Trifluoro-acetic acid 1-dimethylthiocarbamoyl-1-methyl-ethyl ester | 139040-84-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代酰胺
• 英文名称: Trifluoro-acetic acid 1-dimethylthiocarbamoyl-1-methyl-ethyl ester
• 英文别名: [1-(Dimethylamino)-2-methyl-1-sulfanylidenepropan-2-yl] 2,2,2-trifluoroacetate；[1-(dimethylamino)-2-methyl-1-sulfanylidenepropan-2-yl] 2,2,2-trifluoroacetate
• CAS: 139040-84-9
• 化学式: C₈H₁₂F₃NO₂S
• 分子量: 243.25
• InChiKey: VAXNJAWRKFRWGK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Trifluoro-acetic acid 1-dimethylthiocarbamoyl-1-methyl-ethyl ester 在 溶剂黄146 作用下， 生成 N,N-dimethylthioacrylamide
  参考文献：
  名称：

  Solvolytic elimination reactions of tertiary .alpha.-CSNMe2-substituted systems

  摘要：

  The tertiary benzylic alpha-CSNMe2-substituted p-nitrobenzoates and trifluoroacetates of general structure Ar(CH3)C(CSNMe2)(OCOR), 7 and 8, solvolyze to give exclusively elimination products H2C = C(CSNMe2)Ar. A Hammett study gave a nonlinear correlation. Variation in rate with solvent ionizing power was small for the unsubstituted trifluoroacetate derivative of 8, and the beta-CD3 isotope effect on rate was negligible. There is, however, a large isotope effect (2.5-2.8) in formation of the elimination product when Ph(CH2D)C(CSNMe2)(OCOCF3) solvolyzes. It is concluded that an intermediate must be involved since the product-determining step and the rate-determining step have differing isotope effects. The likely intermediate is an alpha-CSNMe2-substituted cation (as an ion pair), despite the fact that the reaction has few characteristics of a typical E1 reaction. Tertiary norbornyl, cyclohexyl, and 2-propyl alpha-CSNMe2-substituted systems also react to give exclusively elimination products at rates far in excess of alpha-CONMe2 analogues. It is suggested that alpha-CSNMe2 cations are also intermediates and that these cations undergo proton loss at an early ion pair stage. These cations are proposed to derive substantial stabilization by charge delocalization onto sulfur of the thiocarbonyl group. By way of contrast, the secondary system CH3CH(CSNMe2)(OCOCF3), 25, solvolyzes to give mainly a rearranged product CH3CH(CONMe2)(SCOCH3) via a k(DELTA) mechanism involving neighboring thiocarbonyl participation leading to a cyclized ion.

  DOI：

  10.1021/jo00032a051
• 作为产物：
  描述：

  2-Hydroxy-2,N,N-trimethylthiopropionamid 、 三氟乙酸酐 在 2,6-二甲基吡啶 作用下， 以 乙醚 为溶剂， 反应 0.08h， 生成 Trifluoro-acetic acid 1-dimethylthiocarbamoyl-1-methyl-ethyl ester
  参考文献：
  名称：

  Solvolytic elimination reactions of tertiary .alpha.-CSNMe2-substituted systems

  摘要：

  The tertiary benzylic alpha-CSNMe2-substituted p-nitrobenzoates and trifluoroacetates of general structure Ar(CH3)C(CSNMe2)(OCOR), 7 and 8, solvolyze to give exclusively elimination products H2C = C(CSNMe2)Ar. A Hammett study gave a nonlinear correlation. Variation in rate with solvent ionizing power was small for the unsubstituted trifluoroacetate derivative of 8, and the beta-CD3 isotope effect on rate was negligible. There is, however, a large isotope effect (2.5-2.8) in formation of the elimination product when Ph(CH2D)C(CSNMe2)(OCOCF3) solvolyzes. It is concluded that an intermediate must be involved since the product-determining step and the rate-determining step have differing isotope effects. The likely intermediate is an alpha-CSNMe2-substituted cation (as an ion pair), despite the fact that the reaction has few characteristics of a typical E1 reaction. Tertiary norbornyl, cyclohexyl, and 2-propyl alpha-CSNMe2-substituted systems also react to give exclusively elimination products at rates far in excess of alpha-CONMe2 analogues. It is suggested that alpha-CSNMe2 cations are also intermediates and that these cations undergo proton loss at an early ion pair stage. These cations are proposed to derive substantial stabilization by charge delocalization onto sulfur of the thiocarbonyl group. By way of contrast, the secondary system CH3CH(CSNMe2)(OCOCF3), 25, solvolyzes to give mainly a rearranged product CH3CH(CONMe2)(SCOCH3) via a k(DELTA) mechanism involving neighboring thiocarbonyl participation leading to a cyclized ion.

  DOI：

  10.1021/jo00032a051

文献信息

• Solvolytic elimination reactions of tertiary .alpha.-CSNMe2-substituted systems
  作者：Xavier Creary、Holia N. Hatoum、Angela Barton、Timothy E. Aldridge

  DOI：10.1021/jo00032a051

  日期：1992.3

  The tertiary benzylic alpha-CSNMe2-substituted p-nitrobenzoates and trifluoroacetates of general structure Ar(CH3)C(CSNMe2)(OCOR), 7 and 8, solvolyze to give exclusively elimination products H2C = C(CSNMe2)Ar. A Hammett study gave a nonlinear correlation. Variation in rate with solvent ionizing power was small for the unsubstituted trifluoroacetate derivative of 8, and the beta-CD3 isotope effect on rate was negligible. There is, however, a large isotope effect (2.5-2.8) in formation of the elimination product when Ph(CH2D)C(CSNMe2)(OCOCF3) solvolyzes. It is concluded that an intermediate must be involved since the product-determining step and the rate-determining step have differing isotope effects. The likely intermediate is an alpha-CSNMe2-substituted cation (as an ion pair), despite the fact that the reaction has few characteristics of a typical E1 reaction. Tertiary norbornyl, cyclohexyl, and 2-propyl alpha-CSNMe2-substituted systems also react to give exclusively elimination products at rates far in excess of alpha-CONMe2 analogues. It is suggested that alpha-CSNMe2 cations are also intermediates and that these cations undergo proton loss at an early ion pair stage. These cations are proposed to derive substantial stabilization by charge delocalization onto sulfur of the thiocarbonyl group. By way of contrast, the secondary system CH3CH(CSNMe2)(OCOCF3), 25, solvolyzes to give mainly a rearranged product CH3CH(CONMe2)(SCOCH3) via a k(DELTA) mechanism involving neighboring thiocarbonyl participation leading to a cyclized ion.