diisopropyl(fluorocarbethoxymethyl)phosphonate | 110624-86-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diisopropyl(fluorocarbethoxymethyl)phosphonate
• 英文别名: diisopropyl(carboethoxyfluoromethyl)phosphonate；Ethyl 2-di(propan-2-yloxy)phosphoryl-2-fluoroacetate
• CAS: 110624-86-7
• 化学式: C₁₀H₂₀FO₅P
• 分子量: 270.238
• InChiKey: WGZAWXFFPNNUMF-UHFFFAOYSA-N

物化性质

• 沸点：
  130-145 °C(Press: 0.5 Torr)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diisopropyl(fluorocarbethoxymethyl)phosphonate 在 potassium fluoride 、 正丁基锂 、 三甘醇二甲醚 作用下， 反应 28.33h， 生成 3-氟-4-甲氧基苯乙酮
  参考文献：
  名称：

  Alkylation of (fluorocarbethoxymethylene)tri-n-butylphosphorane: a facile entry to .alpha.-fluoroalkanoates

  摘要：

  DOI：

  10.1021/jo00295a016
• 作为产物：
  描述：

  ethyl 2-diethoxyphosphanyl-2-di(propan-2-yloxy)phosphoryl-2-fluoroacetate 在 air 、 二叔丁基过氧化物 作用下， 生成 diisopropyl(fluorocarbethoxymethyl)phosphonate
  参考文献：
  名称：

  Acylation of fluorocarbethoxy-substituted ylides: a simple and general route to .alpha.-fluoro .beta.-keto esters

  摘要：

  (Fluorocarbethoxymethylene)tri-n-butylphosphorane (3) reacts with acid chlorides and anhydrides to form the corresponding carbon acylated phosphonium salts 4, and hydrolysis of 4 under mild basic conditions provides RCOCFHCOOEt (8) in moderate yields. The reaction is applicable to primary, secondary, tertiary, cyclic, aromatic, and ester-substituted acid chlorides. Acylation with ethyl chloroformate and ethyl chlorothioformate leads to the diesters CFH(COOEt)2 and EtSCOCFHCOOEt. Extension of this reaction sequence to perfluorinated and partially fluorinated acid chlorides did not proceed cleanly to give the expected phosphonium salts. However, the anion derived from (EtO)2P(O)CFHC(O)OEt reacts with R(F)COCl to form the corresponding C-acylated phosphonates 10, and hydrolysis of 10 gives R(F)COCFHCOOEt.

  DOI：

  10.1021/jo00001a052

文献信息

• APPLICATION OF FLUOROCARBETHOXY-SUBSTITUTED PHOSPHONATE: A FACILE ENTRY TO SUBSTITUTED 2-FLUORO-3-OXOESTERS
  作者：Hou-Jen Tsai

  DOI：10.1080/10426509708043541

  日期：1997.7.1

  Abstract Diethyl(fluorocarbethoxymethyl)phosphonate 1a or diisopropyl(fluorocarbethoxymethyl)phosphonate 1b, prepared from triethyl phosphite or triisopropyl phosphite with ethyl bromofluoroacetate, react with n-butyllithium in THF to give the corresponding phosphonate carbanions [(RO)2P(O)CFCO2Et]−Li+ 2a (R=Et) and 2b (R=i-Pr). Addition of trimethylsilyltrifluoroacetate CF3C(O)OSiMe3 to a THF solution

