Synthesis Of Benzyl Phosphine Oxides And O-(dialkylphosphinyl)ketone Oximes

Organophosphorus compounds are an important class of organic compounds that exist in the fields of medicines,agricultural chemicals,polymer materials,and organic synthesis.Among them,benzyl phosphine oxides and O-?dialkylphosphinyl?ketone oximes are important derivatives in organic phosphine oxides,and have extensive application prospects.Therefore,it is of great significance to use new methods to synthesize such compounds.The research work of this thesis mainly includes two parts:?1?Benzyl phosphine oxides were synthesized via copper-catalyzed cross coupling reaction of benzyl quaternary ammonium salts and dialkylphosphine oxides via C-N bond cleavage;?2?Molecule iodine-catalyzed oxidative coupling of ketoxime and dihydrocarbylphosphine oxides under the condition of hydrogen peroxide to form N-O-P bond to form O-?dialkylphosphinyl?ketone oximes.The details are as follows:1.In the presence of copper salt,benzyl quaternary ammonium salts undergoes nucleophilic substitution with different dialkylphosphine oxides to generate various C-P bond coupling products,that is,benzyl phosphine oxides.First,we screened the reaction conditions and got the optimized reaction conditions.Then the scope of substrates was investigated under the optimized conditions,and a series of benzyl phosphine oxides with good to excellent yields were synthesized.Finally,a possible reaction mechanism was proposed.2.We have developed a new method of synthesize O-?dialkylphosphinyl?ketone oximes via the oxidative coupling of ketoximes and dialkylphosphine oxides in the presence of hydrogen peroxide and molecule iodine.This method has the advantages of higher atomic economy,no metals and ligands needed,simple operation,wide scope of substrates,good and excellent yields,and gram-scale synthesis.We obtained the relevant spectral characterization of the reaction intermediate,and thus proposed a plausible reaction mechanism.In this paper,some reported compounds and all unknown compounds of the products were characterized by ¹H-,¹³C-and ³¹P-NMR,and HRMS spectrometry.