ethyl 3-<(diethoxyphosphinyl)methyl>furan-2-carboxylate | 50710-43-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃
• 英文名称: ethyl 3-<(diethoxyphosphinyl)methyl>furan-2-carboxylate
• 英文别名: 3-diethoxyphosphorylmethyl-furan-2-carboxylic acid ethyl ester；Ethyl 3-[(diethoxyphosphoryl)methyl]furan-2-carboxylate；ethyl 3-(diethoxyphosphorylmethyl)furan-2-carboxylate
• CAS: 50710-43-5
• 化学式: C₁₂H₁₉O₆P
• 分子量: 290.253
• InChiKey: MHFOSBCHWLZUSI-UHFFFAOYSA-N

物化性质

• 沸点：
  397.6±37.0 °C(Predicted)
• 密度：
  1.180±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  75
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3-<(diethoxyphosphinyl)methyl>furan-2-carboxylate 在 sodium 、 三乙胺 作用下， 以 乙酸乙酯 、 甲苯 为溶剂， 生成 diethyl 1-(2-ethoxycarbonylfur-3-yl)-2-(diethoxyphosphoryloxy)-2-(ethoxycarbonyl)ethenephosphonate
  参考文献：
  名称：

  Enol phosphates of phosphorylated derivatives of furylacetic aldehyde and furylpiruvic acid

  摘要：

  Phosphorylated derivatives of isomeric furylacetic aldehydes and furylpiruvic acids have been synthesized via formylation and oxalylation of dialkyl (ethoxycarbonylfuryl)methanephosphonates under conditions of the Claisen reaction. H-1, C-13, and P-31 NMR spectroscopy studies have shown that the products exist as equilibrium mixtures of the carbonyl compounds and its E- and Z-enol forms in chloroform solutions. Acylation of these substances with diethyl chlorophosphate has yielded the corresponding enol phosphates. Influence of the substituents location in the furan ring on predominance of cis- or trans-configuration has been demonstrated.

  DOI：

  10.1134/s1070363214110188
• 作为产物：
  描述：

  ethyl 3-(bromomethyl)furan-2-carboxylate 、 sodium diethyl phosphite 以 苯 为溶剂， 反应 3.0h， 以39%的产率得到ethyl 3-<(diethoxyphosphinyl)methyl>furan-2-carboxylate
  参考文献：
  名称：

  Pevzner, L. M.; Ignat'ev, V. M.; Ionin, B. I., Journal of general chemistry of the USSR, 1992, vol. 62, # 4.1, p. 658 - 662

  摘要：

  DOI：

文献信息

• Reaction of (ethoxycarbonylfuryl)methanephosphonates with diethyl carbonate in presence of sodium foil
  作者：L. M. Pevzner

  DOI：10.1134/s1070363214070159

  日期：2014.7

  conjugated with the carbanion center of 2-furylmethanephosphonate, addition of the carbanion to the carbonyl group of diethyl carbonate takes place to give 2-furylacetic acid derivatives in high yield. Sodium salts of these CH-acids are synthesized, isolated, and characterized. Their alkylation with alkyl bromoacetates is carried out. If ethoxycarbonyl group is not conjugated with the carbanion center, conversion

  研究了钠箔存在下（乙氧基羰基呋喃基）甲烷膦酸酯与碳酸二乙酯的反应。结果表明，如果酸化基团与2-呋喃基甲烷膦酸酯的碳负离子中心共轭，则将碳负离子加到碳酸二乙酯的羰基上可以高产率地得到2-呋喃基乙酸衍生物。合成，分离和表征这些CH-酸的钠盐。用溴乙酸烷基酯进行它们的烷基化。如果乙氧羰基不与碳负离子中心共轭，则起始膦酸酯的转化率和加合物的产率急剧降低。在用碳酸二乙酯酰化之后，立即将烷基（2-和4-乙氧基羰基糠-3-基）甲烷膦酸酯用碳酸二乙酯钠系统还原，以形成烷基1-（2-和4-乙氧基羰基糠-3-基）乙烷膦酸酯。中间还原产物的形成，磷酸化的呋喃基乙醛也经光谱固定。与起始膦酸酯和1-（3-呋喃基）乙烷膦酸酯烷基酯的酯基的还原脱烷基同时发生，得到羧酸盐。（2-甲基-5-乙氧基羰基呋喃-3-基）甲烷膦烷基酯不参与缩合反应。它仅产生在碳酸二乙酯形成的乙醇酸钠作用下的脱烷基化产物。与起始膦酸酯和1-（3-呋
• Phosphonomethylated Acetoxymethyl Derivatives of Acetylfurans and Alkyl Furoates with the Remote Location of Substituents: Synthesis and Further Transformations
  作者：L. M. Pevzner、A. I. Ponyaev

  DOI：10.1134/s1070363223030088

  日期：2023.3

  Abstract Methods of synthesis of phosphonomethylated acetoxymethyl derivatives of acetylfurans and furancarboxylates with the remote location of functional groups have been developed. Investigation of methanolysis of these compounds in the presence of sodium methoxide showed that total transesterification of acetates is achieved only with an equivalent amount of base due to high acidity of furan alcohols

  摘要 开发了具有远程功能基团的乙酰呋喃和呋喃甲酸酯的膦酰甲基化乙酰氧基甲基衍生物的合成方法。对这些化合物在甲醇钠存在下的甲醇分解的研究表明，由于呋喃醇的高酸度，仅使用等量的碱即可实现乙酸酯的完全酯交换。如果乙酰氧基甲基位于呋喃环的3位，而二乙氧基磷酰甲基位于2位，则在反应过程中会发生P-C键的断裂。如果膦酰基甲基位于3位，乙酰氧基甲基占据2位或4位，则膦酸酯中的酯基发生酯交换，P-C键不受影响。酯基在任何情况下都被酯交换。根据柯林斯，所得醇被氧化成相应的醛。通过甲基 2-(diethoxyphosphorylmethyl)-5-formylfuran-3-carboxylate 与 2-aminothiophenol 2-furylbenzo[合成了在呋喃环上具有酯和二乙氧基磷酰甲基的d ]噻唑。
• Acylation of diethyl (ethoxycarbonylfuryl)methanephosphonates under the conditions of claisen reaction
  作者：L. M. Pevzner

  DOI：10.1134/s1070363212120067

  日期：2012.12

  O,O-Diethyl (ethoxycarbonylfuryl)methanephosphonates are formylated with ethyl formate in the presence of sodium foil at the methylene group adjacent to phosphorus atom to form sodium salts of phosphonoacetic aldehyde. When the substituents in the furan ring are remote from one another, and also in the case of 3, 4-disubstituted isomer these salts in DMSO solution exist in the carbanion form. Anions of salts of (2-ethoxycarbonylfur-3-yl)phosphonoacetic aldehyde and the isomer with the reversed location of substituents in DMSO solution take part in the dynamic equilibrium between the carbanion and the enolate form. The alkylation of all salts obtained with allyl bromide and dimethyl sulfate proceeds exclusively at the oxygen to form a mixture of Z- and E-isomers of phosphorylated vinyl ethers.