1,1-Difluoro-3-iodo-4,4-dimethylpentyl phenyl ketone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-Difluoro-3-iodo-4,4-dimethylpentyl phenyl ketone
• 化学式: C₁₄H₁₇F₂IO
• 分子量: 366.19
• InChiKey: IBXPOYFBKDFCDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  一氯二氟苯乙酮 在 四(三苯基膦)钯 、 碘 、 锌 作用下， 以 乙腈 为溶剂， 反应 8.5h， 生成 1,1-Difluoro-3-iodo-4,4-dimethylpentyl phenyl ketone
  参考文献：
  名称：

  Synthesis of .alpha.,.alpha.-Difluoro-Functionalized Ketones

  摘要：

  In the presence of a catalytic amount of tetrakis(triphenylphosphine) palladium [Pd(PPh(3))(4)], iododifluoromethyl alkyl and phenyl ketones 1 react with alkenes to give the corresponding alpha,alpha-difluoro-gamma-iodo ketones in high yields at room temperature either neat or in hexane at 60 degrees C. A variety of functional groups, such as alkyl, trimethylsilyl, hydroxy, epoxy, ketone, and ester, are tolerated under the reaction conditions. The reaction can be completely suppressed by a radical inhibitor, di-tert-butyl nitroxide or hydroquinone. A ring closure reaction occurs when 1 reacts with diethyl diallylmalonate in the presence of a catalytic amount of Pd(PPh(3))(4). Under UV irradiation, the reaction of 1 with diallyl ether gives a tetrahydrofuran derivative. All these results are consistent with a radical chain mechanism initiated by single electron transfer from Pd(PPh(3))(4) to 1. In the presence of a catalytic amount of nickel dichloride hexahydrate, the iodine in the 1:1 addition adducts is readily reduced by zinc in moist THF under mild conditions to give the corresponding alpha,alpha-difluoro ketones in high yields. A one-pot addition-reduction reaction has been developed for the synthesis of alpha,alpha-difluoro ketones without the isolation of the 1:1 addition adducts, which provides a new, efficient, and practical method for the preparation of a variety of alpha,alpha-difluoro-functionalized ketones.

  DOI：

  10.1021/jo00122a044

文献信息

• Synthesis of .alpha.,.alpha.-Difluoro-Functionalized Ketones
  作者：Zai-Ming Qiu、Donald J. Burton

  DOI：10.1021/jo00122a044

  日期：1995.9

  In the presence of a catalytic amount of tetrakis(triphenylphosphine) palladium [Pd(PPh(3))(4)], iododifluoromethyl alkyl and phenyl ketones 1 react with alkenes to give the corresponding alpha,alpha-difluoro-gamma-iodo ketones in high yields at room temperature either neat or in hexane at 60 degrees C. A variety of functional groups, such as alkyl, trimethylsilyl, hydroxy, epoxy, ketone, and ester, are tolerated under the reaction conditions. The reaction can be completely suppressed by a radical inhibitor, di-tert-butyl nitroxide or hydroquinone. A ring closure reaction occurs when 1 reacts with diethyl diallylmalonate in the presence of a catalytic amount of Pd(PPh(3))(4). Under UV irradiation, the reaction of 1 with diallyl ether gives a tetrahydrofuran derivative. All these results are consistent with a radical chain mechanism initiated by single electron transfer from Pd(PPh(3))(4) to 1. In the presence of a catalytic amount of nickel dichloride hexahydrate, the iodine in the 1:1 addition adducts is readily reduced by zinc in moist THF under mild conditions to give the corresponding alpha,alpha-difluoro ketones in high yields. A one-pot addition-reduction reaction has been developed for the synthesis of alpha,alpha-difluoro ketones without the isolation of the 1:1 addition adducts, which provides a new, efficient, and practical method for the preparation of a variety of alpha,alpha-difluoro-functionalized ketones.