6-difluoromethyl-4-oxo-4H-pyran-2-carboxylic acid | 1083402-18-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 6-difluoromethyl-4-oxo-4H-pyran-2-carboxylic acid
• 英文别名: 6-(difluoromethyl)comanic acid；6-[difluoromethyl]comanic acid；6-difluoromethylcomanic acid；6-(Difluoromethyl)-4-oxo-4H-pyran-2-carboxylic acid；6-(difluoromethyl)-4-oxopyran-2-carboxylic acid
• CAS: 1083402-18-9
• 化学式: C₇H₄F₂O₄
• mdl: MFCD08447733
• 分子量: 190.103
• InChiKey: YDEDDZCIGHZUAK-UHFFFAOYSA-N

物化性质

• 熔点：
  202-203 °C
• 沸点：
  326.0±42.0 °C(Predicted)
• 密度：
  1.600±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6-difluoromethyl-4-oxo-4H-pyran-2-carboxylic acid 以77%的产率得到2-difluoromethyl-4H-pyran-4-one
  参考文献：
  名称：

  First synthesis of 4-oxo-6-trifluoromethyl-4H-thiopyran-2-carboxylic acid and its derivatives

  摘要：

  用硫氢化钠处理6-三氟甲基香豆酸，首次得到4-氧代-6-三氟甲基-4H-噻喃-2-甲酸（6-三氟甲基硫代香豆酸）。当加热或用 H2SO4 处理时，该酸很容易发生脱羧反应，生成 2-三氟甲基-4H-噻喃-4-酮。因此，6-三氟甲硫代康马酸乙酯和甲酯的产率较低（15-23%）。 6-三(二)氟甲基香豆酸脱羧得到2-三(二)氟甲基-4H-吡喃-4-酮，产率77-80%。

  DOI：

  10.1007/s11172-010-0171-7
• 作为产物：
  描述：

  ethyl 6-difluoromethyl-4-oxo-4H-pyran-2-carboxylate 在 盐酸 、 水 作用下， 反应 1.0h， 以88%的产率得到6-difluoromethyl-4-oxo-4H-pyran-2-carboxylic acid
  参考文献：
  名称：

  First synthesis of 4-oxo-6-trifluoromethyl-4H-thiopyran-2-carboxylic acid and its derivatives

  摘要：

  用硫氢化钠处理6-三氟甲基香豆酸，首次得到4-氧代-6-三氟甲基-4H-噻喃-2-甲酸（6-三氟甲基硫代香豆酸）。当加热或用 H2SO4 处理时，该酸很容易发生脱羧反应，生成 2-三氟甲基-4H-噻喃-4-酮。因此，6-三氟甲硫代康马酸乙酯和甲酯的产率较低（15-23%）。 6-三(二)氟甲基香豆酸脱羧得到2-三(二)氟甲基-4H-吡喃-4-酮，产率77-80%。

  DOI：

  10.1007/s11172-010-0171-7

文献信息

• Reactions of 2-Mono- and 2,6-Disubstituted 4-Pyrones with Phenylhydrazine as General Method for the Synthesis of 3-(N-Phenylpyrazolyl)Indoles
  作者：D. L. Obydennov、B. I. Usachev、V. Ya. Sosnovskikh

  DOI：10.1007/s10593-014-1603-3

  日期：2015.1

  in protic and aprotic solvents, leading to phenylhydrazones of 3-(3-R-1-phenylpyrazol-5-yl)- or 3-(5-R-1-phenylpyrazol-3-yl)pyruvic acids (or esters), respectively. 6-Di(tri)fluoromethylcomanic acids (or esters) reacted analogously, forming the corresponding phenylhydrazones with RF group in the side chain. The obtained phenylhydrazones underwent Fischer reaction under acidic conditions, forming the

  苯肼在质子和非质子溶剂中与6-取代的4-吡喃-2-羧酸（或酯）发生区域选择性反应，生成3-（3-R-1-苯基吡唑-5-基）-或3-（5 -R-1-苯基吡唑-3-基）丙酮酸（或酯）。6-二（三）氟甲基甲酸酯（或酯）类似地反应，形成具有R F的相应苯hydr组在侧链中。所得的苯Fi在酸性条件下进行费歇尔反应，形成各自的3-（N-苯基吡唑基）吲哚。与马来酸及其酯相反，2-取代的4-吡喃酮的反应非选择性地发生，并给出了区域异构的吡唑与侧链上的苯基hydr基团或3-（N-苯基吡唑基）吲哚的混合物。提出了一种机制来解释溶剂对反应过程的影响。
• Regioselective synthesis of 2- and 5-trifluoromethyl-or 2- and 5-difluoromethylpyrazolo[1,5-c]pyrimidines based on 7,7,7-trifluoro-or 7,7-difluoro-2,4,6-trioxoheptanoic and 6-trifluoromethyl-or 6-difluoromethylcomanic acids
  作者：B. I. Usachev、D. L. Obydennov、V. Ya. Sosnovskikh

