ethyl 2-ethoxymethylidene-4,4,5,5,6,6,6-heptafluoro-3-oxohexanoate | 1029076-35-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: ethyl 2-ethoxymethylidene-4,4,5,5,6,6,6-heptafluoro-3-oxohexanoate
• 英文别名: ethyl 2-ethoxymethylidene-3-oxo-3-heptafluoropropylpropionate；Ethyl 2-ethoxymethylidene-4,4,5,5,6,6,6-hepta-fluoro-3-oxohexanoate；ethyl 2-(ethoxymethylidene)-4,4,5,5,6,6,6-heptafluoro-3-oxohexanoate
• CAS: 1029076-35-4
• 化学式: C₁₁H₁₁F₇O₄
• 分子量: 340.195
• InChiKey: PCUONLCWRSHAKC-UHFFFAOYSA-N

物化性质

• 沸点：
  142-144 °C(Press: 15-17 Torr)
• 密度：
  1.367±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  ethyl 2-ethoxymethylidene-4,4,5,5,6,6,6-heptafluoro-3-oxohexanoate 以 四氢呋喃 、 溶剂黄146 为溶剂， 生成 ethyl 7-(1,1,2,2,3,3,3-heptafluoropropyl)-2-hydroxypyrazolo[1,5-a]pyrimidin-6-carboxylate
  参考文献：
  名称：

  Peculiarities of cyclization of ethyl 2-ethoxymethylene-3-oxo-3-(polyfluoroalkyl)propionates with 3-amino-5-hydroxypyrazole

  摘要：

  The reactions of ethyl 2-ethoxymethylene-3-oxo-3-(polyfluoroalkyl)propionates with 3-amino-5-hydroxypyrazole result in ethyl 2,7-dihydroxy-7-(polyfluoroalkyl)-4,7-dihydropyrazolo[1,5-a]pyrimidin-6-carboxylates under mild conditions. These products undergo recyclization in refluxing ethanol to form ethyl 3-hydroxy-4-(polyfluoroalkyl)-1H-pyrazolo[3,4-b]pyridin-5-carboxylates, whereas in refluxing glacial acetic acid they are dehydrated to ethyl 2-hydroxy-7-(polyfluoroalkyl)pyrazolo[1,5-a]pyrimidin-6-carboxylates. The non-fluorinated ethyl 2-ethoxymethylene-3-oxo esters in the reactions with 3-amino-5-hydroxypyrazole in ethanol (or glacial acetic acid) under reflux form only ethyl 2-hydroxy-7-phenyl(hydroxy)pyrazolo[1,5-c]pyrimidin-6-carboxylates. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2013.01.005
• 作为产物：
  描述：

  七氟丁酰基乙酸乙酯 、 原甲酸三乙酯 在 乙酸酐 作用下， 生成 ethyl 2-ethoxymethylidene-4,4,5,5,6,6,6-heptafluoro-3-oxohexanoate
  参考文献：
  名称：

  1,3-二羰基化合物的水溶性2-氨基亚甲基衍生物的合成及性能

  摘要：

  从相应的2-乙氧基亚甲基衍生物和N，N-二甲基乙二胺开始，首次合成了一系列[（2-二甲基氨基）乙基氨基]亚甲基-1，3-二羰基化合物。结果表明，氨基亚甲基衍生物与甲基碘的进一步烷基化在叔氮原子上区域选择性地发生。所得的季铵化产物在盐酸介质中对低碳钢具有较高的腐蚀抑制作用。

  DOI：

  10.1134/s1070363213070050

文献信息

• Synthesis and complexing ability of 2-(2-ethoxycarbonyl-3-oxo-3-polyfluoroalkylprop-1-enylamino) benzoic acids
  作者：Yu. S. Kudyakova、M. V. Goryaeva、Ya. V. Burgart、V. I. Saloutin、P. A. Slepukhin

  DOI：10.1007/s11172-009-0161-9

  日期：2009.6

  The condensation of ethyl 2-ethoxymethylidene-3-oxo-3-polyfluoroalkylpropionates with 2-aminobenzoic acid occurs at the ethoxymethylidene substituent and gives 2-(2-ethoxy-carbonyl-3-oxo-3-polyfluoroalkylprop-1-enylamino)benzoic acids. These compounds serve as new O,N,O-tridentate ligands capable of forming nickel(ii) and copper(ii) complexes.

  2-ethoxymethylidene-3-oxo-3-polyfluoroalkylpropionates 与 2-aminobenzoic acid 的缩合发生在亚乙氧基亚甲基上，并得到 2-(2-ethoxy-carbonyl-3-oxo-3-polyfluoroalkylprop-1-enylamino)苯甲酸。这些化合物作为新的 O，N，O-三叉配体，能够形成镍（ii）和铜（ii）络合物。
• Synthesis of pyrimidine derivatives based on ethyl 2-ethoxymethylidene-3-polyfluoroalkyl-3-oxopropionates and urea
  作者：M. V. Goryaeva、Ya. V. Burgart、V. I. Saloutin

  DOI：10.1007/s11172-009-0164-6

  日期：2009.6

  Ethyl 2-ethoxymethylidene-3-polyfluoroalkyl-3-oxopropionates under mild conditions undergo regioselective condensation with urea at the ethoxymethylidene substituent giving rise to ethyl 3-polyfluoroalkyl-3-oxo-2-(ureidomethylidene)propionates. Under more drastic conditions, the latter cyclize at the fluoroacyl fragment to form ethyl 4-polyfluoroalkyl-4-hydroxy-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates.

