Alkaline Hydrolysis Of (4-(2-Alkenoyl) Phenyl) Triarylphosphonium Salts

Aryl quaternary phosphonium salts and biaryl compounds have extremely broad applications in organic synthesis,materials and biomedicine.β-Diarylphosphoryl ketones have been used as extractants,extractant precursors and ligands.This dissertation mainly focuses on the following two aspects to carry out research.One is to study the synthesis of aryl quaternary phosphonium salts.We chose4’-bromoacetophenone and methyldiphenylphosphine as model compounds to study their reaction to form(4-acetylphenyl)methyldiphenylphosphonium bromide in refluxing phenol.The effects of reaction time,molar ratio of starting materials and solvent amount on the yield of the product were investigated by ~1H NMR.Nineteen groups of NMR data were collected,analyzed and calculated,and the corresponding curves were drawn.The results show that the yield of the product increases with the increase of reaction time(1–5 h),and the optimal reaction time is 5 h,further prolonging the reaction time cannot improve the yield of the product.Increasing the molar ratio of methyldiphenylphosphine to 4-bromoacetophenone generally reduces the product yield.The yield of the product decreased with the increase of phenol amount.Anotheristostudyalkalinehydrolysisof(4-(2-alkenoyl)phenyl)triarylphosphonium salts.When the phosphonium salts are hydrolyzed under alkaline conditions,an aryl-aryl coupling reaction occurs first to generate biaryl-containing?,?-unsaturated ketones with concurrent formation of diphosphine oxide anion,followed by their phospha-Micaheal addition reaction,producing?–diphenylphosphoryl ketones.The quaternary phosphonium salts are readily prepared from bromo-substituted chalcones and triarylphosphine using nickel bromide as catalyst in refluxing pheol.The hydrolysis of these salts using potassium hydroxide in water and ketone for 3 h produces theβ-diarylphosphoryl ketones in moderate to good yields,therefore providing a facile route to synthesizeβ-diarylphosphoryl ketones.