二氟马来酸酐 | 669-78-3

• 物质功能分类: 化学试剂 - 有机试剂 - 羧酸酐
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 中文名称: 二氟马来酸酐
• 中文别名: 3,4-二氟马来酸酐
• 英文名称: difluoromaleic anhydride
• 英文别名: difluoro-maleic acid anhydride；Difluor-maleinsaeure-anhydrid；3,4-difluoro-furan-2,5-dione；Difluormaleinsaeure-anhydrid；Difluormaleinsaeureanhydrid；3,4-difluorofuran-2,5-dione
• CAS: 669-78-3
• 化学式: C₄F₂O₃
• mdl: MFCD09867910
• 分子量: 134.039
• InChiKey: DZTLWXJLPNCYDV-UHFFFAOYSA-N

物化性质

• 熔点：
  20 °C
• 沸点：
  128 °C
• 密度：
  1.66±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 海关编码：
  2917190090

反应信息

• 作为反应物：
  描述：

  二氟马来酸酐 在 水 作用下， 以 四氢呋喃 为溶剂， 生成 difluoromaleic acid
  参考文献：
  名称：

  Hydrogen-Bond Symmetry in Difluoromaleate Monoanion

  摘要：

  The symmetry of the hydrogen bond in hydrogen difluoromaleate monoanion is probed by X-ray crystallography and by the NMR method of isotopic perturbation in water, in two aprotic organic solvents, and in an isotropic liquid crystal. The X-ray crystal structure of potassium hydrogen difluoromaleate shows a remarkably short O-O distance of 2.41 angstrom and equal O-H distances of 1.206 angstrom, consistent with a strong and symmetric hydrogen bond. Incorporation of O-18 into one carboxyl group allows investigation of the symmetry of the H-bond in solution by the method of isotopic perturbation. The F-19 NMR spectra of the mono-O-18-substituted monoanion in water, CD2Cl2, and CD3CN show an AB spin system, corresponding to fluorines in different environments. The difference is attributed to the perturbation of the acidity of a carboxylic acid by O-18, not to the mere presence of the O-18, because the mono-O-18 dianion shows equivalent fluorines. Therefore, it is concluded that the monoanion exists as an equilibrating pair of interconverting tautomers and not as a single symmetric structure not only in water but also in organic solvents. However, in the isotropic liquid crystal phase of 4-cyanophenyl 4-heptylbenzoate, tetrabutylammonium hydrogen difluoromaleate-O-18 shows equivalent fluorines, consistent with a single symmetric structure. These results support earlier studies, which suggested that the symmetry of hydrogen bonds can be determined by the local environment.

  DOI：

  10.1021/ja2117848
• 作为产物：
  描述：

  difluoromaleic acid 在 四磷十氧化物 作用下， 以40%的产率得到二氟马来酸酐
  参考文献：
  名称：

  溶液中氢键对称性的同位素扰动 NMR 研究：OHO 和 ODO 氢键的温度依赖性和比较

  摘要：

  氢键是对称的，氢位于两个供体原子之间，还是不对称的，氢更靠近一个但跳到另一个？同位素扰动的 NMR 方法已被用于区分这些。以前同位素变化的证据表明，多种二羧酸单阴离子是不对称的，以互变异构体的快速平衡混合物形式存在。然而，跨非谐势能表面的氢轨迹计算可以重现观察到的邻苯二甲酸酯单阴离子的同位素位移。因此得出的结论是，这些同位素位移与对称势能表面上同位素诱导的去对称化一致。为了区分这两种解释，18O 诱导的同位素对环己烯-1 的 13C NMR 化学位移的影响，已经研究了氯仿-d 中的 2-二羧酸单阴离子和二氟马来酸单阴离子在 D2O 中的 19F NMR 化学位移。在这两种情况下，同位素效应在较低温度下更大，氢键中也有氘。得出的结论是，这些行为与不对称互变异构体之间平衡的扰动一致，与对称势能表面上同位素诱导的去对称化不一致。

  DOI：

  10.1021/jacs.9b08492

文献信息

• Process for the preparation of difluoromaleic anhydride
  申请人：E. I. Du Pont de Nemours and Company

  公开号：US05112993A1

  公开（公告）日：1992-05-12

  A process for producing difluoromaleic anhydride by reacting sulfur trioxide with a fluorinated precursor selected from the group consisting of hexafluoro-2,5-dihydrofuran, hexafluoro-2,5-dihydrothiophene, difluoro-2,5-dihydrothiophene-2,5-dione and tetrafluoro-2,5-dihydrothiophene-2-one. Also disclosed are the compounds difluoro-2,5-dihydrothiophene-2,5-dione and tetrafluoro-2,5-dihydrothiophene-2-one. Difluoromaleic anhydride is useful for example as a component of fluoropolymers.

