N-methyl-N-thiopivaloylhydroxamic acid

• 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-thiopivaloylhydroxamic acid
• 英文别名: N-hydroxy-N-methylthiopivalamide；N-hydroxy-N,2,2-trimethylpropanethioamide
• 化学式: C₆H₁₃NOS
• 分子量: 147.241
• InChiKey: ZYPKIZYZTUBUND-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 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

• 作为产物：
  描述：

  1-(三甲基乙酰基)咪唑 在 5,5-dimethyl-2-thiolo-2-thiono-1,3,2-dioxaphosphorinane 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 氯仿 、 苯 为溶剂， 反应 4.5h， 生成 N-methyl-N-thiopivaloylhydroxamic acid
  参考文献：
  名称：

  Synthesis of S-thioacyl dithiophosphates, efficient and chemoselective thioacylating agentsProofs for the reversibility of isomerisation of anhydrides 1 to 2, melting points of amides and thioamides obtained from anhydrides 5–7 and 1H, 13C NMR and IR data of isolated anhydrides 5–7, 17 are available as supplementary data. For direct access, see http://www.rsc.org/suppdata/p1/b2/b201233b/

  摘要：

  容易获得的酰基二硫代磷酸酯不稳定，特别是在加热条件下，可以可逆地异构化为O-硫代酰基单硫代磷酸酯。转变为S-硫代酰基单硫代磷酸酯的过程要慢得多，但可能是不可逆的。由于建立了平衡状态，S-硫代酰基（单）硫代磷酸酯的形成较慢，反应混合物通常既含有硫代酰化剂也含有酰化剂，因此无法用于高效的硫代酰化反应。另一方面，将异构酸酐混合物与过量的二硫代磷酸反应，会导致仅形成S-硫代酰基二硫代磷酸酯。它们似乎是非常优秀的硫代酰化剂：相对稳定，对水和氧气不敏感，因此易于处理。它们在常温下与氮或硫亲核试剂的反应非常迅速，产生相应的硫代酰基衍生物。产品的分离非常简单。由于S-硫代酰基二硫代磷酸酯对氧亲核试剂的反应性较低，因此它们可以用于直接硫代酰化多功能亲核试剂，而不需要保护羟基。使用其他方法不易获得相应的硫代酰基衍生物。

  DOI：

  10.1039/b201233b

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。
• New, efficient and chemoselective method of thioacylation, starting from carboxylic acids
  作者：Leszek Doszczak、Janusz Rachon

  DOI：10.1039/b005911k

  日期：——

  S-Acylation of dithiophosphoric acids yields mixed anhydrides 3; they readily isomerize to O-thioacyl 4 and S-thioacyl monothiophosphates 5, which treated with the excess of dithiophosphoric acid 2 can be easily converted into thioacyl dithiophosphates 6, excellent thioacylating reagents.

  二硫代磷酸的S-酰基化反应生成混合酸酐3；它们容易异构化为O-硫代酰基4和S-硫代酰基单硫代磷酸酯5，这些化合物与过量的二硫代磷酸2反应后可以轻松转化为硫代酰基二硫代磷酸酯6，这是一种出色的硫代酰化试剂。
• 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.
• Synthesis of S-thioacyl dithiophosphates, efficient and chemoselective thioacylating agentsProofs for the reversibility of isomerisation of anhydrides 1 to 2, melting points of amides and thioamides obtained from anhydrides 5–7 and 1H, 13C NMR and IR data of isolated anhydrides 5–7, 17 are available as supplementary data. For direct access, see http://www.rsc.org/suppdata/p1/b2/b201233b/
  作者：Leszek Doszczak、Janusz Rachon

  DOI：10.1039/b201233b

  日期：2002.5.10

  Easily available acyl dithiophosphates are not stable and isomerise reversibly to O-thioacyl monothiophosphates, especially when subjected to heating. Much slower but probably irreversible isomerisation to S-thioacyl monothiophosphates occurs. Since equilibrium states are established and S-thioacyl (mono)thiophosphates form slowly, reaction mixtures contain generally both thioacylating and acylating agents, and consequently cannot be used for efficient thioacylation. On the other hand, treatment of a mixture of isomeric anhydrides with an excess of a dithiophosphoric acid leads to exclusive formation of S-thioacyl dithiophosphates. They appear to be excellent thioacylating agents: relatively stable, inert towards water and oxygen and therefore easy to handle. Reactions with nitrogen or sulfur nucleophiles proceed very rapidly under ambient conditions, yielding respective thioacyl derivatives. Isolation of the products is very simple. Due to the low reactivity of S-thioacyl dithiophosphates towards oxygen nucleophiles they can be used for direct thioacylation of multifunctional nucleophiles with unprotected hydroxy groups. Respective thioacyl derivatives cannot readily be obtained using other methods.

  容易获得的酰基二硫代磷酸酯不稳定，特别是在加热条件下，可以可逆地异构化为O-硫代酰基单硫代磷酸酯。转变为S-硫代酰基单硫代磷酸酯的过程要慢得多，但可能是不可逆的。由于建立了平衡状态，S-硫代酰基（单）硫代磷酸酯的形成较慢，反应混合物通常既含有硫代酰化剂也含有酰化剂，因此无法用于高效的硫代酰化反应。另一方面，将异构酸酐混合物与过量的二硫代磷酸反应，会导致仅形成S-硫代酰基二硫代磷酸酯。它们似乎是非常优秀的硫代酰化剂：相对稳定，对水和氧气不敏感，因此易于处理。它们在常温下与氮或硫亲核试剂的反应非常迅速，产生相应的硫代酰基衍生物。产品的分离非常简单。由于S-硫代酰基二硫代磷酸酯对氧亲核试剂的反应性较低，因此它们可以用于直接硫代酰化多功能亲核试剂，而不需要保护羟基。使用其他方法不易获得相应的硫代酰基衍生物。