Synthesis And Exploration Of The Disubstituted Adamantane Derivatives

Wide application of adamantane and its derivatives has been found in the fieldsof medicine, polymer, surfactant, catalyst and photosensitive material and so on.Consequently, adamantane and its derivatives are known as "the fine chemicals ofnew generation". Many disubstituted adamantane derivatives show good to excellentanti-virus effect. Besides, due to the difunctional groups present, they can be used forthe synthesis of other adamantane derivatives such as various polymer materials,which may find wide application in the fields of new organic materials and showpromising perspective especially in photocommunications. However, the researchconcerning the disubstituted adamantane derivatives is rarely reported in our country.Therefore, our exploration of the synthesis and application of the disubstitutedadamantane derivatives is of significance.This dissertation focuses mainly on the synthesis of disubstituted adamantanederivative 1,3-adamantanedicarboxylic acid. The quantitative analysis of1,3-adamantanedicarboxylic acid by GC was performed at the same time. Based onthe research results, other adamantane derivatives such as 1,3-adamantanedimethanol,1,3-adamantanediacetic acid and chiral 3-Hydroxy-1-oxazolineadamantane were alsoprepared and their structures were characterized. More concrete contents of thedissertation are described as the following.1. Two methods were exploited for the synthesis of 1,3-adamantanedicarboxylicacid using adamantane as starting material. One method involved dibromizationof adamantane to form the bromide, which was then hydrolyzed to produce thecorresponding diol. Final Koch-Haft reaction of the diol afforded the expected1,3-Adamantanedicarboxylic acid. The other follows the stepwise brominationand then Koch-Haff reaction. This section also established the a method for thequantitative analysis of 1,3-adamantanedicarboxylic acid by GC. 2. 1,3-Adamantanedicarboxylic acid was esterfied and then reduced byNaBHB_4B/LiCl to give 1,3-adamantanedimethanol. The method for thepreparation of 1,3-adamantanedimethanol has the potential for large-scalemanufacture because it involved only mild reaction conditions and easymanipulation.3. 1-Adamantaneacetic acid was synthesized from 1-hydroxyadamantane viareaction with 1,1-dichloroethene, bromination, hydrolysis and then reaction with1,1-dichloroethene again.4. 3-Hydroxy-adamantanecarboxylic acid was used as the starting material for thesynthesis of chiral oxazoline via a series of reactions including protection of thehyroxy, transformation of the carboxyl to acyl chloride, acylation of the chiralamino alcohol, cyclization and then deprotection.5. Chiral aminol alcohol was condensed with urea under solvent-free conditionsaffording chiral 2-oxazolidinones. The short reaction time, eco-friendliness andsimple operation make the reaction preferable for the synthesis of chiral2-oxazolidinones.