  通过将三氧化硫与来自包括六氟-2,5-二氢呋喃、六氟-2,5-二氢噻吩、二氟-2,5-二氢噻吩-2,5-二酮和四氟-2,5-二氢噻吩-2-酮的氟化前体之一反应，制备二氟马来酸酐的方法。还披露了化合物二氟-2,5-二氢噻吩-2,5-二酮和四氟-2,5-二氢噻吩-2-酮。例如，二氟马来酸酐可用作氟聚合物的组分。
• [EN] TRIAZOLE DERIVATIVES AS WNT SIGNALING PATHWAY INHIBITORS<br/>[FR] DÉRIVÉS DE TRIAZOLE EN TANT QU'INHIBITEURS DE LA VOIE DE SIGNALISATION WNT
  申请人：OSLO UNIVERSITY HOSPITAL HF

  公开号：WO2012076898A1

  公开（公告）日：2012-06-14

  The present invention relates to compounds of formula (I), to processes for their preparation, to pharmaceutical formulations containing such compounds and to their use in therapy: Such compounds find particular use in the treatment and/or prevention of conditions or diseases which are affected by over-activation of signaling in the Wnt pathway and increased presence of nuclear β-catenin. For example, these may be used in preventing and/or retarding proliferation of tumor cells and metastasis, for example carcinomas such as colon carcinomas.

  本发明涉及公式(I)的化合物，其制备方法，含有这些化合物的药物配方以及它们在治疗中的应用：这些化合物在治疗和/或预防受Wnt途径信号过度激活和核β-连接蛋白存在增加影响的疾病或病症方面具有特殊用途。例如，这些化合物可用于预防和/或延缓肿瘤细胞和转移的增殖，例如结肠癌等癌症。
• Difluoromaleic anhydride as a source of matrix isolated difluoropropadienone, difluorocyclopropenone and difluoroacetylene
  作者：John C. Brahms、William P. Dailey

  DOI：10.1021/ja00206a039

  日期：1989.11

  A 240 nm, reaction de la difluoro-3,4 dihydro-2,5 furannedione-2,5. Obtention de la difluoro-2,3 cyclopropenone, du difluoro acetylene et de la difluoro-3,3 propanedienone

  A 240 nm，反应 de la difluoro-3,4 dihydro-2,5 furannedione-2,5。获得 de la difluoro-2,3 cyclopropenone, du difluoroacetylene et de la difluoro-3,3 propanedienone
• Synthesis of the first fluorinated cantharidin analogues
  作者：Michael Essers、Birgit Wibbeling、Günter Haufe

  DOI：10.1016/s0040-4039(01)01056-5

  日期：2001.8

  time. The key step in each synthesis is an exo-selective Diels–Alder reaction of furan with the appropriate fluorinated maleic anhydride. 17O NMR measurements of 5–7 and the corresponding non-fluorinated parent compounds were undertaken to show the influence of the fluorine substituent(s) on the electronic properties of the oxygen atoms.

  氟化邻苯二酚类似物（4 – 7）是首次合成。在每个合成的关键步骤是一个外的呋喃-选择性狄尔斯-阿尔德反应与合适的氟化的马来酸酐。17个的O- NMR测量5 - 7和相应的非氟化的母体化合物开展了以显示氟取代基的在氧原子的电子性能的影响（多个）。
• Process for the preparation of difluoromaleic anhydride and intermediate
  申请人：E. I. Du Pont de Nemours and Company

  公开号：US05235069A1

  公开（公告）日：1993-08-10

  A process for producing difluoromaleic anhydride by reacting sulfur trioxide with a fluorinated precursor selected from the group consisting of hexafluoro-2,5-dihydrofuran, hexafluoro-2,5-dihydrothiophene, difluoro-2,5-dihydrothiophene-2,5-dione and tetrafluoro-2,5-dihydrothiophene-2-one. Also disclosed are the compounds difluoro-2,5-dihydrothiophene-2,5-dione and tetrafluoro-2,5-dihydrothiophene-2-one.

  一种通过将三氧化硫与选择自六氟-2,5-二氢呋喃、六氟-2,5-二氢噻吩、二氟-2,5-二氢噻吩-2,5-二酮和四氟-2,5-二氢噻吩-2-酮的氟化前体反应制备二氟马来酸酐的方法。本发明还公开了化合物二氟-2,5-二氢噻吩-2,5-二酮和四氟-2,5-二氢噻吩-2-酮。