Metal-free Photoinduced Synthesis Of Amine Derivatives

In this thesis,the synthesis of N-CF₃ compounds,hydroxylamine and amide compounds under photo-induced conditions without the participation of transition-metals are studied.The research includes the following aspects:（1）An efficient synthesis of N-CF₃ hydroxylamine compounds by transition-metal free conditions induced by lightObjective:A series of N-CF₃ hydroxylamine compounds are synthesized in a gentle,simple and efficient manner.Methods:Trifluoromethylated hydroxylamine was synthesized from nitosobenzene and Sodium trifluoromethanesulfinate.The solvents,alkali,temperature and reaction time were screened respectively.The optimal reaction conditions were established and the applicability of the substrate was investigated.Results:We established the optimal reaction conditions for the synthesis of trifluoromethylated hydroxylamine:acetic acid as the additive,H₂O and acetone as the solvent at room temperature for 12 h.A total of 20 trifluoromethylated hydroxylamine compounds were synthesized in yields from 68%to 81%.Conclusion:A method for the synthesis of trifluoromethylated hydroxylamine under UV conditions with simple operation and high yields was established.（2）An efficient synthesis of acetyl hydroxylamines or amides by photo-induced and transition-metal free reactionObjective:A series of acetyl hydroxylamines or amides are synthesized in a gentle,simple and efficient method.Methods:1)Acetyl hydroxylamines was synthesized from nitosobenzene and diacetyl.The solvents,additive,temperature and reaction time were screened respectively.The optimal reaction conditions were established and the substrate scope was investigated;2)Amides was synthesized from nitosobenzene and diacetyl.The solvents,additive,temperature and reaction time were screened respectively,the optimal reaction conditions were established and the applicability of the substrate was investigated.Results:We determined the optimal reaction conditions:acetic acid as additive,H₂O as solvent,and the best reaction at room temperature for 12 h.A total of 20 acetyl hydroxylamines and a total of 20 amides were synthesized in a yield of 72%to 94%.Conclusion:The photo-redox reaction for the synthesis of acetyl hydroxylamines or amides was realized under visible light under mild conditions with simple operation and high yields.