalkoxide Complexes: Structural Features and Reactivity

  摘要：

  The fluorinated aminoether alcohols (1-aza-12-crown-4)CH2C(CF3)(2)OH ({RO1F}H), (MeOCH2CH2)(2)NCH2C-(CF3)(2)OH ({RO2F}H), and (MeOCH2CH2)(Me)NCH2C(CF3)(2)OH ({RO3F}H) have been synthesized and used to prepare the heteroleptic calcium amido complexes {ROxF}Ca(N(SiMe2R)(2)) (47; x = 2, 3, R = H, Me). The ability to form stable complexes varies with the chelating and electron-donating ability of the aminoether alkoxide ligand, as exemplified by our failure to isolate cleanly the elusive {RO1F}Ca(N(SiMe2R)(2)). X-ray diffraction studies show that, in the solid state, intramolecular Ca center dot center dot center dot F interactions help reach coordinative saturation in the dimeric [{RO2F}Ca(N(SiMe3)(2))](2) ([4](2)), [{RO2F}Ca(N(SiMe2H)(2))](2) ([5](2)), [{RO3F}Ca(N(SiMe3)(2))](2) ([6](2)), and [{RO3F}Ca(N(SiMe2H)(2))](2) ([7](2)), which crystallized free of solvent coligands. Similar stabilizing K center dot center dot center dot F patterns were found in the polymetallic potassium fluoroalkoxides [{RO1F}K](2) ([1](2)), [{RO2F}K](4) ([2](4)), and [{RO3F}K](4) ([3](4)); [2](4) and [3](4) form heterocubanes in the solid state. Examination of the XRD data for [1](2)[7](2) shows that metal center dot center dot center dot F interactions can be favored over binding of O-ether atoms for calcium and potassium. Pulse-gradient spinecho NMR spectroscopy shows that the complexes remain aggregated in aromatic solvents. The solvent-free salts [{ROxF}Ca+]center dot[H2N{B(C6F5)(3)}(2) ] (x = 1 (8), 2 (9), 3 (10)) are obtained by treating 47 with [H(OEt2)(2)(+)]center dot[H2N{B(C6F5)(3)}(2) ] or by reacting Ca(N(SiMe3)(2))(2) with [{ROxF}HH+]center dot[H2N{B(C6F5)(3)}(2) ]; the solid-state structures of [8 center dot H2O](2) and [9 center dot H2O](2) again showed the presence of Ca center dot center dot center dot F contacts. Complexes 57 are promising catalysts for the regiospecific anti-Markovnikov hydrophosphination of styrene with diphenylphosphine, affording TOF values as high as 52 mol(subst) mol(Ca)(1) h(1) with up to 400 equiv of substrates within 12 h at 60 degrees C.

  DOI：

  10.1021/om500343w
• 作为产物：
  描述：

  3,3,3,-三氟-2-(三氟甲基)-1,2-氧化丙烯 、 氮杂-15-冠醚-5 以 乙醚 为溶剂， 以76%的产率得到2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-1,1,1,3,3,3-hexafluoropropan-2-ol
  参考文献：
  名称：

  离散的无溶剂碱土金属阳离子：金属···氟相互作用和 ROP 催化活性

  摘要：

  已经设计了用于合成大碱土 (Ae) 金属 (Ca、Sr、Ba) 及其较小的 Zn 和 Mg 类似物的明确、无溶剂阳离子的有效协议。2,4-二叔丁基-6-(吗啉甲基)苯酚({LO(1)}H), 2-{[双(2-甲氧基乙基)氨基]甲基}-4,6-二-叔丁基苯酚 ({LO(2)}H), 2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-4,6-di-tert-butylphenol ({LO (3)}H) 和 2-[(1,4,7,10-tetraoxa-13-azacyclo-pentadecan-13-yl)methyl]-1,1,1,3,3,3-hexafluoropropan-2 -ol ({RO(3)}H) 与 [H(OEt(2))(2)](+)[H(2)N{B(C(6)F(5))(3)}( 2)](-) 很容易得到双酸性前配体

  DOI：

  10.1021/ja2024977

文献信息

• Potassium and Well-Defined Neutral and Cationic Calcium Fluoroalkoxide Complexes: Structural Features and Reactivity
  作者：Sorin-Claudiu Roşca、Thierry Roisnel、Vincent Dorcet、Jean-François Carpentier、Yann Sarazin