  DOI：10.1007/s11172-012-0212-5

  日期：2012.8

  6-Tri- and 6-difluoromethylcomanic acids and their ethyl esters reacted with aminoguanidine, predominantly giving 5-RF-pyrazolo[1,5-c]pyrimidines, whereas the reaction of the openchain synthetic equivalents, i.e., ethyl 7,7,7-trifluoro- and 7,7-difluoro-2,4,6-trioxoheptanoates, with this polynucleophile allowed us to obtain regioselectively 2-RF-pyrazolo[1,5-c]pyrimidines.

  6-三氟和 6-二氟甲基烟酸及其乙酯与氨基胍反应，主要生成 5-RF-吡唑并[1,5-c]嘧啶，而开链合成等价物，即7,7,7-三氟和 7,7-二氟-2,4,6-三氧代庚酸乙酯与这种多核亲和剂的反应，使我们能够获得具有区域选择性的 2-RF-吡唑并[1,5-c]嘧啶。
• Reactions of 6-(tri- and 6-(difluoromethyl))comanic acids and their ethyl esters with aniline and its 2-substituted derivatives
  作者：Dmitrii L. Obydennov、Boris I. Usachev

  DOI：10.1016/j.jfluchem.2012.06.003

  日期：2012.9

  Reactions of 6-(tri- and 6-(difluoromethyl))comanic acids with aniline, o-phenylenediamine and o-aminophenol were investigated. RF-containing derivatives of 4-pyridones, benzodiazepines and quinoxalinones were synthesized. Electrophilic properties of 6-(trifluoromethyl)comanic acid were evaluated.

  研究了6-（三和6-（二氟甲基））甲酸与苯胺，邻苯二胺和邻氨基苯酚的反应。ř ˚F的4-吡啶酮，苯并二氮杂并喹喔啉酮的含衍生物的合成。评价了6-（三氟甲基）门甲酸的亲电性能。
• The reaction of 6-substituted 4-pyrone-2-carboxylic acids with o-phenylenediamine. Synthesis and structure of 3-(1H-1,5-benzodiazepin-2(3Н)-ylidenemethyl)quinoxalin-2(1H)-ones
  作者：Dmitrii L. Obydennov、Vyacheslav Ya. Sosnovskikh

  DOI：10.1007/s10593-015-1696-3

  日期：2015.3

  [GRAPHICS]6-Aryl(alkyl)-4-pyrone-2-carboxylic acids upon refluxing in n-BuOH react with two equivalents of.-phenylenediamine, giving 26-85% yields of 3-(1H-1,5-benzodiazepin-2(3H)-ylidenemethyl)quinoxalin-2(1H)-ones, which exist in two tautomeric forms. The direction of the initial nucleophilic attack on the pyrone ring and the tautomeric composition of the obtained products is mainly determined by the substituent at the.-6 atom. Quantum-chemical calculations were used to estimate the stability of tautomers in the gas phase.
• First synthesis of 4-oxo-6-trifluoromethyl-4H-thiopyran-2-carboxylic acid and its derivatives
  作者：B. I. Usachev、S. A. Usachev、G.-V. Röschenthaler、V. Ya. Sosnovskikh

  DOI：10.1007/s11172-010-0171-7

  日期：2010.4

  Treatment of 6-trifluoromethylcomanic acid with sodium hydrosulfide afforded for the first time 4-oxo-6-trifluoromethyl-4H-thiopyran-2-carboxylic acid (6-trifluoromethylthiocomanic acid). When heated or treated with H2SO4, this acid easily underwent decarboxylation leading to 2-trifluoromethyl-4H-thiopyran-4-one. Because of this, both ethyl and methyl 6-tri-fluoromethylthiocomanates were obtained in low yields (15–23%). Decarboxylation of 6-tri-(di)fluoromethylcomanic acids gave 2-tri(di)fluoromethyl-4H-pyran-4-ones in 77–80% yields.

  用硫氢化钠处理6-三氟甲基香豆酸，首次得到4-氧代-6-三氟甲基-4H-噻喃-2-甲酸（6-三氟甲基硫代香豆酸）。当加热或用 H2SO4 处理时，该酸很容易发生脱羧反应，生成 2-三氟甲基-4H-噻喃-4-酮。因此，6-三氟甲硫代康马酸乙酯和甲酯的产率较低（15-23%）。 6-三(二)氟甲基香豆酸脱羧得到2-三(二)氟甲基-4H-吡喃-4-酮，产率77-80%。