The Design And Synthesis Of The Derivatives Of BINOL And1,3-dithiolanes

1,1’-Binaphthyl-2.2’-diol (BINOL) and its derivatives find wide application in asymmetric synthesis, molecular recognition, new functional materials and other research fields. Based on recent BINOL research development, mono-alkylation in2’position hydroxyl group of2’-alkyloxy-1,1’-binaphthyl-3-carboxamide was designed. Additionally, we also design the synthesis of2-(2-nitro-4-methoxyformyl)-1,3-dithiolanes.Most probally this compound has important research value and application prospect in the field of the perfume and pharmaceutical intermediate areas.Firstly, skeleton compound2,2’-dihydroxy-1,1’-binaphthyl-3-aldehyde was obtained from BINOL, successively by two hydroxy groups’protection, di-MOM BINOL’s metallation by n-BuLi and reaction with DMF, deprotection. The product was characterized by IR, MS,1H NMR, etc. The effects were investigated by molar ratio, catalyst, time and temperature on yield, and the yield can reach63%.Secondly,2,2’-dihydroxy-1,1’-binaphthyl-3-aldehyde was prepared as the important intermediate, explore KF.2H2O, Cs2CO3, Copper Complexes and NaH these four methods to complete mono-alkylation in2’position hydroxyl group. The route which is possible was improved. The route of NaH is feasible, and the yield can reach52%.Finally,2-(2-nitro-4-methoxyformyl)-1,3-dithiolanes was prepared with3-nitro-4-methyl benzoic acid as the major starting material, successively by esterification, condensation, oxidation and the protection of aldehyde group by ethanedithiol to change the methyl group into1,3-dithiolanes group. The structures of the target compound and some important intermediates were characterized by IR, ESI-MS, and1H NMR, etc.