2-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-3,3-dimethylbutanoic acid methyl ester | 136911-68-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-3,3-dimethylbutanoic acid methyl ester
• 英文别名: Methyl 3,3-dimethyl-2-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)butanoate
• CAS: 136911-68-7
• 化学式: C₁₀H₁₇N₃O₄
• 分子量: 243.263
• InChiKey: MNXZMYGLFANLCE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  79
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-<4-methyl-3--4,5-dihydro-5-oxo-1,2,4-triazol-1-yl>-3,3-dimethylbutanoic acid methyl ester 以 乙醚 、 氘代氯仿 、 Petroleum ether 为溶剂， 反应 4.0h， 生成 2-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-3,3-dimethylbutanoic acid methyl ester
  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

文献信息

• E/Z isomerization, solvolysis, addition, and cycloaddition reactions of (E)-tert-butylketene methyl tert-butyldimethylsilyl acetal
  作者：Waldemar Adam、Xiaoheng Wang

  DOI：10.1021/jo00026a013

  日期：1991.12

  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.