N-(1-phenylethyl)-O-thiopivaloylhydroxylamine | 476686-97-2

• 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: N-(1-phenylethyl)-O-thiopivaloylhydroxylamine
• 英文别名: O-thiopivaloyl-N-(1-phenylethyl)hydroxylamine；O-(1-phenylethylamino) 2,2-dimethylpropanethioate
• CAS: 476686-97-2
• 化学式: C₁₃H₁₉NOS
• 分子量: 237.366
• InChiKey: MFOQTPOMBYYDSY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  53.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,5-dimethyl-2-thiolo-2-thiono-1,3,2-dioxaphosphorinane 、 N-(1-phenylethyl)-O-thiopivaloylhydroxylamine 在 2,6-二甲基巯基苯酚 、 三乙胺 作用下， 以 氘代氯仿 为溶剂， 反应 0.5h， 生成 pivaloyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphinan-2-yl) disulfide
  参考文献：
  名称：

  New reaction of dithiophosphoric acids with O-thioacylhydroxylamines. Nucleophilic substitution or single electron transfer process?

  摘要：

  二取代的或受立体阻碍的羟胺与大体积的 S-硫代酰基二硫代磷酸反应生成 O-硫代酰基羟胺。O- 硫代酰羟胺与二硫代磷酸反应生成酰基硫代磷酰二硫化物和二硫代磷酸铵。自由基陷阱对反应产率的影响强烈表明，自由基参与了这一过程的机理。二硫代磷酸铵的氧化还原电位较低、O-硫代酰羟胺的光化学稳定性以及光对酰基硫代磷酸二硫化物产率的影响，都意味着所研究的反应涉及单电子转移过程。

  DOI：

  10.1039/b203619n
• 作为产物：
  描述：

  pivaloyl 2-(5,5-dimethyl-2-thiono-1,3,2-dioxaphosphorinanyl)sulfide 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 4.25h， 生成 N-(1-phenylethyl)-O-thiopivaloylhydroxylamine
  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

• 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。
• New reaction of dithiophosphoric acids with O-thioacylhydroxylamines. Nucleophilic substitution or single electron transfer process?
  作者：Leszek Doszczak、Witold Przychodzeń、Dariusz Witt、Janusz Rachon

  DOI：10.1039/b203619n

  日期：——

  Disubstituted or sterically hindered hydroxylamines react with bulky S-thioacyl dithiophosphates yielding O-thioacylhydroxylamines. The reaction of O-thioacylhydroxylamines with dithiophosphoric acids yields acyl thiophosphoryl disulfides and ammonium dithiophosphates. The influence of radical traps on the reaction yield strongly suggests that radicals are involved in the mechanism of the process. The low redox potential of dithiophosphates, the observed photochemical stability of O-thioacylhydroxylamines and the influence of light on acyl thiophosphoryl disulfides yield imply involvement of a single electron transfer process in the investigated reaction.

  二取代的或受立体阻碍的羟胺与大体积的 S-硫代酰基二硫代磷酸反应生成 O-硫代酰基羟胺。O- 硫代酰羟胺与二硫代磷酸反应生成酰基硫代磷酰二硫化物和二硫代磷酸铵。自由基陷阱对反应产率的影响强烈表明，自由基参与了这一过程的机理。二硫代磷酸铵的氧化还原电位较低、O-硫代酰羟胺的光化学稳定性以及光对酰基硫代磷酸二硫化物产率的影响，都意味着所研究的反应涉及单电子转移过程。