Synthesis,Characterization And Biological Activities Of Pine Resin Acids Derivatives

Producing high value products through chemical modification of main component ofnatural resources is the important direction of natural product research. Rosin is an importantnatural resource of China, pine resin acids are the main components of rosin, they have beenattracted great interest for their special chemical structures and wide range of biologicalactivities. In this paper, 48 compounds with six characteristics of pine resin acids derivativescontainied tricyclic diterpene structure of Schiff bases, metal complexes, aminophosphonats,amides, isocyanate and ureas were synthesized through condensation reaction, additionreaction and hoffman reaction by using of pine resin acids and their derivatives as rawmaterials through the idea of connecting of active groups. Those 30 compounds which fluorinecontaining Schiff bases and amides, aminophosphonates and ureas were synthesized for thefirst time. Their structures were characterized by elemental analysis, IR, UV-Vis, NMR,TG-DSC, MS spectroscopy and single crystal X-ray diffraction. The antibacterial, antifeedantand antitumor bioactivities of pine resin acids derivaties were investigated.Six compounds with four characteristics of pine resin acids derivaties single crystals wereobtained and their structures were analysized for the first time, crystals (2i) and (2e) containedclassic configuration of dehydroabietic group with t_ricyclic hydrophenanthrene structure, threesix-membered rings exhibited plane, half-chair and chair conformations, respectively. Twomethyl groups were in the same side of rings, three chiral carbon atoms exhibited R-, S- and R-configurations, respectively. C=N bond exhibited trans conformation. Crystal (3a) exhibitedclassic N₂O₂ ligand metal complex containing dehydroabietic group with tricyclichydrophenanthrene structure, two crystallorgraphieally independent molecules co-exist in thestructure. Crystals (5g) and (5l) contained classic configuration of dehydroabietic group withtricyclic hydrophenanthrene structure, the introduced piperidine ring exhibited classic chairconfiguration. Crystal (6d) contained the classic tricyclic hydrophenanthrene structure, theintroduced benzyl ring with two methyl groups are in the same plane.The antibacterial activities of Schiff bases, metal complexes, amides, isocyanate and ureasderivatives of pine resin acids were investigated by using of disc paper method for the firsttime, three kinds of bacterials such as E.Coli., S.Aureus. and B.Subtilis. which haverepresentative characteristic were selected in the experiments. It has been found that, degradeddehydroabietic isocyanate (6a) has wide ranges and high activities to selected gram positive,gram negative and subtilis organisms, the diameters of antibacterial rings reached 2.17, 2.70 and 2.90cm at the concentration of 2000μg/mL, respectively. Other compounds have selectivityto organisms, the fluorine containing Schiff bases and ureas, Schiff base copper(â…¡) complex,the alkyl group connected to N atom of amides exhibited higher activities. Compounds (6a),(6e), (6g) and (5h) can be as potential antibacterial reagents for further research.The insects feed activities of some Schiff bases and amides derivatives of pine resin acidswere investigated by using of leaf plate method for the first time. They exhibited selectivity toinsects feed, Schiff bases and amides have little influence to Musca domestica feed, the activityis very low. Schiff bases and amides exhibit insect attractant activities to Spodoptera litura, inwhich dehydroabietic m-fluorine benzaldehyde Schiff base (2e) and dehydroabieticp-tri-fluorine-methyl amide(5k) exhibited 4～7 times of attractant rate compared with blank atthe concentration of 0.01g/mL. However, Schiff bases and amides exhibit strong insectantifeedant activity against Aphid, the antifeedant rate reach 90～100% at the concentration of0.01g/mL. Compounds (2e) and (Sk) can be as attractants to Spodoptera litura. Compounds(2c), (2d) and (5n) can be as antifeedants against Aphid for further research.The antitumor activities of Schiff bases, amides and aminophosphonates derivatives ofpine resin acids were investigated by using of SRB method for the first time.Aminophosphonates exhibited higher activity against SMMC7721 cell than Schiff bases andamide, the inhibition rate reach 70% at the concentration of 0.1μmol/L and 99% at theconcentration of 100μmol/L. The aminophosphonates which containing fluorine, cholrine andnitro group in the benzene ring and the alkyl connected to the phosphorous oxygen with nitrogroup have higher activities. Some compounds exhibited time and amount related activies.Compounds (4d), (4f), (4g), (4h) and (4i) can be as antitumor reagents anginst SMMC7721 forfurther research.