  在温和条件下，2-乙氧基亚甲基-3-聚氟烷基-3-氧代丙酸乙酯在乙氧基亚甲基取代基上与脲发生区域选择性缩合，生成 3-聚氟烷基-3-氧代-2-(脲亚甲基)丙酸乙酯。在更苛刻的条件下，后者会在氟酰基片段发生环化反应，生成 4-聚氟烷基-4-羟基-2-氧代-1,2,3,4-四氢嘧啶-5-羧酸乙酯。
• New enamine ligands derived from ethyl 2-ethoxymethylidene-3-oxo-3-polyfluoroalkylpropionates and o-phenylenediamine
  作者：Yu. S. Kudyakova、M. V. Goryaeva、Ya. V. Burgart、P. A. Slepukhin、V. I. Saloutin

  DOI：10.1007/s11172-010-0281-2

  日期：2010.8

  Diethyl 2,2′ [1,2-phenylenebis(aminomethylidene)]bis(3-oxo-3-polyfluoroalkylpropionates) were synthesized by the condensation of a double excess of ethyl 2-ethoxymethylidene- 3-oxo-3-polyfluoroalkylpropionates with o-phenylenediamine. The use of equimolar ratios of the starting reactants affords ethyl 2-[(2-aminophenyl)aminomethylidene]-3-oxo- 3-polyfluoroalkylpropionates from which nonsymmetric biscondensation

  2,2' [1,2-亚苯基双(氨基亚甲基)]双(3-氧代-3-多氟烷基丙酸酯)二乙酯是通过双过量的2-乙氧基亚甲基-3-氧代-3-多氟烷基丙酸酯与邻-苯二胺。使用等摩尔比的起始反应物得到2-[(2-氨基苯基)氨基亚甲基]-3-氧代-3-多氟烷基丙酸乙酯，通过与含有不同多氟烷基取代基的相关反应物反应，从中合成非对称双缩合产物。铜(II)、镍(II)和钴(II)配合物是在新配体的基础上获得的。
• Synthesis of Fluoroalkylated Dihydroazolo[1,5-a]pyrimidines and Their Ring-Chain Isomerism
  作者：Marina V. Goryaeva、Yanina V. Burgart、Victor I. Saloutin、Elena V. Sadchikova、Evgeny N. Ulomskii

  DOI：10.3987/com-08-11524

  日期：——

  polyfluoroalkylated dihydroazolo[1,5-a]pyrimidines. The latter are subject to ring-chain isomerisation in solutions depending on the solvent and the "length" of the fluoroalkyl substituent to yield ethyl 3-polyfluoroalkyl-3-oxo-2-[(azol-3-yl)aminomethylidene]propionates via opening of the heterocycle at the C-N bond. Dehydration of dihydroazolo[1,5-a]pyrimidine were realized.

  2-乙氧基亚甲基-3-多氟烷基-3-氧代丙酸乙酯与3-氨基-1H-[1,2,4]三唑、3-氨基-5-甲基吡唑、3-氨基吡唑-4-甲酸乙酯和乙酯的环化5-氨基咪唑-4-羧酸盐酸盐导致形成多氟烷基化二氢唑并[1,5-a]嘧啶。后者根据溶剂和氟烷基取代基的“长度”在溶液中进行环链异构化，通过开环产生 3-多氟烷基-3-氧代-2-[(azol-3-yl)氨基亚甲基]丙酸乙酯CN 键上的杂环。实现了二氢唑并[1,5-a]嘧啶的脱水。
• Ring-chain isomerism of ethyl 7-polyfluoroalkyl-7-hydroxy-4,7-dihydro[1,2,4]triazolo[1,5-a]pyrimidine-6-carboxylates
  作者：Marina V. Pryadeina、Yanina V. Burgart、Viktor I. Saloutin、Oleg N. Chupakhin

  DOI：10.1016/j.mencom.2008.09.017

  日期：2008.9

  Cyclisation of ethyl 2-ethoxymethylidene-3-oxo-3-polyfluoroalkylpropionates with 3-amino-1H-[1,2,4]triazole gives ethyl 7-polyfluoroalkyl-7-hydroxy-4,7-dihydro[1,2,4]triazolo[1,5-a]pyrimidine-6-carboxylates that are subject to ring-chain isomerisation in solution, depending on the solvent and the length of the polyfluoroalkyl substituent, to yield ethyl 3-polyfluoroalkyl-3-oxo2-([1,2,4]triazol-3-yl)aminomethylidene}propionates via heterocyclic ring opening at the C(7)-N(8) bond.