Chemical Combination Of Dehydrobietic Acid And Dehydrobietic Amine With Spice

Rosin is a very abundant,natural,and renewable resource,and the output of rosin in Guangxi is ranked first in China.Rosin and its derivatives are widely used in a variety of industries.It has become one of the research focuses for forest chemistry and chemistry of organic synthesis to synthesize various derivatives with new functions by chemical modification of functional groups in rosin.Dehydroabietic acid and dehydroabietic amine,the respective main components of disproportionated rosin and disproportionated rosin amine,are a diterpenoid compound which has phenanthrene ring skeleton,several chiral centres,and two reaction centres of carboxyl(or amino)group and benzene ring,and is close to many natural active compounds in structural skeleton.In this thesis,dehydroabietic acid-alcohol spice esters and dehydroabietic amine-aldehyde spice Schiff bases were synthesized by chemical modification of carboxyl group in dehydroabietic acid and amino group in dehydroabietic amine,and by chemical combination of dehydroabietyl group with alcohol spice or aldehyde spice.This research aims at providing experimental data for the application of the target compounds as ultraviolet absorbent in sunscreen cosmetic,and providing a new way for the deep development and utilization of dehydroabietic acid and dehydroabietic amine.In this thesis,dehydroabietic acid 1 was separated and purified from disproportionated rosin,and converted into its acyl chloride 2.Then,four dehydroabietic acid-alcohol spice esters 3a-3d including dehydroabietic acid-cinnamyl alcohol ester 3a,dehydroabietic acid-fenchanol ester 3b,dehydroabietic acid-camphol ester 3c,and dehydroabietic acid-menthol ester 3d,in which dehydroabietic acid-cinnamyl alcohol ester 3a and dehydroabietic acid-fenchanol ester 3b were novel compounds,were synthesized by the O-acylation reaction of dehydroabietic acid chloride 2 with four corresponding alcohol spices including cinnamyl alcohol,fenchanol,camphol,and menthol,which can be obtained by extraction or conversion from natural products,using dehydroabietic acid 4 as starting material.The synthetic conditions were investigated preliminarily,and the target compounds were characterized by means of IR,UV,MS,1HNMR,13C NMR,and elemental analysis.Besides,the single crystal of 3b was obtained by solvent evaporation method,and its absolute configuration was determined by single crystal x-ray diffraction.Also,dehydroabietic amine 4 was separated and purified from disproportionated rosin amine at first.Then,three dehydroabietic amine-aldehyde spice Schiff bases 5a-5c including dehydroabietic amine-cinnamaldehyde Schiff base 5a,dehydroabietic amine-anisaldehyde Schiff base 5b,and dehydroabietic amine-vanillin Schiff base 5c,which were not reported in literature,were synthesized by the condensation reaction of dehydroabietic amine 4 with three corresponding aldehyde spices including cinnamaldehyde,anisaldehyde,and vanillin,which can be obtained by extraction or conversion from natural products,using dehydroabietic amine 4 as starting material.The synthetic conditions were investigated preliminarily,and the target compounds were characterized by means of IR,UV,MS,1H NMR,13C NMR,and elemental analysis.