diethyl (trifluoromethyl)phosphonite | 64149-08-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: diethyl (trifluoromethyl)phosphonite
• 英文别名: Trifluormethyldiethoxyphosphin；(Trifluoromethyl)diethoxyphosphine；diethoxy(trifluoromethyl)phosphane
• CAS: 64149-08-2
• 化学式: C₅H₁₀F₃O₂P
• 分子量: 190.102
• InChiKey: KJRNXCVBRVQXJW-UHFFFAOYSA-N

物化性质

• 沸点：
  23-25 °C(Press: 10 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl (trifluoromethyl)phosphonite 在 三甲基乙酸 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 三氟甲基膦酸二乙酯
  参考文献：
  名称：

  Facile Synthesis of Fluorinated Phosphonates via Photochemical and Thermal Reactions

  摘要：

  Under UV irradiation (254 nm) at ambient temperature, a degassed mixture of (EtO)(2)POP(OEt)(2) and RfI {R-f=CF3, C2F5, C4F9, C6F13, (CF3)(2)CF, CF2CF=CF2, ClCF2CF2, BrCF2CF2, C6F5, ClCF2CFClCF2CF2, I(CF2)(3), I(CF2)(4), FO2S(CF2)(4), FO2S(CF2)(2)O(CF2)(2)} affords the fluorinated phosphonite, [RfP(OEt)(2)]. Oxidation of the phosphonites, [RfP(OEt)(2)], with Me3COOH gave the corresponding fluorinated phosphonates, (EtO)(2)P(O)R-f(1-14), in 35-80% isolated yields. CF3CCl2I reacts with (EtO)(2)POP(OEt)(2) at room temperature in the absence of UV irradiation to afford [CF3CCl2P(OEt)(2)] which upon oxidation gave a 52% yield of CF3CCl2P(O)(OEt)(2) (15). The reaction of (EtO)(2)POP(OEt)(2) and RfI (R-f=ClCF2CF2, BrCF2CF2, C2F5) at 125 degrees C in the presence of Me3COOCMe3 and subsequent oxidation of the resultant phosphonites afforded phosphonates (2, 7, and 8) albeit in lower yields (49-62%) compared to those of the photochemical reaction (58-80%). (RO)(2)P(O)CF2CF2I (R=Et, i-Pr) (16 and 17) was obtained (42-48%) when a degassed mixture of (RO)(3)P and BrCF2CF2I was subjected to UV irradiation (254 nm) at ambient temperature via a unique photochemical transformation.

  DOI：

  10.1021/ja971345t
• 作为产物：
  描述：

  (三氟甲基)二氯磷 在 C₂H₅OH 作用下， 以63%的产率得到diethyl (trifluoromethyl)phosphonite
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: F: PerFHalOrg.SVol.1, 5.2.7.1, page 104 - 132

  摘要：

  DOI：

文献信息

• Cyclisation reactions with hexafluoroacetone and phosphonous acid derivatives containing the trifluoromethyl and pentafluoropropenyl group; molecular structures of two 1,3,2λ5σ5-dioxaphospholanes
  作者：Alexander N. Chernega、Alexander A. Kolomeitsev、Yurij L. Yagupolskij、Andreas Gentzsch、Rolf-Dieter Hund、Gerd-Volker Röschenthaler

  DOI：10.1016/s0022-1139(00)80041-x

  日期：1993.2

  1,3,2λ5σ5-Dioxaphospholanes have been obtained from trifluoromethylphosphonous aciddiethyl ester, the corresponding bis(diethyldiamide), (Z)-1,2,3,3,3-pentafluoropropenyl-phosphonous acid diethyl ester and hexafluoroacetone. (Z)-1,2,3,3,3-Pentafluoropropenylphosphonousacid bis(diethylamide) furnished, unexpectedly, 2-bis(diethylamino)-2,3-difluoro-4,5,5-tris(trifluoromethyl)-1,2λ5σ5-oxaphospholene-(3)