  摘要 由亚磷酸三乙酯或亚磷酸三异丙酯与溴氟乙酸乙酯制备的二乙基（氟碳乙氧基甲基）膦酸酯 1a 或二异丙基（氟碳乙氧基甲基）膦酸酯 1b 与正丁基锂在 THF 中反应得到相应的膦酸酯碳负离子 [(RO)2P(O)CFCO2Et]- Li+ 2a (R=Et) 和 2b (R=i-Pr)。将三甲基甲硅烷基三氟乙酸酯 CF3C(O)OSiMe3 添加到膦酸酯碳负离子的 THF 溶液中，形成三氟乙酰氟乙酸乙酯 [CF3C(O)CFCO2Et]-Li+3 的烯醇化物。随后烯醇化物的质子化、烷基化或烯丙基化得到取代的 2,4,4,4 -四氟-3-氧代酯 CF3C(O)CFR1CO2Et 10
• Tetrafluorine-Containing Ketones and Acetoacetates: Synthesis and Mechanistic Study
  作者：Hou-Jen Tsai、Chi-Wei Hsieh

  DOI：10.1002/jccs.200700107

  日期：2007.6

  corresponding intermediates [CF 3 C(O)CFPh] - Li + (10) and [CF 3 C(O)CFCO 2 Et]Li + (11), respectively. Subsequent protonation, alkylation or allylation of 10 and 11 afforded trifluoromethyl fluorobenzyl ketones 12 and ethyl 2,4,4,4-tetrafluoroacetoacetates 13. Based on the results obtained, a plausible mechanism was proposed.

  将三氟乙酸三甲基甲硅烷基酯加入到 α-氟苄基膦酸酯 (3) 或二异丙基(氟代甲氧基甲基) 膦酸酯 (9) 的碳负离子中，形成相应的中间体 [CF 3 C(O)CFPh] - Li + (10) 和 [CF 3 C( O)CFCO 2 Et]Li + (11)，分别。随后对 10 和 11 进行质子化、烷基化或烯丙基化，得到三氟甲基氟苄基酮 12 和 2,4,4,4-四氟乙酰乙酸乙酯 13。基于所得结果，提出了一种合理的机理。
• Synthesis of phenyl substituted fluoro-olefins
  作者：Hou-Jen Tsai

  DOI：10.1016/0040-4039(95)02218-x

  日期：1996.1

  The anion derived from diethyl α-fluorobenzyl phosphonate (EtO)2P(O)-CFHPh (2) and lithium diisopropylamide in THF underwent the reaction with aldehydes and ketones to afford a moderate to good yields of phenyl substituted fluoro-olefins RR′C=CFPh (6).

  α-氟代苄基膦酸二乙酯（EtO）2 P（O）-CFHPh（2）和二异丙基氨基化锂在THF中的阴离子与醛和酮反应制得中等至良好收率的苯基取代的氟代烯烃RR'C ＝ CFPh（6）。
• Functional Analysis of an Aspartate-Based Epoxidation Catalyst with Amide-to-Alkene Peptidomimetic Catalyst Analogues
  作者：Charles E. Jakobsche、Gorka Peris、Scott J. Miller

  DOI：10.1002/anie.200802223

  日期：2008.8.18
• SYNTHESIS OF PHENYL AND ESTER SUBSTITUTED VINYL FLUORIDES VIA REDUCTION AND OLEFINATION OF ESTERS
  作者：Hou-jen Tsai、Donald J. Burton

  DOI：10.1080/10426509808035739

  日期：1998.9.1

  A reduction-olefination sequence has been used to convert ethyl pentafluoropropanoate 6 to 1-fluoro-1-phenyl-2-pentafluoroethyl ethene 7 and ethyl 2,4,4,5,5,5-hexafluoro-2-pentenoate 8. Addition of lithium diethyl alpha -fluorobenzylphosphonate [(EtO)(2)P(O)CFPh](-) Li+ 4 or lithium fluorocarboethoxymethylene dialkylphosphonate [(RO)(2)P(O)CFCO2Et](-) Li+ 5 (R = Et, i-Pr) to a THF solution of fluorinated aldehydes prepared in situ from 6 and diisobutylaluminum hydride (DIBAL) affords the vinyl fluorides C2F5CH=CFPh 7 and C2F5CH=CFCO2Et 8 in good yields. However, yields of the final products 7 and 8 are low when in situ reduction of 6 to aldehyde was performed in the presence of lithium salts of 4 or 5.