1-Ethoxy-1,2,3,4,5,6-hexahydro-3-methylphosphinine 1-Oxide | 186760-53-2

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦酸及其衍生物
• 英文名称: 1-Ethoxy-1,2,3,4,5,6-hexahydro-3-methylphosphinine 1-Oxide
• 英文别名: 1-ethoxy-3-methyl-1,2,3,4,5,6-hexahydrophosphinine 1-oxide；6-Methyl-2-oxo-2-ethoxy-1,2-oxaphosphorinan；1-Ethoxy-3-methyl-1lambda5-phosphinane 1-oxide；1-ethoxy-3-methyl-1λ5-phosphinane 1-oxide
• CAS: 186760-53-2
• 化学式: C₈H₁₇O₂P
• 分子量: 176.196
• InChiKey: PKUTWSKGCIVVON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  11
• 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：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-Ethoxy-1,2,3,4,5,6-hexahydro-3-methylphosphinine 1-Oxide 在 盐酸 、 水 作用下， 反应 10.0h， 以100%的产率得到1-hydroxy-3-methyl-1,2,3,4,5,6-hexahydrophosphinine 1-oxide
  参考文献：
  名称：

  环状次膦酸盐酸水解的研究：1-烷氧基-3-膦1-氧化物、1-乙氧基-3-甲基膦1-氧化物和1-乙氧基-3-甲基-1,2,3,4,5 ,6-六氢膦1-氧化物

  摘要：

  AbstractThe hydrochloric acid‐catalyzed hydrolysis of phosphinates was studied on 1‐alkoxy‐3‐phospholene 1‐oxides, 1‐ethoxy‐3‐methylphospholane 1‐oxide, and 1‐ethoxy‐3‐methyl‐1,2,3,4,5,6‐hexahydrophosphinine 1‐oxide as the model compounds. Under the conditions applied, the isomerization of the 3‐phospholene moiety to the 2‐phospholene ring also occurred leading to mixtures of the corresponding 1‐hydroxy‐3‐phospholene oxide and 1‐hydroxy‐2‐phospholene oxide. According to our optimized method, using 3 equivalents (0.5 mL) of concentrated hydrochloric acid in 1 mL of water per ca. 2 mmol of the substrate at reflux, the completion required 3‐10 hour. The hydrolyses were characterized by pseudo‐first‐order rate constants and the isomerizations by rate constants. The application of p‐toluenesulfonic acid under microwave irradiation at 140°C in the hydrolysis of 1‐alkoxy‐3‐methyl‐3‐phospholene oxides associated with reaction times of 1‐3 hour. The reactivity order of the 5‐ and 6‐ring phosphinates in hydrolysis was set up.

  DOI：

  10.1002/hc.21394
• 作为产物：
  描述：

  6,6-Dichloro-3-ethoxy-1-methyl-3lambda5-phosphabicyclo[3.1.0]hexane 3-oxide 在 palladium on activated charcoal 氢气 作用下， 生成 1-Ethoxy-1,2,3,4,5,6-hexahydro-3-methylphosphinine 1-Oxide
  参考文献：
  名称：

  Keglevich, Gyoergy; Kovacs, Attila; Ujszaszy, Kalmam, Phosphorus, Sulfur and Silicon and the Related Elements, 1992, vol. 70, # 3/4, p. 219 - 228

  摘要：

  DOI：

文献信息

• Direct Estirification and Amidation of Phosphinic Acids Under Microwave Conditions
  作者：György Keglevich、Nóra Zsuzsa Kiss、Tamás Körtvélyesi、Zoltán Mucsi

  DOI：10.1080/10426507.2012.743542

  日期：2013.1.1

  Abstract Phosphinic acids may be efficiently esterified in microwave-assisted reactions with alcohols. Especially alcohols with longer alkyl chain are suitable reagents for direct esterifications. At the same time, the direct amidation cannot be complete under such conditions. Hence, the tradional amidations via the phosphinic chloride intermediates have to be applied. The values of activation enthalpies

