7,7-difluoronadic dimethyl ester | 1310675-20-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 7,7-difluoronadic dimethyl ester
• 英文别名: dimethyl (1R,2R,3S,4S)-7,7-difluorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
• CAS: 1310675-20-7
• 化学式: C₁₁H₁₂F₂O₄
• 分子量: 246.211
• InChiKey: GYKNBSVCWKJGKX-SOSBWXJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• 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：
  6

反应信息

• 作为反应物：
  描述：

  7,7-difluoronadic dimethyl ester 在 potassium carbonate 、 盐酸 作用下， 以 甲醇 、 水 为溶剂， 反应 120.0h， 以84%的产率得到anti-7,7-difluoro-5-norbornene-2-endo,3-exo-dicarboxylic acid
  参考文献：
  名称：

  The synthesis of fluorinated endcaps: Part 1. The effect of C-7 fluorination on the base-catalyzed monohydrolysis of 5-norbornenyl-2,3-diesters

  摘要：

  In an attempt to improve the thermo-oxidative stability of aerospace polyimides, we have explored the preparation of 7-fluorinated nadic endcaps. The latter are 5-norbonenyl acid esters in a 2-endo,3-endo configuration, which is required for imidization. The most obvious precursor is the corresponding diester and, hence, we carried out a preliminary study of the saponification of the symmetric dimethyl esters of various 7-mono- and 7,7-disubstituted nadic acids (5-norbornenyl-2-endo,3-endo-dicarboxylic acids). These included the 7-fluoro (7c) and 7,7-difluoro (7e) derivatives, as well as the 7,7-diprotio (7a), 7-hydroxy (7b) and 7-oxo (7d) analogs for the purpose of comparison. Contrary to previous reports, and depending on the substitution pattern and the basic conditions used, various amounts of hydrolysis and configuration inversion were observed giving various yields of 2-endo,3-endo monoacid monoesters 8, 2-endo,3-exo monoacids monoester 13, 2-endo,3-endo diacids 6, and/or 2-endo,3-exo diacids 15. Interestingly, the inversion in configuration always occurred at C-3 - i.e., on the carbon alpha to the remaining ester - and the 2-exo,3-endo acid ester 14 was not observed. Overall, the order of increasing configuration inversion is dependant on the C-7-substituent(s) with H-2 < OH

  DOI：

  10.1016/j.jfluchem.2013.01.029
• 作为产物：
  描述：

  7-oxonadic acid 在 乙醇 、 二乙胺基三氟化硫 作用下， 以 乙醚 、 二氯甲烷 、 丙酮 为溶剂， 反应 4.0h， 生成 7,7-difluoronadic dimethyl ester
  参考文献：
  名称：

  降冰片烯C 7桥的立体特异性单氟化和二氟化

  摘要：

  在半导体和高温聚酰亚胺工业中，氟化降冰片烯是非常理想的单体。我们在这里描述了一种合成策略，用于降冰片烯系统中C 7碳的立体定向单氟化或二氟化，从7酮基酸酐1开始。特别地，抗-7-氟甲基二酯4及其7,7-二氟萘类似物7可以从3步或4步中的1步制备：皂化，还原（对于4），酯化，用DAST氟化。另外，由环氧化物14获得抗-7-氟-顺-7-氟甲基二酯16。，以及来自酮15的7,7-二氟双环[2.2.2]辛-5-烯-2,3-二羧酸二甲酯（17）。降冰片烯双键的对映体辅助可引导引入立体定向抗烯键的攻击性氟阴离子。

  DOI：

  10.1016/j.jfluchem.2011.03.009

文献信息

• Stereospecific mono- and difluorination of the C7-bridge of norbornenes
  作者：David E. Rajsfus、Sari Alter-Zilberfarb、Pessia Sharon、Mary Ann B. Meador、Aryeh A. Frimer

  DOI：10.1016/j.jfluchem.2011.03.009

  日期：2011.5

  describe herein a synthetic strategy for the stereospecific mono- or difluorination of the C7-carbon in norbornene systems beginning with 7-ketonadic anhydride 1. In particular, anti-7-fluoro methyl diester 4 and its 7,7-difluoronadic analog 7 can be prepared from 1 in 3 or 4 steps: saponification, reduction (for 4), esterification, fluorination with DAST. In addition, anti-7-fluoro-syn-7-fluoromethylnadic

  在半导体和高温聚酰亚胺工业中，氟化降冰片烯是非常理想的单体。我们在这里描述了一种合成策略，用于降冰片烯系统中C 7碳的立体定向单氟化或二氟化，从7酮基酸酐1开始。特别地，抗-7-氟甲基二酯4及其7,7-二氟萘类似物7可以从3步或4步中的1步制备：皂化，还原（对于4），酯化，用DAST氟化。另外，由环氧化物14获得抗-7-氟-顺-7-氟甲基二酯16。，以及来自酮15的7,7-二氟双环[2.2.2]辛-5-烯-2,3-二羧酸二甲酯（17）。降冰片烯双键的对映体辅助可引导引入立体定向抗烯键的攻击性氟阴离子。
• The synthesis of fluorinated endcaps: Part 1. The effect of C-7 fluorination on the base-catalyzed monohydrolysis of 5-norbornenyl-2,3-diesters
  作者：David E. Rajsfus、Sari Alter-Zilberfarb、Aryeh A. Frimer

  DOI：10.1016/j.jfluchem.2013.01.029

  日期：2013.4

  In an attempt to improve the thermo-oxidative stability of aerospace polyimides, we have explored the preparation of 7-fluorinated nadic endcaps. The latter are 5-norbonenyl acid esters in a 2-endo,3-endo configuration, which is required for imidization. The most obvious precursor is the corresponding diester and, hence, we carried out a preliminary study of the saponification of the symmetric dimethyl esters of various 7-mono- and 7,7-disubstituted nadic acids (5-norbornenyl-2-endo,3-endo-dicarboxylic acids). These included the 7-fluoro (7c) and 7,7-difluoro (7e) derivatives, as well as the 7,7-diprotio (7a), 7-hydroxy (7b) and 7-oxo (7d) analogs for the purpose of comparison. Contrary to previous reports, and depending on the substitution pattern and the basic conditions used, various amounts of hydrolysis and configuration inversion were observed giving various yields of 2-endo,3-endo monoacid monoesters 8, 2-endo,3-exo monoacids monoester 13, 2-endo,3-endo diacids 6, and/or 2-endo,3-exo diacids 15. Interestingly, the inversion in configuration always occurred at C-3 - i.e., on the carbon alpha to the remaining ester - and the 2-exo,3-endo acid ester 14 was not observed. Overall, the order of increasing configuration inversion is dependant on the C-7-substituent(s) with H-2 < OH