4-(2,2,2-trifluoroethanethioyl)morpholine | 4675-80-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: 4-(2,2,2-trifluoroethanethioyl)morpholine
• 英文别名: 1-(morpholin-4-yl)-2,2,2-trifluoroethanethione；4-(trifluoro-thioacetyl)-morpholine；2,2,2-trifluoro-1-morpholin-4-ylethanethione
• CAS: 4675-80-3
• 化学式: C₆H₈F₃NOS
• 分子量: 199.197
• InChiKey: KONWUGFOIHNHKS-UHFFFAOYSA-N

物化性质

• 沸点：
  168.3±50.0 °C(Predicted)
• 密度：
  1.382±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  44.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-(2,2,2-trifluoroethanethioyl)morpholine 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 methyl 6-(methylthio)-6-(trifluoromethyl)perhydropyrrolo[2,3-c][1,4]oxazine-8-carboxylate
  参考文献：
  名称：

  由三氟硫代乙酰胺或氰基硫代甲酰胺衍生的新的偶氮甲亚胺的非对映选择性1,3-偶极环加成

  摘要：

  三氟甲基或氰基硫代dium盐的去质子化反应生成新的偶氮甲亚胺，它们以高非对映选择性环加成至双极性亲核体。还描述了新的三氟甲基化杂环的差向异构，水解和还原。

  DOI：

  10.1016/s0040-4020(02)00308-3
• 作为产物：
  描述：

  N-三氟乙酰基吗啉 在 tetraphosphorus decasulfide 、 碳酸氢钠 作用下， 以 乙二醇二甲醚 为溶剂， 以88%的产率得到4-(2,2,2-trifluoroethanethioyl)morpholine
  参考文献：
  名称：

  Synthesis and Reactivity of Trifluorodithioacetates Derived from Trifluorothioacetamides

  摘要：

  A general synthesis of trifluorodithioacetates is described by thiolysis of trifluorothioamidium salts, derived from trifluorothioacetamides. The reactivity of these CF3 bearing C-2 building blocks has been investigated towards nucleophiles and in cycloaddition reactions. Trifluorodithioacetates react with dienes to give thiopyrans and with diazo compounds to give trifluoromethyl vinyl sulphides via thiirane intermediates. With amines, trifluorodithioacetates give rise to trifluorothioacetamides while thiols add by thiophilic attack leading to new trifluoroethane dithioacetal disulphide. Two equivalents of phosphite furnish one equivalent of thiophosphate and one of phosphorylated trifluoroethane.

  DOI：

  10.1002/prac.199733901128

文献信息

• Reaction of N,N-disubstituted perfluoroalkanethioamides with trialkyl phosphites. A new method for the synthesis of polyfluorinated α-aminophosphonates
  作者：Sergiy S. Mykhaylychenko、Nadiia V. Pikun、Yuriy G. Shermolovich

  DOI：10.1016/j.tetlet.2011.07.037

  日期：2011.9

  The first examples of the reactions of perfluoroalkanethiocarboxylic acid amides and trialkyl phosphites are presented. The reactions are shown to be dependent on the perfluoroalkyl chain length and the presence of proton-donating reagents. New fluorinated α-aminophosphonate derivatives are obtained in moderate to good yields.

  给出了全氟链烷硫基羧酸酰胺与亚磷酸三烷基酯反应的第一个实例。已表明反应取决于全氟烷基链的长度和质子给体试剂的存在。以中等至良好的产率获得了新的氟化α-氨基膦酸酯衍生物。
• Reaction of <i>N,N</i> ‐Disubstituted Polyfluoroalkanethioamides with Diazomethane: Entry to New Thiirane Derivatives
  作者：Yuriy G. Shermolovich、Aleksandr I. Khyzhan、Eduard B. Rusanov、Alexander V. Mazepa、Ildar M. Rakipov、Sergiy S. Mykhaylychenko

  DOI：10.1002/ejoc.202001104

  日期：2021.12.21

  The first examples of the reaction between polyfluoroalkanethioamides and diazomethane are presented. New fluorinated thiiranamines are smoothly converted to 1‐polyfluoroalkyl enamines. Unexpected formation of functionalized 1,4‐dioxanes occurs as a result of the oxidation of the obtained thiiranes and enamines with m‐chloroperoxybenzoic acid. Stereochemical aspects of new 1,4‐dioxane derivatives are

