1,1-difluoro-10-tert-butyl-3,3,7,7-tetrakis(trifluoromethyl)-4,6-benzo-1-ioda-2,8-dioxabicyclo<3.3.0>octane | 136213-44-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1,1-difluoro-10-tert-butyl-3,3,7,7-tetrakis(trifluoromethyl)-4,6-benzo-1-ioda-2,8-dioxabicyclo<3.3.0>octane
• 英文别名: 1,1-difluoro-10-tert-butyl-3,3,7,7-tetrakis(trifluoromethyl)-4,6-benzo-1-ioda-2,8-dioxabicyclo[3.3.0]octane；9-tert-butyl-4,4-difluoro-2,2,6,6-tetrakis(trifluoromethyl)-4λ5-ioda-3,5-dioxatricyclo[5.3.1.04,11]undeca-1(10),7(11),8-triene
• CAS: 136213-44-0
• 化学式: C₁₆H₁₁F₁₄IO₂
• 分子量: 628.144
• InChiKey: OVUSOJDWVQBJJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.03
• 重原子数：
  33.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,1-difluoro-10-tert-butyl-3,3,7,7-tetrakis(trifluoromethyl)-4,6-benzo-1-ioda-2,8-dioxabicyclo<3.3.0>octane 以 氘代氯仿 、 二氯甲烷 为溶剂， 反应 768.0h， 生成 1-(1-<2,2,2-trifluoro-1-phenyl-1-(trifluoromethyl)ethoxy>-10-tert-butyl-3,3,7,7-tetrakis(trifluoromethyl)-4,6-benzo-1-ioda-2,8-dioxabicyclo<3.3.0>octyl) trifluoromethanesulfonate
  参考文献：
  名称：

  An organic tridentate ligand stabilizing a 10-I-4 iodinane oxide and related species

  摘要：

  The tridentate ligand of iodinane 7, with electronegative apical oxygens joined by five-membered rings to an electropositive equatorial carbon, strongly stabilizes pseudo-trigonal-bipyramidal (PSI-TBP) 10-I-3 species 7, as well as 10-I-4 species such as iodinane oxide 5. Fluorination of 7 forms a pseudooctahedral (PSI-Oc) 12-I-5 periodinane, 4, which is easily hydrolyzed to 5, or reacts with Lewis acids to form 10-I-4 fluoroperiodonium cation 8. The equatorial I+-O- bond of 5 reacts with electrophiles at the oxygen [with trifluoroacetyl triflate (TFAT) to give 10-I-4 (trifluoroacetoxy)periodonium triflate 12; with triflic acid (TfOH) to form the 10-I-4 hydroxyperiodonium triflate 9; and with trifluoroacetic anhydride (TFAA) to form the 12-I-5 bis(trifluoroacetoxy)periodinane 11]. Small amounts of tetrabutylammonium hydroxide give nucleophilic addition to the iodine of 5 to form 12-I-5 intermediates (18) leading to rapid inversion of geometry at the 10-I-4 center of the iodinane oxide. Excess KOH cleaves the C-I bond of 5, forming the reduced arenediol 17. Diphenyldialkoxysulfurane 14 converts 5 to dialkoxyperiodinane 13, forming diphenyl sulfoxide. Iodine oxide 5 is a strong oxidizing agent, rapidly oxidizing HCl to Cl2, or pinacol to acetone. Oxidation of a diaryl sulfide to the sulfoxide and the sulfone occurs unselectively, but slowly, at 160-degrees-C with pure 5. With a catalytic amount of TFAA, selective oxidation of the diaryl sulfide to the sulfoxide by 5 is rapid at room temperature.

  DOI：

  10.1021/jo00023a022
• 作为产物：
  描述：

  4-叔-丁基-2,6-二(1-羟基-1-(三氟甲基)-2,2,2-三氟乙基)碘苯 在 fluorine 作用下， 反应 0.25h， 以100%的产率得到1,1-difluoro-10-tert-butyl-3,3,7,7-tetrakis(trifluoromethyl)-4,6-benzo-1-ioda-2,8-dioxabicyclo<3.3.0>octane
  参考文献：
  名称：

  An organic tridentate ligand stabilizing a 10-I-4 iodinane oxide and related species

  摘要：

  The tridentate ligand of iodinane 7, with electronegative apical oxygens joined by five-membered rings to an electropositive equatorial carbon, strongly stabilizes pseudo-trigonal-bipyramidal (PSI-TBP) 10-I-3 species 7, as well as 10-I-4 species such as iodinane oxide 5. Fluorination of 7 forms a pseudooctahedral (PSI-Oc) 12-I-5 periodinane, 4, which is easily hydrolyzed to 5, or reacts with Lewis acids to form 10-I-4 fluoroperiodonium cation 8. The equatorial I+-O- bond of 5 reacts with electrophiles at the oxygen [with trifluoroacetyl triflate (TFAT) to give 10-I-4 (trifluoroacetoxy)periodonium triflate 12; with triflic acid (TfOH) to form the 10-I-4 hydroxyperiodonium triflate 9; and with trifluoroacetic anhydride (TFAA) to form the 12-I-5 bis(trifluoroacetoxy)periodinane 11]. Small amounts of tetrabutylammonium hydroxide give nucleophilic addition to the iodine of 5 to form 12-I-5 intermediates (18) leading to rapid inversion of geometry at the 10-I-4 center of the iodinane oxide. Excess KOH cleaves the C-I bond of 5, forming the reduced arenediol 17. Diphenyldialkoxysulfurane 14 converts 5 to dialkoxyperiodinane 13, forming diphenyl sulfoxide. Iodine oxide 5 is a strong oxidizing agent, rapidly oxidizing HCl to Cl2, or pinacol to acetone. Oxidation of a diaryl sulfide to the sulfoxide and the sulfone occurs unselectively, but slowly, at 160-degrees-C with pure 5. With a catalytic amount of TFAA, selective oxidation of the diaryl sulfide to the sulfoxide by 5 is rapid at room temperature.

  DOI：

  10.1021/jo00023a022