N-(5-carbomethoxythiopentanoyl)-N-methylhydroxylamine

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N-(5-carbomethoxythiopentanoyl)-N-methylhydroxylamine
• 英文别名: Methyl 6-[hydroxy(methyl)amino]-6-sulfanylidenehexanoate；methyl 6-[hydroxy(methyl)amino]-6-sulfanylidenehexanoate
• 化学式: C₈H₁₅NO₃S
• 分子量: 205.278
• InChiKey: IUNVHXOEDJZXDH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  81.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  甲基脂肪酰氯 在 5,5-dimethyl-2-thiolo-2-thiono-1,3,2-dioxaphosphorinane 、 三乙胺 作用下， 以 氯仿 、 苯 为溶剂， 反应 0.5h， 生成 N-(5-carbomethoxythiopentanoyl)-N-methylhydroxylamine
  参考文献：
  名称：

  S-Thioacyldithiophosphates in the Synthesis of Thiohydroxamic Acids and O-Thioacylhydroxylamines

  摘要：

  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。

  DOI：

  10.1055/s-2002-31957

文献信息

• Substituent effects on15N NMR chemical shifts in selectedN-alkylthiohydroxamic acids. A comparative study
  作者：Witold Przychodze?、Leszek Doszczak、Janusz Rachon

  DOI：10.1002/mrc.1497

  日期：2005.1

  that the inductive effect of the hydroxyl group rather than steric hindrance is responsible for non‐additivity of the effect of substituents. Additionally, N‐hydroxyl diminishes the effect of aromatic ring substituents on the 15N chemical shifts in the thiohydroxamic acids 3 which is approximately half that in the respective thiobenzamides 6. The chemical shift values correlate best with Brown's σ+

  测量了三种 N-烷基-δ-碳甲氧基戊硫代异羟肟酸 (2) 和六种合成的 N-异丙基苯并硫代异羟肟酸 (3) 的 15N NMR 光谱，并与结构相似的羟胺 (1)、苯异羟肟酸 (4)、苯甲酰胺 ( 5) 和硫代苯甲酰胺 (6)。正在研究的硫代异羟肟酸的化学位移分析表明，羟基的诱导作用而不是空间位阻是取代基作用非可加性的原因。此外，N-羟基减少了芳环取代基对硫代异羟肟酸 3 中 15N 化学位移的影响，这大约是相应硫代苯甲酰胺 6 中的一半。化学位移值与布朗的 σ+ 参数相关性最好。版权所有 © 2004 John Wiley & Sons, Ltd.
• 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.
• 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。