Separation Of Abietic-type Resin Acids And Synthesis, Biological Activities Of Their Derivatives

Separating monomeric compounds from biomass resources and then using them to synthesize new compounds with biological activity is a significant way in deep processing of high value-added biomass resources products. Resin is an important biomass resource in China. Abietic type resin acid is the main ingredient of rosin. Separation of them and synthesis, biological activities of their derivatives are of great signfication in development of advanced-processed products of resin.In this paper, Abietic acid with 90.9% and 97.5% purity were obtained using A amine salt method and B amine salt method for the first time. The costs of abietic acid separating with A amine salt method and B amine salt method were 1/5 and 1/3 of cost separating with di-n-amylamine salt reported in the literature respectively. The isomerization of resin acid was studied by HCl catalysis method, high temperature catalysis method and microwave-assisted method. Separation of abietic acid was analyzed with recrystallization method and many organic amine salt methods; Using abietic acid separated from resin acid as raw materials, 6 compounds of abietic-type resin acid derivetives were synthesized.Dehydroabietic acids with 98.3% and 89.8% high purity were obtained byα-ethanol amine method and sodium salt adidification method. Using solvent method and high temperature melting method, S, I2 and Pd/C catalysts, disproportionation resin with 75%⁸3% dehydroabietic acid was gained.Using dehydroabietic acid separated from resin acid as raw materials, 42 compounds of abietic-type resin acid derivatives included sulphur acid salts, diazoles, hydrazines and hydrazones were prepared. In those compounds, 26 ones were new compounds. Their sturctures were charaterized by GC, MS, IR, 1H MNR, UV, elemental analysis and X-ray diffraction.The antigastric ulcer activities of 5c and 5e were investigatied with pyloric ligation-mice, acetate-rat , indomethacin -rat, flooding stress-rat and anhydrous alcohol-rat as gastric ulcer model. The ulcer inhibition rates of dehydroabietic acid acid-sulfonated double-ferrous salt and dehydroabietic acid acid-sulfonated potassium salt were 95% and 94% at the dosage of 100 mg·kg^-1 in indomethacin rat model. The antigastric ulcer results showed that the biological activity of former compound was better than that of the latter one. The antigastric ulcer mechanism of various models were analysed.Antibacterials including Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Shigella dysentery bacilli and Streptococcus activities of 32 compounds were tested by using filter paper method. Compounds dehydroabietical -2,3,4 - three hydroxy hydrazone 6f, dehydroabietical -2,3,4 - three fluorophenyl hydrazone 6i and dehydroabietical benzene hydrazone 6l showed excellent antibacterial activities with dose of 5 mgï¹’mL-1. The three compounds can be used as potential antimicrobial agent. The antibacterial activities showed that substituent position and introduction of the group greatly affect antibacterial activity.Antifeedant activity on the housefly of 8 compounds were investigated by leaf butterfly method. With dose of 0.01 g/mL, dehydroabietical -2,3,4 - three fluorophenyl hydrazone 6i, dehydroabietical benzene hydrazide 7a, 2- dehydroabietical -5-fluoride benzene- 1,3,4- oxadiazole 8d and 2- dehydroabietical -5-fluoride benzene-1,3,4-thiadiazole 8i had antifeedant activities, dehydroabietical ethoxy double hydrazide 7e, dehydroabietical benzene double hydrazide 7f and 2,5 - dehydroabietic-1, 3,4 - oxadiazole 8g showed feed attractant acitivities. Substitute group has notable effect on antifeedant activity of compounds.Three single crystals of N-nitrobenzene, N-acyl dehydroabietic hydrazine 7c single water compounds, N, N-acyl dehydroabietic hydrazine 7l and 2,5 - dehydroabietic-1, 3,4 - oxadiazole 8g were obtained for the first time. X-ray diffraction analysis of these crystals showed dehydroabietic acid skeletons were contained in these crystal molecules.