Preparation Of Dehydropartic Acid/Amine Immobilized Chiral Ionic Liquid And Their Adsorption Performance For Enantiomers

Dehydroabietic acid is a tricyclic diterpene monobasic resin acid isolated from disproportionated rosin.It is a natural optically pure chiral compound and a potential chiral resolving agent.Immobilized ionic liquid is a kind of ionic liquid which fixed on the carrier surface with either simple physical adsorption or covalent/non-covalent interaction.In this thesis,two immobilized chiral ionic liquids were prepared by chemical bonding with dehydropartic acid/amide as raw materials,and SiO₂ microspheres as carriers.The preparation conditions of immobilized chiral ionic liquids were optimized by single factor and orthogonal experiments,and the adsorption of enantiomers on the chiral ionic liquids were studied.The main contents are as follows:?1?Dehydropartic acid and imidazole are used to prepare 1-?dehydroabionic acid-1-methyl?-imidazole.Dehydroabietic acids immobilized chiral ionic liquid [PDHAMIm⁺][Cl^-]@SiO₂ was obtained by chemical bonding method with SiO₂ microspheres as carriers.By single factor and orthogonal experiments,the effects of feeding ratio,reaction temperature,reaction time,solid-liquid ratio bonding rate were investigated to optimize the synthesis process factors of [PDHAMIm⁺] [Cl^-]@SiO₂.The optimal conditions are listed,feeding ratio of 1:3,reaction temperature of 120?,reaction time of 48 h,liquid-solid ratio of 1:8,and then the bonding rate is 17%.?2?Dehydroabietyl amine is converted to N,N-dimethyldehydroabamectin.With SiO₂ microspheres as carriers,dehydroabietylamine immobilized chiral ionic liquid [NDHAM₂⁺][Cl^-]@SiO₂ was prepared,and identified by HPLC,FT-IR and TG.By single factor and orthogonal experiments,the effects of feeding ratio,reaction temperature,reaction time and catalyst amount on the bonding rate were studied.The optimized conditions for [NDHAM₂⁺][Cl^-]@SiO₂ are as follows,feed ratio of 1:3,reaction temperature of 105?,reaction time of 3d,catalyst dosage of 1:3,and then the bonding rate is 21%.?3?[PDHAMIm⁺][NTf₂^-]@SiO₂ and [MDHAH2+][NTf₂^-]@SiO₂ were used for mandelic acid,propranolol and valsartan enantiomers resolution as adsorbents,respectively.The effects were tested by HPLC.The results showed that [PDHAMIm⁺][NTf₂^-]@SiO₂ and [MDHAM₂⁺] [NTf₂^-]@SiO₂ have a better resolution for mandelic acid enantiomers using methanol as solvent,which e.e are 18.7% and 23.8% respectively;and ethanol as solvent,propranolol enantiomers have a better resolution result with e.e of 16.0% and 25.4% respectively;but using methanol,ethanol,ethyl acetate as the solvent,[PDHAMIm⁺][NTf₂^-] @SiO₂ and [MDHAM₂⁺][NTf₂^-]@SiO₂ have no effect on the resolution of valsartan enantiomers.