ethyl 2-ethoxymethylidene-4,4,5,5-tetrafluoro-3-oxopentanoate | 1029076-33-2

• 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-tetrafluoro-3-oxopentanoate
• 英文别名: Ethyl 2-ethoxymethylidene-4,4,5,5-tetrafluoro-3-oxo-pentanoate；ethyl 2-(ethoxymethylidene)-4,4,5,5-tetrafluoro-3-oxopentanoate
• CAS: 1029076-33-2
• 化学式: C₁₀H₁₂F₄O₄
• 分子量: 272.196
• InChiKey: KZRSFHNBGHHDLZ-UHFFFAOYSA-N

物化性质

• 沸点：
  135-140 °C(Press: 115-117 Torr)
• 密度：
  1.258±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  ethyl 2-ethoxymethylidene-4,4,5,5-tetrafluoro-3-oxopentanoate 以 四氢呋喃 、 乙醇 为溶剂， 生成 ethyl 2-hydroxy-7-(1,1,2,2-tetrafluoroethyl)pyrazolo[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：

  原甲酸三乙酯 、 反应 1.0h， 以66%的产率得到ethyl 2-ethoxymethylidene-4,4,5,5-tetrafluoro-3-oxopentanoate
  参考文献：
  名称：

  Synthesis and structure of 2-ethoxy- and 2-aminomethylidene-3-fluoroalkyl-3-oxopropionates

  摘要：

  Condensation of ethyl 3-polyfluoroalkyl-3-oxopropionates with excess triethyl orthoformate gave ethyl 3-polyfluoroalkyl-2-ethoxymethylidene-3-oxopropionates which reacted with primary aliphatic, aromatic, and heterocyclic amines to form ethyl 2-alkyl(aryl, hetaryl)aminomethylidene-3-polyfluoroalkyl-3-oxopropionates. According to the X-ray diffraction and IR data, the latter exist in the crystalline state as the corresponding E isomers, while in solution (NMR data), as mixtures of Z and E isomers. Condensation of ethyl 2-ethoxymethylidene-3-oxopropionates with secondary heterocyclic amines (morpholine and pyrrolidine) led to the formation of 2-morpholino(pyrrolidin-1-yl)methylidene-3-fluoroalkyl-3-oxopropionates which were shown to exist as Z isomers both in the crystalline state and in solution.

  DOI：

  10.1134/s1070428007070019

文献信息

• The reactions of 2-ethoxymethylidene-3-oxo esters and their analogues with 5-aminotetrazole as a way to novel azaheterocycles
  作者：Marina V Goryaeva、Yanina V Burgart、Marina A Ezhikova、Mikhail I Kodess、Viktor I Saloutin

  DOI：10.3762/bjoc.11.44

  日期：——

  The interaction of 2-ethoxymethylidene-3-oxo esters and their analogues with 5-aminotetrazole is an efficient synthetic approach to novel azaheterocycles. 2-Ethoxymethylidene-3-oxo esters bearing alkyl substituents react with 5-aminotetrazole to form ethyl 2-azido-4-alkylpyrimidine-5-carboxylates which are capable of subsequent nucleophilic substitution. The use of diethyl 2-ethoxymethylidenemalonate in this reaction resulted in ethyl 7-hydroxytetrazolo[1,5-a]pyrimidine-6-carboxylate, while ethyl 2-ethoxymethylidenecyanoacetate yielded 5-[2,6-diamino-3,5-bis(ethoxycarbonyl)pyridinium-1-yl]tetrazol-1-ide through an alternative pathway. Ethyl 2-benzoyl-3-ethoxyprop-2-enoate reacted with 5-aminotetrazole by two reaction routes to form ethyl 2-benzoyl-3-(1H-tetrazol-5-ylamino)prop-2-enoate and ethyl 7-(1-ethoxy-1,3-dioxo-3-phenylpropan-2-yl)-5-phenyl-4,7-dihydrotetrazolo[1,5-a]pyrimidine-6-carboxylate.

  2-乙氧甲基亚甲基-3-酮基酯及其类似物与5-氨基四唑的相互作用是一种有效的合成新型氮杂环化合物的方法。带有烷基取代基的2-乙氧甲基亚甲基-3-酮基酯与5-氨基四唑反应，形成乙酰基2-氮杂嘧啶-5-羧酸酯，这些化合物能够进行进一步的亲核取代反应。在此反应中使用二乙酰乙二酯，可以得到乙酰基7-羟基四唑并环[1,5-a]嘧啶-6-羧酸乙酯，而使用乙酸乙酯基2-乙氧甲基亚甲基丙烯酸酯，则通过另一种途径生成5-[2,6-二氨基-3,5-双(乙氧羰基)吡啶-1-基]四唑-1-化物。乙酰基2-苯甲酰基-3-乙氧基丙烯酸酯通过两种反应途径与5-氨基四唑反应，形成乙酰基2-苯甲酰基-3-(1H-四唑-5-基)丙烯酸酯和乙酯基7-(1-乙氧基-1,3-二氧杂环戊烷-3-苯基丙基)-5-苯基-4,7-二氢四唑并环[1,5-a]嘧啶-6-羧酸乙酯。
• 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。