N-methyl-N-thiobutyrylhydroxylamine

• 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: N-methyl-N-thiobutyrylhydroxylamine
• 英文别名: N-methyl-N-hydroxythiobutyramide；N-hydroxy-N-methylbutanethioamide
• 化学式: C₅H₁₁NOS
• 分子量: 133.214
• InChiKey: NMZDDJCGMCBMDI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  55.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  N-甲基羟胺 、 thiobutyryl 2-(5,5-dimethyl-2-thiono-1,3,2-dioxaphosphorinanyl)sulfide 在 三乙胺 作用下， 以83%的产率得到N-methyl-N-thiobutyrylhydroxylamine
  参考文献：
  名称：

  May Dithiophosphoric Acid Participate in the SET Process?

  摘要：

  Recently we have developed a convenient method for the synthesis of S-thioacyl dithiophosphates 1, excellent thioacylating reagents. When hydroxylanzines with one bulky group or two substituents on the nitrogen atom are treated with S-thioacyl dithiophosphates I O-thioacyl hydroxylamines 3 are produced exclusively. What is more important, compounds 3 undergo interesting reaction with dithiophosphoric acid 4 yielding amine and acyl thiophosphoryl disulfide 5. The disulfide 5 can be formed as a product of thiophilic attack of the dithiophosphate anion on the thiocarbonyl group in protonated O-thioacyl hydroxylamine 3. On the other hand, it is well known that dithiophosphate anions easily undergo one electron oxidation. Hence the dithiophosphate anion can act as single electron donor and disulfide 5 can be formed as a product of the SET reaction. The influence of light and radical traps strongly suggests that the second possibility operates in the reaction in focus.

  DOI：

  10.1080/10426500212210

文献信息

• S-Thioacyldithiophosphates in the Synthesis of Thiohydroxamic Acids and O-Thioacylhydroxylamines
  作者：Leszek Doszczak、Janusz Rachon

  DOI：10.1055/s-2002-31957

  日期：——

  S-Thioacyldithiophosphates proved to be excellent thioacylating agents. They are easily available from carboxylic acids. Due to their low reactivity towards oxygen nucleophiles and high reactivity towards nitrogen ones they found application in the synthesis of thiohydroxamic acids directly from hydroxylamines without protection on the hydroxy group. However, in cases of steric hindrance O-thioacyl hydroxylamines are formed and can be isolated with high yield.

  S-硫代酰基二硫代磷酸盐被证明是非常优秀的硫代酰化试剂，它们可从羧酸中容易地获得。由于它们对氧亲核试剂的反应性低，但对氮亲核试剂的反应性高，因此它们在直接从羟胺合成硫代羟肟酸时无需对羟基进行保护。然而，在存在立体阻碍的情况下会形成O-硫代酰基羟胺，并且可以高产率地分离出来。
• Lawesson's reagent for direct thionation of hydroxamic acids: Substituent effects on LR reactivity
  作者：Witold Przychodzeń

  DOI：10.1002/hc.20259

  日期：——

  To explore the generality and scope of direct thionation of hydroxamic acids (HAs), the reaction of various structurally diverse HAs with Lawesson's reagent was investigated. The yield of thiohydroxamic acid (THAs) is poor when HAs possess bulky acyl and/or N-substituents, acidic α-hydrogen atoms, or an N-phenyl ring. THAs yields were correlated with Brown sigma parameter. The relative rates of two

  为了探索异羟肟酸 (HA) 直接硫化的一般性和范围，研究了各种结构不同的 HA 与劳森试剂的反应。当 HA 具有庞大的酰基和/或 N-取代基、酸性 α-氢原子或 N-苯环时，硫代异羟肟酸 (THA) 的产率很低。THA 产量与 Brown sigma 参数相关。还测量了两个后续过程 k 和 k 的相对速率。还发现了 N-异丙基苯并硫代异羟肟酸的次甲基质子化学位移的相关性。© 2006 Wiley Periodicals, Inc. 杂原子化学 17:676–684, 2006; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20259
• May Dithiophosphoric Acid Participate in the SET Process?
  作者：Leszek Doszczak、Witold Przychodzen、Dariusz Witt、Janusz Rachon

  DOI：10.1080/10426500212210

  日期：2002.6.1

  Recently we have developed a convenient method for the synthesis of S-thioacyl dithiophosphates 1, excellent thioacylating reagents. When hydroxylanzines with one bulky group or two substituents on the nitrogen atom are treated with S-thioacyl dithiophosphates I O-thioacyl hydroxylamines 3 are produced exclusively. What is more important, compounds 3 undergo interesting reaction with dithiophosphoric acid 4 yielding amine and acyl thiophosphoryl disulfide 5. The disulfide 5 can be formed as a product of thiophilic attack of the dithiophosphate anion on the thiocarbonyl group in protonated O-thioacyl hydroxylamine 3. On the other hand, it is well known that dithiophosphate anions easily undergo one electron oxidation. Hence the dithiophosphate anion can act as single electron donor and disulfide 5 can be formed as a product of the SET reaction. The influence of light and radical traps strongly suggests that the second possibility operates in the reaction in focus.