2-methyl-2-(1',1',2',2',3',3',4',4'-nonafluoroheptyloxymethyl)-1,3-propanediol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-2-(1',1',2',2',3',3',4',4'-nonafluoroheptyloxymethyl)-1,3-propanediol
• 英文别名: 2-Methyl-2-(4,4,5,5,6,6,7,7,7-nonafluoroheptoxymethyl)propane-1,3-diol
• 化学式: C₁₂H₁₇F₉O₃
• 分子量: 380.251
• InChiKey: DUMWTXXOCNCFGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  1,1,1-三(羟甲基)乙烷 在 palladium on activated charcoal 氢气 、 potassium carbonate 、 C.I.酸性橙108 、 copper(l) chloride 作用下， 以 甲醇 、 丙酮 、 叔丁醇 为溶剂， 反应 84.0h， 生成 2-methyl-2-(1',1',2',2',3',3',4',4'-nonafluoroheptyloxymethyl)-1,3-propanediol
  参考文献：
  名称：

  Syntheses, Derivatives, Solubility, and Interfacial Properties of 2-Methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols:  Potential Building Blocks for Syntheses of Amphiphatic Macromolecules

  摘要：

  2-Hydroxymethyl-2-methyl-1,3-propanediol (A) was reacted with (Me3Si)(2)NH and toluenesulfonyl chloride (TsCl) to give mainly CH3C(CH2OSiMe3)(3) (1), and CH3C(CH2OTs)(3) (2), respectively. With allyl bromide, the products were CH3C(CH2OCH2CH=CH2)(2)(CH,OH) (3) and CH3C(CH2OCH2CH= CH2)(CH2OH)(2).H2O (4). The reactions of 4 with perfluoroalkyl iodides (RfI) were catalyzed by Cu(I)Cl to form 2-methyl-2-pol,fluoroalkenyloxymethyl-1,3-propanediols: (RfCH=CHCH2OCH2)C(Me)(CH2OH)2 [R-f = C4F9 (5), C(8)F17 (6), and (CF2CF2)(4)OCF(CF3)(2) (7)]. Reduction of 5 and 6 with hydrogen gave two new 2-methyl-2-polyfluoroalkyloxymethyl-1,3-propanediols, 8 and 9. The sodium salt of 9 was reacted with allyl bromide or acetyl chloride to form (C8F17CH2CH2CH2OCH2)C(Me)(CH2OX)(CH2OH)(2) [where X = CH2CH=CH2 (10) or C(O)CH3 (12)] and (C8F17CH2CH2CH2OCH2)C(Me)(CH2OX)2 [where X = CH2CH=CH2 (11) or C(O)CH3 (13)]. Reaction of tolenesulfonyl chloride with 7 gave the monotosylate, 14, as the sole product. With 4-trifluoromethylbenzyl bromide, the sodium salt of 4 gave (4-CF3C6H4CH2OCH2)C(Me)(CH2CH=CH2)(CH2OH)-H2O (15). The compounds were characterized by NMR (H-1, C-13, F-19, Si-29), GC-MS, and high-resolution MS or elemental analyses. LTV evidence was obtained for partitioning of 9, 12, 14, and 15 between perfluorodecalin and n-octanol. The test compounds acted as surfactants by facilitating the solubility of phenol and Si(CH CI-12)4 in perfluorodecalin. The single-crystal X-ray structure of 8 was also obtained. It crvstallized in the monoc linic space group P21/c, and unit cell dimensions were a = 24.966(2) Angstrom (alpha = 90degrees), b = 6.1371(6) Angstrom ( beta = 100.730(2)degrees), and c = 10.5669(10) Angstrom (gamma = 90degrees).

  DOI：

  10.1021/jo016166f

文献信息

• Syntheses, Derivatives, Solubility, and Interfacial Properties of 2-Methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols:  Potential Building Blocks for Syntheses of Amphiphatic Macromolecules
  作者：Bamidele A. Omotowa、Matthew R. Judd、Brendan Twamley、Jean'ne M. Shreeve

  DOI：10.1021/jo016166f

  日期：2002.3.1

  2-Hydroxymethyl-2-methyl-1,3-propanediol (A) was reacted with (Me3Si)(2)NH and toluenesulfonyl chloride (TsCl) to give mainly CH3C(CH2OSiMe3)(3) (1), and CH3C(CH2OTs)(3) (2), respectively. With allyl bromide, the products were CH3C(CH2OCH2CH=CH2)(2)(CH,OH) (3) and CH3C(CH2OCH2CH= CH2)(CH2OH)(2).H2O (4). The reactions of 4 with perfluoroalkyl iodides (RfI) were catalyzed by Cu(I)Cl to form 2-methyl-2-pol,fluoroalkenyloxymethyl-1,3-propanediols: (RfCH=CHCH2OCH2)C(Me)(CH2OH)2 [R-f = C4F9 (5), C(8)F17 (6), and (CF2CF2)(4)OCF(CF3)(2) (7)]. Reduction of 5 and 6 with hydrogen gave two new 2-methyl-2-polyfluoroalkyloxymethyl-1,3-propanediols, 8 and 9. The sodium salt of 9 was reacted with allyl bromide or acetyl chloride to form (C8F17CH2CH2CH2OCH2)C(Me)(CH2OX)(CH2OH)(2) [where X = CH2CH=CH2 (10) or C(O)CH3 (12)] and (C8F17CH2CH2CH2OCH2)C(Me)(CH2OX)2 [where X = CH2CH=CH2 (11) or C(O)CH3 (13)]. Reaction of tolenesulfonyl chloride with 7 gave the monotosylate, 14, as the sole product. With 4-trifluoromethylbenzyl bromide, the sodium salt of 4 gave (4-CF3C6H4CH2OCH2)C(Me)(CH2CH=CH2)(CH2OH)-H2O (15). The compounds were characterized by NMR (H-1, C-13, F-19, Si-29), GC-MS, and high-resolution MS or elemental analyses. LTV evidence was obtained for partitioning of 9, 12, 14, and 15 between perfluorodecalin and n-octanol. The test compounds acted as surfactants by facilitating the solubility of phenol and Si(CH CI-12)4 in perfluorodecalin. The single-crystal X-ray structure of 8 was also obtained. It crvstallized in the monoc linic space group P21/c, and unit cell dimensions were a = 24.966(2) Angstrom (alpha = 90degrees), b = 6.1371(6) Angstrom ( beta = 100.730(2)degrees), and c = 10.5669(10) Angstrom (gamma = 90degrees).