2-[(diethoxyphosphinoyl)methyl]-5-methylfuran | 83837-65-4

• 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: 2-[(diethoxyphosphinoyl)methyl]-5-methylfuran
• 英文别名: diethyl (5-methylfurfuryl)phosphonate；diethyl 5-methylfurfurylphosphonate；Diethyl [(5-methylfuran-2-yl)methyl]phosphonate；2-(diethoxyphosphorylmethyl)-5-methylfuran
• CAS: 83837-65-4
• 化学式: C₁₀H₁₇O₄P
• 分子量: 232.216
• InChiKey: OUOPEZKNGAFONG-UHFFFAOYSA-N

物化性质

• 熔点：
  230-250 °C
• 沸点：
  102 °C(Press: 1 Torr)
• 密度：
  1.1114 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  48.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-[(diethoxyphosphinoyl)methyl]-5-methylfuran 在 吡啶 、 溴 、 水 作用下， 以 氯仿 为溶剂， 生成 磷酸二乙酯
  参考文献：
  名称：

  Synthesis of isomeric bromo(diethoxyphosphorylmethyl)furans

  摘要：

  Series of the previously unknown bromo(diethoxyphosphorylmethyl)furans including four of six possible regioisomers is synthesized. The target products were obtained by bromination of the corresponding (diethoxyphosphorylmethyl)furans or by a four-step synthesis including bromination of isomeric methyl-furancarboxylates, reduction of the products formed to the corresponding alcohols, substitution of hydroxy group with halogen and phosphorylation by the Michaelis-Becker reaction. It was established for the first fime that in the course of bromination of alkyl carboxylates and phosphonates of the furan series under the typical conditions of electrophilic reaction (Br(2) + 10% molar of AlCl(3), chloroform) the substituent enters not only into the heteroring, but also into the side chain. In the case of 5-methyl-2-(diethoxyphosphorylmethyl)furan only the last reaction pathway is observed. It is shown that bromo(chloromethyl)furans react with sodium diethyl phosphite not only according to the Michaelis-Becker scheme leading to phosphonates, but also by the pathway of debromination of the furan ring. The last unexpected reaction may acquire a practical use for removing a substituent protecting the alpha-position of the furan ring under mild conditions.

  DOI：

  10.1134/s1070363209030050
• 作为产物：
  描述：

  在 sodium acetate 作用下， 以 溶剂黄146 为溶剂， 反应 0.5h， 生成 2-[(diethoxyphosphinoyl)methyl]-5-methylfuran
  参考文献：
  名称：

  Synthesis of 2-(1-Phosphorylalkyl)- and 2-(1-Alkenyl)furans through Nitrile Oxide Cycloaddition Route

  摘要：

  提出了一种在呋喃环上带有各种取代基的2-(1-磷酰基烷基)呋喃的新合成方法。将(二乙氧基磷酰基)乙腈氧化物与O-保护的烯丙基醇进行环加成反应，随后通过包括Raney Ni还原和酸处理的简单顺序步骤，得到2-(1-磷酰基甲基)呋喃。由磷功能化呋喃衍生的磷稳定碳负离子应用于烷基化、氧氧化或烯化反应，分别得到2-(1-磷酰基烷基)呋喃、2-酰基呋喃或2-(1-烯基)呋喃。还描述了其他一些合成应用。

  DOI：

  10.1246/bcsj.61.2133

文献信息

• Chloroalkylation of (diethoxyphosphinoylmethyl)furans
  作者：L. M. Pevzner

  DOI：10.1134/s1070363208020096

  日期：2008.2

  2-(Diethoxyphosphinoylmethyl)- and 2-(diethoxyphosphinoylmethyl)-5-methyl-furans react with the paraformaldehyde-hydrogen chloride system in chloroform in the presence of zinc chloride to form moderately stable 5- and 4-chloromethyl derivatives, respectively. The chloromethylanephosphonates obtained were used as alkylating agents in reactions with sodium butanethiolate, diethylamine, and morpholine. 2-(Diethoxyphosphinoylmethyl)- and 2-(diethoxyphosphinoylmethyl)-5-methyl-furan react with acetaldehyde and hydrogen chloride in the presence of zinc chloride form a complex mixture of substances. Its vacuum distillation allowed isolation of dehydrochlorination products, 2-diethoxyphosphinoylmethyl-5-vinyl-, and 2-(diethoxyphosphinoylmethyl)-5-methyl-4-vinylfurans.

  2-(二乙氧基膦酰基甲基)-和2-(二乙氧基膦酰基甲基)-5-甲基-呋喃在氯仿中在氯化锌存在下与多聚甲醛-氯化氢体系反应，分别形成中等稳定的5-和4-氯甲基衍生物。所得氯甲基膦酸酯在与丁硫醇钠、二乙胺和吗啉的反应中用作烷基化剂。 2-(二乙氧基膦酰基甲基)-和2-(二乙氧基膦酰基甲基)-5-甲基-呋喃在氯化锌存在下与乙醛和氯化氢反应形成复杂的物质混合物。其真空蒸馏可分离脱氯化氢产物、2-二乙氧基膦酰基甲基-5-乙烯基-和2-(二乙氧基膦酰基甲基)-5-甲基-4-乙烯基呋喃。
• Pevzner, L. M.; Terekhova, M. I.; Ignat'ev, V. M., Journal of general chemistry of the USSR, 1984, vol. 54, # 9, p. 1775 - 1778
  作者：Pevzner, L. M.、Terekhova, M. I.、Ignat'ev, V. M.、Petrov, E. S.、Ionin, B. I.

  DOI：——

  日期：——
• Pevzner, L. M.; Ignat'ev, V. M.; Ionin, B. I., Journal of general chemistry of the USSR, 1987, vol. 57, p. 2020 - 2022
  作者：Pevzner, L. M.、Ignat'ev, V. M.、Ionin, B. I.

  DOI：——

  日期：——
• Pevzner, L. M.; Ignat'ev, V. M.; Ionin, B. I., Journal of general chemistry of the USSR, 1985, vol. 55, # 9, p. 1782 - 1784
  作者：Pevzner, L. M.、Ignat'ev, V. M.、Ionin, B. I.

  DOI：——

  日期：——
• Pevzner, L. M.; Ignat'ev, V. M.; Ionin, B. I., Russian Journal of General Chemistry, 1993, vol. 63, # 7.2, p. 1101 - 1105
  作者：Pevzner, L. M.、Ignat'ev, V. M.、Ionin, B. I.

  DOI：——

  日期：——