  DOI：10.1021/om500343w

  日期：2014.10.27

  The fluorinated aminoether alcohols (1-aza-12-crown-4)CH2C(CF3)(2)OH (RO1F}H), (MeOCH2CH2)(2)NCH2C-(CF3)(2)OH (RO2F}H), and (MeOCH2CH2)(Me)NCH2C(CF3)(2)OH (RO3F}H) have been synthesized and used to prepare the heteroleptic calcium amido complexes ROxF}Ca(N(SiMe2R)(2)) (47; x = 2, 3, R = H, Me). The ability to form stable complexes varies with the chelating and electron-donating ability of the aminoether alkoxide ligand, as exemplified by our failure to isolate cleanly the elusive RO1F}Ca(N(SiMe2R)(2)). X-ray diffraction studies show that, in the solid state, intramolecular Ca center dot center dot center dot F interactions help reach coordinative saturation in the dimeric [RO2F}Ca(N(SiMe3)(2))](2) ([4](2)), [RO2F}Ca(N(SiMe2H)(2))](2) ([5](2)), [RO3F}Ca(N(SiMe3)(2))](2) ([6](2)), and [RO3F}Ca(N(SiMe2H)(2))](2) ([7](2)), which crystallized free of solvent coligands. Similar stabilizing K center dot center dot center dot F patterns were found in the polymetallic potassium fluoroalkoxides [RO1F}K](2) ([1](2)), [RO2F}K](4) ([2](4)), and [RO3F}K](4) ([3](4)); [2](4) and [3](4) form heterocubanes in the solid state. Examination of the XRD data for [1](2)[7](2) shows that metal center dot center dot center dot F interactions can be favored over binding of O-ether atoms for calcium and potassium. Pulse-gradient spinecho NMR spectroscopy shows that the complexes remain aggregated in aromatic solvents. The solvent-free salts [ROxF}Ca+]center dot[H2NB(C6F5)(3)}(2) ] (x = 1 (8), 2 (9), 3 (10)) are obtained by treating 47 with [H(OEt2)(2)(+)]center dot[H2NB(C6F5)(3)}(2) ] or by reacting Ca(N(SiMe3)(2))(2) with [ROxF}HH+]center dot[H2NB(C6F5)(3)}(2) ]; the solid-state structures of [8 center dot H2O](2) and [9 center dot H2O](2) again showed the presence of Ca center dot center dot center dot F contacts. Complexes 57 are promising catalysts for the regiospecific anti-Markovnikov hydrophosphination of styrene with diphenylphosphine, affording TOF values as high as 52 mol(subst) mol(Ca)(1) h(1) with up to 400 equiv of substrates within 12 h at 60 degrees C.
• Discrete, Solvent-Free Alkaline-Earth Metal Cations: Metal···Fluorine Interactions and ROP Catalytic Activity
  作者：Yann Sarazin、Bo Liu、Thierry Roisnel、Laurent Maron、Jean-François Carpentier

  DOI：10.1021/ja2024977

  日期：2011.6.15

  [LO(3)}M](+)[X](-) (M = Zn, 8; Mg, 9; Ca, 10; Sr, 11; Ba, 12) and [RO(3)}M](+)[X](-) (M = Zn, 13; Mg, 14; Ca, 15; Sr, 16; Ba, 17) were synthesized in high yields (70-90%) by reaction of 3 or 4 with the neutral precursors M[N(SiMe(3))(2)](2)(THF)(x) (M = Zn, Mg, x = 0; M = Ca, Sr, Ba, x = 2). All compounds were fully characterized by spectroscopic methods, and the solid-sate structures of compounds 1, 3, 7, 8, 13

  已经设计了用于合成大碱土 (Ae) 金属 (Ca、Sr、Ba) 及其较小的 Zn 和 Mg 类似物的明确、无溶剂阳离子的有效协议。2,4-二叔丁基-6-(吗啉甲基)苯酚(LO(1)}H), 2-[双(2-甲氧基乙基)氨基]甲基}-4,6-二-叔丁基苯酚 (LO(2)}H), 2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-4,6-di-tert-butylphenol (LO (3)}H) 和 2-[(1,4,7,10-tetraoxa-13-azacyclo-pentadecan-13-yl)methyl]-1,1,1,3,3,3-hexafluoropropan-2 -ol (RO(3)}H) 与 [H(OEt(2))(2)](+)[H(2)NB(C(6)F(5))(3)}( 2)](-) 很容易得到双酸性前配体