dimethyl hexafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate | 199917-44-7

• 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: dimethyl hexafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate
• 英文别名: Dimethyl perfluorobicyclo[1,1,1]pentane-1,3-dicarboxylate；dimethyl 2,2,4,4,5,5-hexafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate
• CAS: 199917-44-7
• 化学式: C₉H₆F₆O₄
• 分子量: 292.135
• InChiKey: IGTTXGRJWPYCOQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  dimethyl hexafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate 在 sodium hydroxide 、 溴 、 magnesium sulfate 、 mercury(II) oxide 作用下， 以 甲醇 为溶剂， 反应 37.0h， 生成 1,3-dibromohexafluorobicyclo[1.1.1]pentane
  参考文献：
  名称：

  Preparation, Structure, and Properties of Symmetrically 1,3-Difunctionalized Penta- and Hexafluorobicyclo[1.1.1]pentanes

  摘要：

  Exhaustive direct fluorination of dimethyl bicyclo[1.1.1]pentane-1,3-dicarboxylate leads to dimethyl pentafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate (2) and hexafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate (3). The latter was hydrolyzed to the diacid (4) and converted to the 1,3-dibromo and 1,3-diiodo analogues (5 and 6) by the Hunsdieker reaction followed by treatment with SmI2. Na/NH3 reduction of the disodium salt 10 causes cage C-C bond cleavage. Single-crystal X-ray diffraction analysis of 3 revealed very short nonbonded F-F separations of 2.41 Angstrom and an interbridgehead distance of 1.979 Angstrom, long compared with 1.875 Angstrom in 1,3-diacetylbicyclo[1.1.1]pentane [19; cf. 1.954 Angstrom calculated (MP2/6-31G*) for 2,2,4,4,5,5-hexafluorobicyclo[1.1.1]pentane (13)]. Calculation suggests a strain energy of 101 kcal/mol (MP2/6-31G*) for the hexafluorinated cage, compared with 68 kcal/mol for the parent bicyclo[1.1.1]pentane (20). The remarkably low pK(a) values of 4 [0.73 and 1.34; cf. 3.22 and 4.26 for the parent diacid 24] originate in a direct field effect of fluorine atoms, combined with an increased s character of the exocyclic hybrid orbital on the bridgehead carbon in 4 (calculated 34% in 13) relative to 24 (calculated 30% in 20). Analysis of the strongly coupled nuclear spin systems of 2 and 3, based on a combination of two-dimensional NMR, spectral simulations, and GIAO-HF/6-31G* calculations of chemical shifts, revealed large and stereospecific long-range H-1-C-13, H-1-F-19, C-13-F-19, and F-19-F-19 spin-spin coupling constants.

  DOI：

  10.1021/ja9710518
• 作为产物：
  描述：

  1,3-二甲酸甲酯双环[1.1.1]戊烷 在 fluorine 作用下， 以 1,1,2-三氯三氟乙烷（CFC-113） 为溶剂， 反应 4.0h， 以40%的产率得到dimethyl hexafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate
  参考文献：
  名称：

  Preparation, Structure, and Properties of Symmetrically 1,3-Difunctionalized Penta- and Hexafluorobicyclo[1.1.1]pentanes

  摘要：

  Exhaustive direct fluorination of dimethyl bicyclo[1.1.1]pentane-1,3-dicarboxylate leads to dimethyl pentafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate (2) and hexafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate (3). The latter was hydrolyzed to the diacid (4) and converted to the 1,3-dibromo and 1,3-diiodo analogues (5 and 6) by the Hunsdieker reaction followed by treatment with SmI2. Na/NH3 reduction of the disodium salt 10 causes cage C-C bond cleavage. Single-crystal X-ray diffraction analysis of 3 revealed very short nonbonded F-F separations of 2.41 Angstrom and an interbridgehead distance of 1.979 Angstrom, long compared with 1.875 Angstrom in 1,3-diacetylbicyclo[1.1.1]pentane [19; cf. 1.954 Angstrom calculated (MP2/6-31G*) for 2,2,4,4,5,5-hexafluorobicyclo[1.1.1]pentane (13)]. Calculation suggests a strain energy of 101 kcal/mol (MP2/6-31G*) for the hexafluorinated cage, compared with 68 kcal/mol for the parent bicyclo[1.1.1]pentane (20). The remarkably low pK(a) values of 4 [0.73 and 1.34; cf. 3.22 and 4.26 for the parent diacid 24] originate in a direct field effect of fluorine atoms, combined with an increased s character of the exocyclic hybrid orbital on the bridgehead carbon in 4 (calculated 34% in 13) relative to 24 (calculated 30% in 20). Analysis of the strongly coupled nuclear spin systems of 2 and 3, based on a combination of two-dimensional NMR, spectral simulations, and GIAO-HF/6-31G* calculations of chemical shifts, revealed large and stereospecific long-range H-1-C-13, H-1-F-19, C-13-F-19, and F-19-F-19 spin-spin coupling constants.

