1-(2,2,2-trifluoroethoxy)-1-methoxy-1--3,3-dimethylbutane | 136911-61-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1-(2,2,2-trifluoroethoxy)-1-methoxy-1--3,3-dimethylbutane
• 英文别名: Silane, tert-butyl[1-methoxy-3,3-dimethyl-1-(2,2,2-trifluoroethoxy)butoxy]dimethyl-；tert-butyl-[1-methoxy-3,3-dimethyl-1-(2,2,2-trifluoroethoxy)butoxy]-dimethylsilane
• CAS: 136911-61-0
• 化学式: C₁₅H₃₁F₃O₃Si
• 分子量: 344.49
• InChiKey: ZEGMOFNHVNTQFW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.32
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2,2,2-三氟乙醇 、 (E)-tert-Butylketene Methyl tert-Butyldimethylsilyl Acetal 以 四氯化碳 为溶剂， 反应 6.0h， 以97%的产率得到1-(2,2,2-trifluoroethoxy)-1-methoxy-1--3,3-dimethylbutane
  参考文献：
  名称：

  E/Z isomerization, solvolysis, addition, and cycloaddition reactions of (E)-tert-butylketene methyl tert-butyldimethylsilyl acetal

  摘要：

  In the presence of catalytic amounts of CF3COCH3 or CF3COCF3, the silyl ketene acetal E-1 was isomerized into its Z isomer (Z/E ratio 90:10). For this novel E/Z isomerization a mechanism is proposed, in which addition and reelimination of the fluoro ketone, through a 1,4-dipolar intermediate operates. With the protic nucleophiles CH3OH, CF3CH2OH, or PhOH, the ketene acetal E-1 afforded the ortho esters 2 as addition products, while CH3CO2H, CF3CO2H, or H2O led to methyl pivalate as the solvolysis product. This chemistry is readily explained through protonation of the ketene acetal E-1 to generate the corresponding carbenium ion. At low temperature the reaction with TCNE gave the silylketene imine 3 as labile cycloadduct, which underwent on workup desilylation to give the TCNE-incorporated ester 6; the latter eliminated hydrogen cyanide at room temperature to give the ene ester 7. With MTAD the labile silyl ene product 4 was obtained initially, which underwent silyl migration to give N-silylated urazole 8; final desilylation led to the stable urazole 9. Also for the ene reactions of TCNE and MTAD with the silyl ketene acetal E-1, a 1,4-dipolar intermediate is proposed to intervene.

  DOI：

  10.1021/jo00026a013