<p>This study developed an environmental and highly efficient synthetic route for preparation of amino-methyl-N-phenylcarbamate (TMC). Using commercially available nano-iron powder as a heterogeneous catalyst, methyl metholylcarbamate (MTCM) was converted to TMC via direct amination in hexafluoroisopropanol (HFIP) solvent. Key parameters including amination agent, feedstock ratio, catalyst dosage, reaction time and temperature were explored systematically. The optimized reaction conditions were MTCM/amination agent (molar ratio) 1:1.8, nano-iron powder (0.1&#xa0;g) catalyst, conducted at 40&#xa0;℃ for 3&#xa0;h. Under these conditions, the overall TMC yield reached 66.14%. Characterization revealed that the nano-iron powder exhibits high purity (Fe content: 99.20&#xa0;wt.%) and a well-defined crystalline structure, with a surface featuring a mixed Fe<sup>2+</sup>/Fe<sup>3+</sup> oxide layer. The catalyst showed no significant decline in activity after five cycles, indicating excellent stability and industrial application potential. Furthermore, possible reaction pathway involved free radical species and proton transfer step was proposed for the amination.</p>

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A new route for synthesis of amino-methyl-N-phenylcarbamate with organic amination agent over iron-based catalyst

  • Yu Jiang,
  • Qiusheng Yang,
  • Yanji Wang,
  • Yao Lu,
  • Peng Zhai,
  • Dongsheng Zhang

摘要

This study developed an environmental and highly efficient synthetic route for preparation of amino-methyl-N-phenylcarbamate (TMC). Using commercially available nano-iron powder as a heterogeneous catalyst, methyl metholylcarbamate (MTCM) was converted to TMC via direct amination in hexafluoroisopropanol (HFIP) solvent. Key parameters including amination agent, feedstock ratio, catalyst dosage, reaction time and temperature were explored systematically. The optimized reaction conditions were MTCM/amination agent (molar ratio) 1:1.8, nano-iron powder (0.1 g) catalyst, conducted at 40 ℃ for 3 h. Under these conditions, the overall TMC yield reached 66.14%. Characterization revealed that the nano-iron powder exhibits high purity (Fe content: 99.20 wt.%) and a well-defined crystalline structure, with a surface featuring a mixed Fe2+/Fe3+ oxide layer. The catalyst showed no significant decline in activity after five cycles, indicating excellent stability and industrial application potential. Furthermore, possible reaction pathway involved free radical species and proton transfer step was proposed for the amination.