  DOI：

  10.1021/ja9710518

文献信息

• Partially Bridge-Fluorinated Dimethyl Bicyclo[1.1.1]pentane-1,3-dicarboxylates:  Preparation and NMR Spectra
  作者：Alexander B. Shtarev、Evgueni Pinkhassik、Michael D. Levin、Ivan Stibor、Josef Michl

  DOI：10.1021/ja0000495

  日期：2001.4.1

  Direct fluorination of dimethyl bicyclo[1.1.1]pentane-1,3-dicarboxylate, obtained from [1.1.1]propellane prepared by an improved synthetic procedure, furnished esters of 14 of the 15 possible bridge-fluorinated bicyclo[1.1.1]pentane-1,3-dicarboxylic acids, isolated by preparative GC. Calculated geometries reflect the substitution pattern in a regular fashion compatible with Bent's rules. Considerable

  双环[1.1.1]戊烷-1,3-二甲酸二甲酯的直接氟化，从通过改进的合成程序制备的[1.1.1]丙烷获得，提供15种可能的桥氟化双环[1.1.1]中的14种酯戊烷-1,3-二羧酸，通过制备型 GC 分离。计算出的几何图形以与本特规则兼容的常规方式反映替代模式。通过多氟化作用将相当多的额外应变引入双环[1.1.1]戊烷笼中；经计算，六取代可高达 33-35 kcal/mol。氟取代基的三种排列尤其富含应变：成对、邻近和 W 相关。(1)H、(13)C 和 (19)F NMR 光谱表现出惊人的各种化学位移和长程耦合常数。这些与忽略 GIAO-RHF/6-31G//RHF/6-31G 和 GIAO-RHF/6-31G//MP2/6-的所有化学位移的桥头取代基计算的结果非常一致31G 方法和 EOM-CCSD/6-311G//MP2/6-311G 方法的许多耦合常数。近似 (4)J(FF) 常数特别大
• Preparation, Structure, and Properties of Symmetrically 1,3-Difunctionalized Penta- and Hexafluorobicyclo[1.1.1]pentanes
  作者：Michael D. Levin、Steven J. Hamrock、Piotr Kaszynski、Alexander B. Shtarev、Galina A. Levina、Bruce C. Noll、Martin E. Ashley、Richard Newmark、George G. I. Moore、Josef Michl

  DOI：10.1021/ja9710518

  日期：1997.12.1

  Exhaustive direct fluorination of dimethyl bicyclo[1.1.1]pentane-1,3-dicarboxylate leads to dimethyl pentafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate (2) and hexafluorobicyclo[1.1.1]pentane-1,3-dicarboxylate (3). The latter was hydrolyzed to the diacid (4) and converted to the 1,3-dibromo and 1,3-diiodo analogues (5 and 6) by the Hunsdieker reaction followed by treatment with SmI2. Na/NH3 reduction of the disodium salt 10 causes cage C-C bond cleavage. Single-crystal X-ray diffraction analysis of 3 revealed very short nonbonded F-F separations of 2.41 Angstrom and an interbridgehead distance of 1.979 Angstrom, long compared with 1.875 Angstrom in 1,3-diacetylbicyclo[1.1.1]pentane [19; cf. 1.954 Angstrom calculated (MP2/6-31G*) for 2,2,4,4,5,5-hexafluorobicyclo[1.1.1]pentane (13)]. Calculation suggests a strain energy of 101 kcal/mol (MP2/6-31G*) for the hexafluorinated cage, compared with 68 kcal/mol for the parent bicyclo[1.1.1]pentane (20). The remarkably low pK(a) values of 4 [0.73 and 1.34; cf. 3.22 and 4.26 for the parent diacid 24] originate in a direct field effect of fluorine atoms, combined with an increased s character of the exocyclic hybrid orbital on the bridgehead carbon in 4 (calculated 34% in 13) relative to 24 (calculated 30% in 20). Analysis of the strongly coupled nuclear spin systems of 2 and 3, based on a combination of two-dimensional NMR, spectral simulations, and GIAO-HF/6-31G* calculations of chemical shifts, revealed large and stereospecific long-range H-1-C-13, H-1-F-19, C-13-F-19, and F-19-F-19 spin-spin coupling constants.