N-(2,2,2-trifluoro-1-thioxoethyl)-piperidine | 200802-63-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: N-(2,2,2-trifluoro-1-thioxoethyl)-piperidine
• 英文别名: 2,2,2-Trifluoro-1-piperidin-1-ylethanethione
• CAS: 200802-63-7
• 化学式: C₇H₁₀F₃NS
• 分子量: 197.224
• InChiKey: BLCSGUBUTLJLLZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  35.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(2,2,2-trifluoro-1-thioxoethyl)-piperidine 在 氯 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以78%的产率得到N-(2,2,2-trifluoro-1,1-dichloroethyl)-piperidine
  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
• 作为产物：
  描述：

  1-三氟乙酰基哌啶 在 tetraphosphorus decasulfide 、 碳酸氢钠 作用下， 以 乙二醇二甲醚 为溶剂， 以93%的产率得到N-(2,2,2-trifluoro-1-thioxoethyl)-piperidine
  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

• Dual thiophilic or carbophilic reactivity of N,N-dialkyl perfluorocarboxylic thioamides with organometallic reagents
  作者：Vadim M. Timoshenko、Yuriy G. Shermolovich、Fabienne Grellepois、Charles Portella

  DOI：10.1016/j.jfluchem.2005.12.035

  日期：2006.5

  perfluorothiocarboxylic acids react with organomagnesium and organolithium reagents via thiophilic or carbophilic attack of carbanion on the CS bond. The chemoselectivity depends on the nature of the organometallic species. Lithium reagents react at sulfur, with a subsequent β-elimination of fluoride, giving an N,S-ketene acetal. Simple organomagnesium reagents do not react, whereas allylmagnesium halide

  全氟硫代羧酸的N，N-二烷基酰胺与碳镁对CS键的亲硫或嗜碳攻击，使其与有机镁和有机锂试剂反应。化学选择性取决于有机金属物质的性质。锂试剂在硫磺下反应，随后氟化物经β消除，生成N，S-烯酮缩醛。简单的有机镁试剂不反应，而烯丙基卤化镁在碳上反应，生成加合物，该加合物可被甲基碘捕获并转化为相应的N，S-缩醛。后者可以通过氧化转化为全氟烷基二烯胺。
• New fused dithiabicyclic compounds from the reaction of N,N-dialkyl perfluorothioamides with allylmagnesium halides
  作者：Fabienne Grellepois、Vadim M. Timoshenko、Eduard B. Rusanov、Yuriy G. Shermolovich、Charles Portella

  DOI：10.1016/j.jfluchem.2010.06.008

  日期：2010.9

  Allylmagnesium reagents react with N,N-dialkylperfluorothioamide to give, at low temperature, an adduct stable enough to be trapped. At room temperature, this adduct can evolve by elimination of either a sulfide salt, leading to an iminium intermediate, and then an N,N-dialkyl-alpha,alpha-bis(allyl)-alpha-perfluoroalkylamine. This process is favoured if an excess of allyl magnesium is used. Alternatively, the adduct eliminates an aminyl moiety giving allyl(perfluoroalkyl)thioketone which is converted in situ into an unprecedented fused bis(perfluoroalkyl) bis(dihydrothiopyrane). A sequence deprotonation of the thioketone - oxidation of the resulting dienethiolate - dimerization of the dienethiyl radical is proposed to rationalize the formation of this unexpected bicyclic compound. (C) 2010 Elsevier B.V. All rights reserved.