2-hydroxy-N,N-dimethyl-2-phenylpropanethioamide-3-d | 139040-86-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-hydroxy-N,N-dimethyl-2-phenylpropanethioamide-3-d
• CAS: 139040-86-1
• 化学式: C₁₁H₁₅NOS
• 分子量: 210.304
• InChiKey: ZQEYECZUODSYQX-MICDWDOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.78
• 重原子数：
  14.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  23.47
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-hydroxy-N,N-dimethyl-2-phenylpropanethioamide-3-d 在 2,6-二甲基吡啶 、 水 、 溶剂黄146 作用下， 以 乙醚 为溶剂， 反应 0.38h， 生成 Benzeneethanethioamide, N,N-dimethyl-a-methylene-
  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：

  1-苯基-1-三甲基硅氧乙烯 、 N,N-二甲基硫代甲酰胺 在 氘代甲醇-d 、 三氟乙酸 、 lithium diisopropyl amide 作用下， 生成 2-hydroxy-N,N-dimethyl-2-phenylpropanethioamide-3-d
  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. Stepwise or concerted?
  作者：Xavier Creary、Vincent P. Casingal、Charlene E. Leahy

  DOI：10.1021/ja00058a018

  日期：1993.3

  lost exclusively when the elimination product forms. A concerted ester pyrolysis type of mechanism is therefore ruled out. The tertiary benzylic trifluoroacetate Ph(CH 3 )C(CONMe 2 )(OCOCF 3 ), 13, solvolyzes to give exclusively an elimination product. The β-CD 3 isotope effect on rate was 1.15. There is, however, a larger isotope effect (2.5) in formation of the elimination product when Ph(CH 2 D)C(CONMe

  2-Aryl-endo-2-norbornyl trifluoroacetates 11 溶剂分解得到很大一部分的氯化产物。氘标记研究表明，外氢仅在消除产物形成时丢失。因此排除了协同酯热解类型的机制。叔苄基三氟乙酸盐Ph(CH 3 )C(CONMe 2 )(OCOCF 3 ), 13 溶解以专门提供消除产物。β-CD 3 同位素对速率的影响为1.15。然而，当 Ph(CH 2 D)C(CONMe 2 )(OCOCF 3 ) 溶解时，消除产物的形成过程中存在较大的同位素效应 (2.5)