Methyl 4,4-difluoro-2-iodo-4-benzoylbutanoate | 156575-49-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 4,4-difluoro-2-iodo-4-benzoylbutanoate
• 英文别名: Methyl 4,4-difluoro-2-iodo-5-oxo-5-phenylpentanoate
• CAS: 156575-49-4
• 化学式: C₁₂H₁₁F₂IO₃
• 分子量: 368.119
• InChiKey: HWIOVXCBZNBFKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl 4,4-difluoro-2-iodo-4-benzoylbutanoate 在 ammonium hydroxide 作用下， 以 水 为溶剂， 反应 24.0h， 以95%的产率得到4-Fluoro-5-phenyl-1H-pyrrole-2-carboxylic acid amide
  参考文献：
  名称：

  A new approach to the synthesis of β-fluoropyrrole derivatives

  摘要：

  beta-Fluoropyrrole derivatives are synthesized in high yields by the reaction of alpha,alpha-difluoro-gamma-iodo-gamma-(electron-withdrawing-group)-substituted ketones and ammonium hydroxide at room temperature; providing a new, simple, and efficient method for the synthesis of beta-fluorinated pyrrole rings. A possible mechanism is proposed.

  DOI：

  10.1016/s0040-4039(00)73343-0
• 作为产物：
  描述：

  丙烯酸甲酯（MA） 、 2,2-二氟-2-碘-1-苯基乙酮 以40%的产率得到Dimethyl 4-(2,2-difluoro-2-benzoyl)ethyl-2-iodo-1,5-pentanedioate
  参考文献：
  名称：

  紫外线引发的碘二氟甲基酮向缺电子烯烃的加成

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)73167-4

文献信息

• 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.
• Zai-Ming Qiu, Burton Donald J., Tetrahedron Lett, 35 (1994) N 25, S 4319-4322
  作者：Zai-Ming Qiu, Burton Donald J.

  DOI：——

  日期：——
• 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 new approach to the synthesis of β-fluoropyrrole derivatives
  作者：Zai-Ming Qiu、Donald J. Burton

  DOI：10.1016/s0040-4039(00)73343-0

  日期：1994.6

  beta-Fluoropyrrole derivatives are synthesized in high yields by the reaction of alpha,alpha-difluoro-gamma-iodo-gamma-(electron-withdrawing-group)-substituted ketones and ammonium hydroxide at room temperature; providing a new, simple, and efficient method for the synthesis of beta-fluorinated pyrrole rings. A possible mechanism is proposed.