  1,3,2λ 5 σ 5 -Dioxaphospholanes已从获得trifluoromethylphosphonous aciddiethyl酯，相应的双（diethyldiamide），（Ž）-1,2,3,3,3-pentafluoropropenyl-亚膦酸二乙酯和六氟丙酮。（Z）-1,2,3,3,3-五氟丙烯基膦酸双（二乙酰胺）意外地提供了2-双（二乙氨基）-2,3-二氟-4,5,5-三（三氟甲基）-1,2λ 5 σ 5 -oxaphospholene-（3）。通过单晶X射线研究证实了两个含有CF 3基团的二氧杂膦酮的结构，并显示出扭曲的三角双锥体，CF 3占据了轴向位置。
• A novel family of (1-aminoalkyl)(trifluoromethyl)- and -(difluoromethyl)phosphinic acids – analogues of α-amino acids
  作者：Natalia V Pavlenko、Tatiana I Oos、Yurii L Yagupolskii、Igor I Gerus、Uwe Doeller、Lothar Willms

  DOI：10.3762/bjoc.10.66

  日期：——

  A series of novel (1-aminoalkyl)(trifluoromethyl)- and -(difluoromethyl)phosphinic acids - analogues of proteinogenic and nonproteinogenic alpha-amino acids were prepared. The synthetic methodology was based on nucleophilic addition of (trifluoromethyl)phosphinic acid or (difluoromethyl)phosphinic acid or its ethyl ester to substrates with C=N or activated C=C double bonds. Analogues of glycine, phenylglycine

  制备了一系列新型 (1-氨基烷基)(三氟甲基)-和-(二氟甲基) 次膦酸-蛋白质和非蛋白质α-氨基酸的类似物。合成方法基于（三氟甲基）次膦酸或（二氟甲基）次膦酸或其乙酯与具有 C=N 或活化的 C=C 双键的底物的亲核加成。由此制备了甘氨酸、苯基甘氨酸、丙氨酸、缬氨酸、脯氨酸、氨基丙二酸和天冬氨酸的类似物。还测试了（三氟甲基）次膦酸和二苄胺与醛的三组分一锅反应以制备标题化合物。
• An electron spin resonance study of fluoroalkoxy- and fluoroalkylphosphoranyl radicals
  作者：Robert W. Dennis、Ian H. Elson、Brian P. Roberts、Robert C. Dobbie

  DOI：10.1039/p29770000889

  日期：——

  Two series of phosphoranyl radicals, containing fluoroalkoxy or trifluoromethyl ligands, respectively, have been generated in solution by radical addition to trivalent phosphorus compounds, and their e.s.r. spectra have been studied. The spectra of the radicals RFOṖ(OR)3 and RFOṖMe(OR)2exhibit large isotropic phosphorus hyperfine splittings and long-range fluorine coupling with (in many cases) fewer

  通过三价磷化合物的自由基加成，在溶液中生成了分别包含氟烷氧基或三氟甲基配体的两个系列的磷烷基，并研究了它们的esr光谱。基团的光谱ř ˚F OP（OR）3和R ˚F OPME（OR）2表现出大的各向同性磷超精细分裂，并用远距离氟耦合（在许多情况下）比化学等价的最大数目更少的19 ˚F核。根据快速构象平衡的存在，观察并解释了温度相关的线形变化。esr光谱与磷烷基的三角双锥体结构一致，其中RF O配体是顶端，CH 3基团是赤道的。
• Maslennikov, I. G.; Lavrent'ev, A. N.; Lyubimova, M. V., Journal of general chemistry of the USSR, 1983, vol. 53, # 12, p. 2417 - 2419
  作者：Maslennikov, I. G.、Lavrent'ev, A. N.、Lyubimova, M. V.、Shvedova, Yu. I.、Lebedev, V. B.

  DOI：——

  日期：——
• Maslennikov, I. G.; Shvedova, Yu. I.; Lavrent'ev, A. N., Journal of general chemistry of the USSR, 1984, vol. 54, # 1, p. 204
  作者：Maslennikov, I. G.、Shvedova, Yu. I.、Lavrent'ev, A. N.

  DOI：——

  日期：——