1,1-二氟-1-碘辛烷-2-酮 | 150542-10-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1,1-二氟-1-碘辛烷-2-酮
• 英文名称: Iododifluoromethyl n-hexyl ketone
• 英文别名: n-hexyl iododifluoromethyl ketone；Iododifluromethyl n-hexyl ketone；2-Octanone, 1,1-difluoro-1-iodo-；1,1-difluoro-1-iodooctan-2-one
• CAS: 150542-10-2
• 化学式: C₈H₁₃F₂IO
• 分子量: 290.092
• InChiKey: ZWLYSPMZQNNVAU-UHFFFAOYSA-N

物化性质

• 沸点：
  217.0±40.0 °C(Predicted)
• 密度：
  1.547±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,1-二氟-1-碘辛烷-2-酮 在 四(三苯基膦)钯 、 nickel dichloride 、 锌 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 6.5h， 生成 7,7-Difluoro-2,8-tetradecanedione
  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
• 作为产物：
  描述：

  1-chloro-1,1-difluoro-2-octanone 在 碘 、 锌 作用下， 以 乙腈 为溶剂， 反应 20.0h， 生成 1,1-二氟-1-碘辛烷-2-酮
  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

• UV initiated addition of iododifluoromethyl ketones to electron-deficient olefins
  作者：Zai-Ming Qiu、Donald J. Burton

  DOI：10.1016/s0040-4039(00)73167-4

  日期：1994.3

  Under UV irradiation, iododifluoromethyl ketones reacted with electron-deficient olefins in the absence of solvent to give high yields of the 1:1 adducts, providing a useful method for the synthesis of α,α-difluoro-γ-iodo-γ-(electron-withdrawing-group) substituted ketones.

  在紫外线照射下，碘二氟甲基酮在没有溶剂的情况下与缺电子的烯烃反应，可高收率地形成1：1的加合物，为合成α，α-二氟-γ-碘-γ-（电子-withdrawing-group）取代的酮。
• A general route to α,α-difluoroketones
  作者：Zai-Ming Qiu、Donald J. Burton

  DOI：10.1016/s0040-4039(00)73671-9

  日期：1993.5

  The reaction of iododifluoromethyl ketones with alkenes catalyzed by Pd(PPh3)4 in the absence of solvent at room temperature gives high yields of the corresponding 1:1 addition products. Treatment of the adducts with Zn/NiCl2.6H2O/THF affords alpha,alpha-difluoroketones. A variety of functional groups in the olefins are tolerated under the reaction conditions, including alkyl, trimethylsilyl, hydroxy, epoxy, carbonyl and ester groups.
• Synthesis of .gamma.-(Electron-withdrawing group)-Substituted .alpha.,.alpha.-Difluoro Ketones by UV-Initiated Addition of Iododifluoromethyl Ketones with Electron-Deficient Alkenes
  作者：Zai-Ming Qiu、Donald J. Burton

  DOI：10.1021/jo00126a032

  日期：1995.10

  Under UV irradiation (254 nm), iododifluoromethyl phenyl, alkyl, and chlorodifluoromethyl ketones [RC(O)CF2I (1), R: Ph (a); n-C4H9 (b), n-C6H13 (c), ClCF2 (d)] were reacted with a series of alkyl acrylates (CH2=CHCO(2)R', R': Et, n-Bu, t-Bu, and Me), N,N-dimethylacrylamide, acrylonitrile, and vinyl methyl ketone in the absence of solvent at ambient temperature. High yields of the corresponding 1:1 addition products [RC(O)CF(2)CH(2)CHICO(2)Et (2)] were obtained when 1 reacted with ethyl acrylates (50-79%). The reaction of la with n-butyl acrylate gave a similar 1:1 adduct (51%). However, an addition-reduction product, PhC(O)CF2CH2CH2CO2H, was isolated in 44% yield when tert-butyl acrylate was reacted with la. More interestingly, both 1:1 and 1:2 [PhC(O)CF2CH2CH(CO(2)Me)CH(2)CHICO(2)Me] adducts were formed in a 1.3:1 ratio when la was reacted with methyl acrylate under similar conditions, which indicated that the ester group exhibited an important effect on reaction selectivity. In the reaction with la, ethyl and methyl acrylates also displayed significantly higher reactivity than that of n- or tert-butyl acrylates. 1 also reacted with N,N-dimethylacrylamide to afford high yields of the 1:1 adducts. However, telomeric products were obtained in the reaction of la with acrylonitrile, and the 1:1 and pure 1:2 addition products were isolated in low yield. The reaction of acrylonitrile with alkyl-substituted iododifluoromethyl ketone, Ib, gave only the reduced product, n-C4H9C(O)CF2H, under similar conditions. With vinyl methyl ketone, the reaction of la produced an addition-reduction product, PhC(O)CF2CH2CH2C(O)Me, in 50% yield. The reactivity of RC(O)CF2I (1) varied with the substituted R groups in the reaction with ethyl acrylate and N,N-dimethylacrylamide: R, CICF2 > Ph > n-C4H9 > n-C6H13. Correspondingly, the reaction of la with ethyl acrylate generated a polymer in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium. Treatment of the adducts with zinc in the presence of a catalytic amount of NiCl2 . 6H(2)O in moist THF afforded the corresponding gamma-(electron-withdrawing group)-substituted alpha,alpha-difluoro ketones in high yields.
• Qiu, Zai-Ming; Burton, Donald J., Tetrahedron Letters, 1995, vol. 36, # 29, p. 5119 - 5122
  作者：Qiu, Zai-Ming、Burton, Donald J.

  DOI：——

  日期：——
• 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.