Study On N-Chiral Quaternary Ammonium Salts Based On Linear L-Amino Acids

This dissertation aims at the studies on N-chiral quaternary ammonium salts (QASs)of linear L-amino acid,including the syntheses,separation,the absolute configuration determination of N-chirality,and their stablity.It consisted of the following three parts:The syntheses and applications of N-chiral QASs in organic syntheses (Riview)Described the finding,syntheses,separation,the absolute configuration determination and applications of N-chiral QASs in organic syntheses.Studies on N-chiral QASs of linear L-amino acid,including the syntheses, separation,the absolute configuration determination of N-chirality.We synthesized tertiary amine using improved"one pot"method from linear L-amino acid,and synthesized twelve paries of linear and cyclic N-chiral QASs successfully.We separated nine pairs of these QASs diastereomers through resolution by chiral BINOL,recrystallization,precipitation and determined the absolute configuration of N-chirality by X-ray single crystallographic analysis for sixteen of them.Studties on the substitute reaction,asymmetric catalyzed reaction and the stability of N-chiral QASsIn the course of synthesis of N-chiral QASs from L-amino acids,when the tertiary amine with a methoxycarbonyl group refluxed with allyl bromide in CH₃CN, diallyl substitued QASs were obtained instead of the expected N-chiral QASs.We studied the reaction conditions such as various substrates,temperature,halogenated hydrocarbon.We believe that the required N-chiral QASs were formed firstly,then they reacted with allyl bromide quickly to obtain the diallyl substitued QASs.The preliminary experiments indicated that the tertiary amine with a methoxy car-bonyl group and the allyl bromide are necessary for the substitute.The preliminary experiment indicated that the N-chiral QASs have a certain extent asymmetric catalyzed activity,but the selectivity is not high.There is no racemization when N-chiral QASs under light,hot,acid and base...