3-(difluoromethoxy)-5,5-dimethylcyclohex-2-en-1-one | 82477-45-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(difluoromethoxy)-5,5-dimethylcyclohex-2-en-1-one
• 英文别名: 3-(difluoromethoxy)-5,5-dimethylcyclohex-2-enone
• CAS: 82477-45-0
• 化学式: C₉H₁₂F₂O₂
• 分子量: 190.19
• InChiKey: JVQICTVBHMVREN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  S-bromodifluoromethyl-S-phenyl-2,3,4,5-tetramethylphenylsulfonium triflate 、 5,5-二甲基-1,3-环己二酮 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以79%的产率得到3-(difluoromethoxy)-5,5-dimethylcyclohex-2-en-1-one
  参考文献：
  名称：

  Selective O-Difluoromethylation of 1,3-Diones by Bromodifluoromethylating Reagents

  摘要：

  The regioselective Odifluoromethylation of 1,3-diones was achieved via in situ generation of difluorocarbene from bromodifluoromethylating reagents in the presence of an organic base. A wide variety of difluormethyl enol ethers were obtained in good to excellent yields. The reaction mechanism is discussed based on ab initio calculations (kcal/mol).

  DOI：

  10.1021/ol4000313

文献信息

• O-Difluoromethylation of 1,3-diones with S-difluoromethyl sulfonium salt
  作者：Chun-Bo Yue、Jin-Hong Lin、Ji Cai、Cheng-Pan Zhang、Gang Zhao、Ji-Chang Xiao、HengFeng Li

  DOI：10.1039/c6ra06338a

  日期：——

  The O-difluoromethylation of 1,3-diones with S-difluoromethyl sulfonium salt is described. The sulfonium salt was previously believed to be a direct difluoromethylation reagent, but our mechanistic investigation reveals that the O-difluoromethylation reaction proceeds not only via the direct transfer of the CF2H group, but also via a difluorocarbene process. This work represents the first protocol

  所述Ô的1,3-二酮与-difluoromethylation小号二氟甲基锍盐进行说明。previously盐以前被认为是直接的二氟甲基化试剂，但是我们的机理研究表明，O-二氟甲基化反应不仅通过CF 2 H基团的直接转移进行，而且还通过二氟卡宾方法进行。这项工作代表了无环1,3-二酮的轻度O-二氟甲基化的第一个方案。
• Base-free O-difluoromethylation of 1,3-diones with difluorocarbene
  作者：Can Liu、Xiao-Yun Deng、Xian-Liang Zeng、Gang Zhao、Jin-Hong Lin、Hongqing Wang、Ji-Chang Xiao

  DOI：10.1016/j.jfluchem.2016.10.011

  日期：2016.12

  The base-free O-difluoromethylation of 1,3-diones with difluorocarbene generated from difluoromethylene phosphobetaine (Ph3P+CF2CO2−) is described. The convenient reactions proceeded smoothly to give difluoromethyl enol ethers in moderate to good yields.

  游离碱- O-的二氟亚甲基从生成磷酸酯1,3-二酮与二氟卡宾二氟甲基（PH 3 P + CF 2 CO 2 - ）进行说明。方便的反应顺利进行，以中等至良好的产率得到二氟甲基烯醇醚。
• A new method for the synthesis of difluoromethyl enol ethers by O-difluoromethylation of 1,3-diones with ClCF₂CO₂Et
  作者：Xiaoxi Lin、Zhiqiang Weng

  DOI：10.1039/c5ob00020c

  日期：——

  single-step protocol for the synthesis of difluoromethyl enol ether derivatives by O-difluoromethylation of 1,3-diones via in situ generation of difluorocarbene from ClCF2CO2Et has been developed. The functional group tolerance, scalability of the reaction, and mild reaction conditions make it an attractive protocol for the synthesis of biologically relevant difluoromethyl ethers of interest to the pharmaceutical

  已经开发了一种简便，有效的单步骤方案，该方案通过从ClCF2CO2Et原位生成二氟卡宾，通过1,3-二酮的O-二氟甲基化合成二氟甲基烯醇醚衍生物。官能团耐受性，反应的可扩展性和温和的反应条件使其成为合成制药和农用化学工业感兴趣的生物学相关二氟甲基醚的有吸引力的方案。
• Rico, Isabelle; Cantacuzene, Danielle; Wakselman, Claude, Journal of the Chemical Society. Perkin transactions I, 1982, p. 1063 - 1066
  作者：Rico, Isabelle、Cantacuzene, Danielle、Wakselman, Claude

  DOI：——

  日期：——