Resolution Of 1,1'-Bi-2-Naphthols With Synthesized Derivant Of L-Glutamic Acid

1,1′-bi-2-naphthols(BINOL) is the best known representative of C2-axially chiral molecules. BINOL have become the most widely used ligand for both stoichiometric and catalytic asymmetric reactions. The synthesis of enantiomerically pure (R)- or (S)-BINOL has been estensively studied, and two major different approaches have been developed, resolution of racemic BINOL and direct stoichiometric or catalytic oxidative coupling synthesis. The main object of this thesis is to investigate the resolution of racemic BINOL with synthesized derivant of L-glutamic acid.The work of this paper is summarized as follow.1. The enantiomer separation of 2-pyrrolidone-5-carboxyanilide(1) was investigated by high performance liquid chromatography(HPLC) on chiral stationary phase derived from L-tartaric acid in the normal-phase mode.1) The effects of the concentration of 2-propanol and flow rate of the mobile phase were examined.2) The best separation was obtained with hexane/2-propanol(90:10) as eluent, at a flow rate of 1.0 mL/min and at room temperature using KR-100-TBB(250mm×4.6mm,5um) column. 3) The retention time of (R)-1 and (S)-1 were 19.2min and 21.5min respectively, and the resolution was 1.51.2. The methods of the synthesis of optically pure (S)-2-pyrrolidone-5-carboxyanilide was studied.1) Optically pure (S)-2-pyrrolidone-5-carboxyanilide was synthesized by aniline reacting with L-glutamic acid(2), L-pyroglutamic acid (3) and L-methyl pyroglutamate (4).2) The effect of the reaction time, reaction temperature and solvent on the racemization were examed.3) Discussed the mechanisms of the racemization during the synthesis and the persent of by-product(5).3. Studied the resolution of racemic BINOL(6) has been developed by modification of a (S)-2-pyrrolidone-5-carboxyanilide resolution procedure.1) Both enantiomers can be easily obtained with >99% adopting the methods of kinetic control crystallizing.2) And the effect of the reaction time, the quantity of chiral reagent, the compose and the volume of solvent to the yield of each enantiomer were examined via orthogonal array experiment.