New Method For Synthesis Of N-Aryl Amides And Synthesis Of 8-(4-Hydroxyphenyl) Octyl Phosphonic Acid

This dissertation contains two parts.The first part: New methodforsyn thesis ofN-arylamidesThe amides, as important organic intermediates, are applied widely in themanufacture of medicines, pesticides, fine-chemicals and military industry. Traditionalmethods for synthesis of amides generally use acid anhydride or acyl chloride asacylation reagents. However, these methods are inconvenient due to the strongly irritant,corrosive behavior and the high cost of the catalysts.In this research, a new synthetic method for amides via aminolysis of esters wasfounded, using esters as N-acylation reagents, aluminum chloride and triethylamine aspromoters. The reaction conditions, such as the ratio of the reactants, reaction time,temperature and solvent, were studied in detail. Finally, we found a better reactioncondition. This method was applied in esters, such as: ethyl acetate, methyl butyrate,benzoate, cinnamate, nicotinate, etc.; for different amines, such as: n-butylamine, benzylamine, substituted anilines, amino-pyridine and piperidine. Taking the advantages ofcheaper raw materials, milder reaction conditions, higher yields and shorter reactiontimes, easier post-processing operation, this new method not only provides a newmethod for the protection of amino in organic synthesis, but also has a larger value inexperimental and industrial application.A reasonable mechanism of the reaction was studied by density functional theory。The second part: Synthesis of 8-(4-hydroxyphenyl)octylp hosphonicacidHydroxyphenyl substituted long-chain phosphonic acid was used as functionalmolecule in nano materials.Two routes were designed for synthesis of 8-(4-hydroxyphenyl) octyl phosphonicacid. Target compound was successfully synthesized by Grignard reaction, Arbuzovrearrangement, hydrolysis and demethylation.1, 8-octanediol was used as raw material, then brominated, gave the yield of 90%;then 4-(8-Bromo-octyl)-anisole was prepared from unilateral coupling of pbromoanisoleGrignard reagent with 1,8-dibromo-octane catalyzed by Li2CuCl4, yields47%; then Arbuzov rearrangement; The phosphate ester was hydrolyzed and demethylated in 40% HBr-CH3COOH, giving the target compound 8-(4-hydroxyphenyl)octyl phosphonic acid in the yield of 34%, Total yield 14%.All the intermediates and target compounds were synthesized and characterized by1H-NMR...