2-Hydroxy-2,N,N-trimethylthiopropionamid | 52417-39-7

• 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: 2-Hydroxy-2,N,N-trimethylthiopropionamid
• 英文别名: N,N-dimethyl-2-hydroxy-2-methylthiopropionamide；2-hydroxy-N,N,2-trimethylthiopropionamide；N,N-Dimethyl-2-hydroxi-2,2-dimethylthioacetamid；Propanethioamide, 2-hydroxy-N,N,2-trimethyl-；2-hydroxy-N,N,2-trimethylpropanethioamide
• CAS: 52417-39-7
• 化学式: C₆H₁₃NOS
• 分子量: 147.241
• InChiKey: WXVFTAGJECXIMT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  55.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Hydroxy-2,N,N-trimethylthiopropionamid 在 2,6-二甲基吡啶 、 溶剂黄146 作用下， 以 乙醚 为溶剂， 反应 0.08h， 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：

  丙酮 以75%的产率得到
  参考文献：
  名称：

  SEEBACH D.; LUBOSCH W.; ENDERS D., CHEM. BER. , 1976, 109, NO 4, 1309-1323

  摘要：

  DOI：

文献信息

• Nucleophile Aminoalkylierung mit Thiopivalamiden
  作者：Winfried Lubosch、Dieter Seebach

  DOI：10.1002/hlca.19800630111

  日期：1980.1.23

  Nucleophilic Aminoalkylation with Thiopivalamides1

  硫代戊酰胺的亲核氨基烷基化1
• Naphthalene-catalysed lithiation of carbamoyl and thiocarbamoyl chlorides under Barbier-type reaction conditions
  作者：Diego J. Ramón、Miguel Yus

  DOI：10.1016/0040-4020(96)00827-7

  日期：1996.10

  The reaction of different carbamoyl or thiocarbamoyl chlorides 1 with carbonyl compounds or imines 2 in the presence of an excess of lithium powder and a catalytic amount of naphthalene (3 mol %) in THF at −78°C leads, after hydrolysis with water, to the expected α-hydroxy or α-amino amides 3, respectively. In the case of allylic or benzylic derivatives 1a,c, when longer reaction times are used, the

  不同的氨基甲酰基或硫代氨基甲酰氯的反应1与羰基化合物或亚胺2在THF过量锂粉末和萘的催化量（3摩尔％）的在-78℃下引线的存在下，用水水解后，以预期的α-羟基或α-氨基酰胺3。在烯丙基或苄基衍生物1a，c的情况下，当使用更长的反应时间时，获得了由脱酰作用或脱​​苄基作用产生的相应产物4。使用DMF或异氰酸苯酯作为亲电试剂可得到取代的乙酰胺5。最后，当预先进行水解时，将过量的烷基氯加入到反应混合物中，形成1，2-二醇6，这是由于将原位生成的烷基锂最后两次加成至最初形成的α-羟基酰胺而产生的。
• Seebach,D. et al., Chemische Berichte, 1976, vol. 109, p. 1309 - 1323
  作者：Seebach,D. et al.

  DOI：——

  日期：——
• Carbamoyl and thiocarbamoyl lithium: A new route by naphthalene-catalysed chlorine-lithium exchange
  作者：Diego J. Ramón、Miguel Yus

  DOI：10.1016/s0040-4039(00)61613-1

  日期：1993.10

  The reaction of N,N-diisopropylcarbamoyl or N,N-dimethylthiocarbamoyl chloride (1a or 1b) with an excess of lithium powder and a catalytic amount of naphthalene (3 mol %) in the presence of a carbonyl compound 2 at temperatures ranging between -78 and 20-degrees-C, under Barbier-type conditions leads, after hydrolysis with water, to the corresponding alpha-hydroxy amides or thioamides 3, respectively.
• LUBOSCH W.; SEEBACH D., HELV. CHIM. ACTA, 1980, 63, NO 1, 102-116
  作者：LUBOSCH W.、 SEEBACH D.

  DOI：——

  日期：——