  摘要 次膦酸可以在与醇的微波辅助反应中有效地酯化。特别是具有较长烷基链的醇是直接酯化反应的合适试剂。同时，在这种条件下，直接酰胺化不能完全。因此，必须应用通过次膦酰氯中间体的传统酰胺化。通过量子化学计算获得的活化焓和反应焓值证明了实验观察是正确的。微波具有克服相对高活化焓的潜力。图形概要
• Keglevich, Gyoergy; Tungler, Antal; Novak, Tibor, Journal of Chemical Research - Part S, 1996, # 12, p. 528 - 529
  作者：Keglevich, Gyoergy、Tungler, Antal、Novak, Tibor、Toke, Laszlo

  DOI：——

  日期：——
• A Study on the Reduction of 4-Chloro-1,2-Dihydrophosphinine Oxides by Transfer Hydrogenation
  作者：Rita Kovács、György T. Balogh、Krisztina Ludányi、László Drahos、György Keglevich

  DOI：10.1080/10426507.2011.608100

  日期：2012.1.1

  Under the conditions of transfer hydrogenation by ammonium formate, the title compounds (6) were converted to a mixture of the corresponding 1,2,3,6-tetrahyidrophosphinine oxide (7), its dechlorinated derivative (8) and the respective 1,2,3,4,5,6-hexahydrophosphinine oxide (9). In the phenyl-substituted instance, the ratios of the components depended on the mode of heating (traditional heating or microwave irradiation), temperature, and the solvent (toluene or [bmim][BF4]) used. In the ethoxy-substituted series, the dechlorinated 1,2-dihydrophosphinine oxide (10b) was detected as an intermediate.
• Synthesis of 1‐Aryl‐1,2,3,4,5,6‐hexahydrophosphinine 1‐Oxides
  作者：György Keglevich、Melinda Sipos、Dóra Lengyel、Henrietta Forintos、Tamás Körtvélyesi、Tímea Imre、László Tőke

  DOI：10.1081/scc-200036618

  日期：2004.12.31

  Possibilities for the synthesis of 1-(2,4,6-triisopropylphenyl-) 1,2,3,4,5,6-hexahydrophosphinine oxide (2) have been explored. The trivial method based on the hydrogenation of the corresponding dihydrophosphinine oxides (8a-e) was suitable only for the preparation of hexahydrophosphinine oxides containing a trimethylphenyl or methylphenyl group on the phosphorus atom (9a-c). The triisopropylphenyl product (2) was synthesized by the stepwise reduction of the double bonds of starting material 1. Hence, the ring contraction side reaction, observed during the catalytic hydrogenation, could be eliminated. The unusual reactivity was studied by quantum chemical calculations.
• A study on the acidic hydrolysis of cyclic phosphinates: 1-Alkoxy-3-phospholene 1-oxides, 1-ethoxy-3-methylphospholane 1-oxide, and 1-ethoxy-3-methyl-1,2,3,4,5,6-hexahydrophosphinine 1-oxide
  作者：György Keglevich、Zita Rádai、Nikoletta Harsági、Áron Szigetvári、Nóra Zsuzsa Kiss

  DOI：10.1002/hc.21394

  日期：2017.9

  AbstractThe hydrochloric acid‐catalyzed hydrolysis of phosphinates was studied on 1‐alkoxy‐3‐phospholene 1‐oxides, 1‐ethoxy‐3‐methylphospholane 1‐oxide, and 1‐ethoxy‐3‐methyl‐1,2,3,4,5,6‐hexahydrophosphinine 1‐oxide as the model compounds. Under the conditions applied, the isomerization of the 3‐phospholene moiety to the 2‐phospholene ring also occurred leading to mixtures of the corresponding 1‐hydroxy‐3‐phospholene oxide and 1‐hydroxy‐2‐phospholene oxide. According to our optimized method, using 3 equivalents (0.5 mL) of concentrated hydrochloric acid in 1 mL of water per ca. 2 mmol of the substrate at reflux, the completion required 3‐10 hour. The hydrolyses were characterized by pseudo‐first‐order rate constants and the isomerizations by rate constants. The application of p‐toluenesulfonic acid under microwave irradiation at 140°C in the hydrolysis of 1‐alkoxy‐3‐methyl‐3‐phospholene oxides associated with reaction times of 1‐3 hour. The reactivity order of the 5‐ and 6‐ring phosphinates in hydrolysis was set up.