  给出了多氟链烷硫酰胺与重氮甲烷之间反应的第一个例子。新的氟化硫胺素可以平稳地转化为1-多氟烷基烯胺。官能化的1,4-二恶烷的意外形成发生作为所获得的硫杂丙环和烯胺与的氧化的结果米氯过氧苯甲酸。讨论了新的1,4-二恶烷衍生物的立体化学方面。
• Synthesis of 2-polyfluoroalkyl-2,3-dihydro-1,3,4-thiadiazoles via regioselective [3+2] cycloaddition of nitrile imines to polyfluoroalkanethioamides
  作者：Sergiy S. Mykhaylychenko、Nadezhda V. Pikun、Eduard B. Rusanov、Alexander B. Rozhenko、Yuriy G. Shermolovich

  DOI：10.1007/s10593-018-2199-9

  日期：2017.11

  [3+2] Cycloaddition reactions of polyfluoroalkanethioamides with nitrile imines, generated in situ by dehydrochlorination of the corresponding hydrazonoyl chlorides, in the presence of triethylamine, were studied. A new method was proposed on the basis of these reactions for the synthesis of 2-polyfluoroalkyl-2,3-dihydro-1,3,4-thiadiazoles.

  [3 + 2]研究了在三乙胺存在下，通过相应的酰氯的脱氯化氢反应原位生成的多氟链烷硫酰胺与腈亚胺的环加成反应。在这些反应的基础上，提出了一种新的合成2-聚氟烷基-2,3-二氢-1,3,4-噻二唑的方法。
• Hetero-Diels–Alder reactions of perfluoroalkyl thioamides with electron-rich 1,3-dienes: synthesis of new 2-aminosubstituted-3,6-dihydro-2H-thiopyrans and related compounds
  作者：Oleksandr S. Kanishchev、Morgane Sanselme、Jean-Philippe Bouillon

  DOI：10.1016/j.tet.2012.11.086

  日期：2013.1

  Hetero-Diels–Alder reactions of perfluoroalkyl thioamides with electron-rich 1,3-dienes such as 2,3-dimethylbutadiene, isoprene or penta-1,3-diene gave a simple and efficient access to new 2-aminosubstituted-3,6-dihydro-2H-thiopyrans. Three different procedures were used depending on the nature of the polyfluoroalkyl chains (RF=CF3, (CF2)nCF3, (CF2)4H) and on the nitrogen substituents of the thioamides

  全氟烷基硫酰胺与富电子的1,3-二烯（例如2,3-二甲基丁二烯，异戊二烯或五，1,3-二烯）的杂狄尔斯-阿尔德反应使新的2-氨基取代的3,6的反应简单有效。 -二氢-2 H-硫代吡喃。根据多氟烷基链的性质（R F = CF 3，（CF 2）n CF 3，（CF 2）4 H）和硫代酰胺的氮取代基（R 1，R 2 = H，对-Tol，吗啉代，Ac）。此外，甲硅烷氧基二烯（1-或2-三甲基甲硅烷氧基-1,3-丁二烯和丹尼舍夫斯基二烯）与N-酰基，N-甲苯基三氟甲基硫代酰胺几乎在所有情况下均提供相应的3，6-二氢-2 H-噻喃或3-氧代-四氢噻喃。对于非对称的1,3-二烯，研究了反应的区域和立体化学（尤其是使用X射线衍射分析），表明与报道的氟代硫代羧基衍生物具有高度相似性。最后，两个甲硅烷基化的3,6-dihydro-2 H -thiopyrans经历了意外的碱基诱导的环收缩，得到了新的1,3-噻唑烷酮-4-酮。
• Highly fluorinated 2,3-dihydro-1,3,4-thiadiazole derivatives via [3+2]-cycloadditions of tertiary thioamides with nitrile imines derived from trifluoroacetonitrile
  作者：Greta Utecht-Jarzyńska、Sergiy S. Mykhaylychenko、Eduard B. Rusanov、Yuriy G. Shermolovich、Marcin Jasiński、Grzegorz Mlostoń

  DOI：10.1016/j.jfluchem.2020.109702

  日期：2021.2

  derivatives were formed in a fully regioselective manner in high yields. In a competition experiment, the non-fluorinated 1-(morpholin-4-yl)ethanethione was shown to be more reactive towards a model nitrile imine than its 2,2,2-trifluoromethylated analogue.

  富氟的1,3,4-噻二唑衍生物是通过将原位生成的N-芳基-三氟乙腈亚胺与叔多氟链烷硫基酰胺（N，N-二烷基硫代酰胺）进行1,3-偶极环加成制备的。在室温下于温和条件下于THF溶液中进行反应。1,3,4-噻二唑衍生物以完全区域选择性的方式高产率形成。在竞争实验中，未氟化的1-（吗啉-4-基）乙硫酮对模型腈亚胺的反应性高于其2,2,2-三氟甲基化类似物。