| Dehydroabietylamine is a kind of modified product from rosin. A series ofdehydroabietylamine derivatives containing acyl group or Schiff base weresynthesized through amino in ring C reaction with protocatechuic acid and caffeicacid using dehydroabietylamine as raw materials in the paper. After introducingcarbonyl for the ring B of dehydroabietylamine, the corresponding amides andlactone were produced under the Beckmann rearrangement, Baeyer-Villigeroxidation rearrangement and reduction conditions. A series of newly compoundswere generated by hydrolysis reactions of the corresponding amides and lactone.These structures of dehydroabietylamine derivatives were characteristed by IR,1H NMR,13C NMR, MS and elemental analysis. We try to find some compoundsowing stronger biological activity though biological activity tests, which canprovide better bases for further drug researchs in the field.(1) Dehydroabietylamine was changed into12,14-diaminodehydroabietylamine(2h) and12-nitro-14-aminodehydroabietylamine (2b) via nitration and reductionreaction, respectively. A series of polyphenols compounds were generated through2b and2h reaction with protocatechuic acid and caffeic acid, protocatechuicaldehyde. The yields were from50.0to88.2%. Dealing with the polyphenols usingdifferent concentrations of oxidants, we explore polymerization of the derivativesand find12,18-di[(3,4-dihydroxybenzylidyne) amino]-14-nitrodehydroabietane (2c)can be polymerized to generate a new type of dimers (2e) under the influence ofH2O2/Vc.The effects of the synthesized polyphenols derivatives on the viability of HepG2cells were evaluated by MTT method, and the results shown that the compounds12,18-di[(3,4-dihydroxybenzylidene)amino]-14-nitrodehydroabietane (2d) and2ihave low cytotoxicity against HepG2than L02. We investigate the effects ofcompounds2d and2i on apoptosis induction in HepG2cells. The results shown that10μg·mL-1of compounds2d and2i have apoptosis induction effect in HepG2cells,but have no effect in L02cells. Our results suggest that the compound2d and2icould be promising candidate in the development of novel class of anticancer agents.Radical scavenging activity of the synthesized polyphenols derivatives againstDPPH· and O2-were tested. The results showed that dehydroabietylamine has loweractivity of scavenging free radicals. Radical scavenging activity ofdehydroabietylamine derivatives can be greatly improved because of introducingcatechol. The compounds with terminal group of catechol had the higher scavengingradical activity. The value of IC50was0.012×103μg·mL-1for12,18-dicaffeoylamino-14-nitrodehydroabietane (2i) against DPPH·.(2) Dehydroabietylamine reacting with chromic acid produced18-acetylamino-7-oxo-dehydroabietane (3a) and18-trifluoroacetylamino-7-oxo-dehydroabietane (4d) under the protection of the acetic anhydride and trifluoroacetic anhydride,respectively. Compounds3a and4d via ammonification, Beckmann rearrangementreaction and reduction reaction can give a series of the corresponding N-heterocyclicand O-heterocyclic compounds after oxidized by H2O2/ZnO, Baeyer–Villigerrearrangement reaction.3-isopropyl-8,11a-dimethyl-8-trifluoroacetamidemethyl-6-oxo-6,7,7a,8,9,10,11,11a-octahydro-5H-dibenzo[b,d]oxepin (4i) can give a newlycompound containing N-heterocyclic isoquinoline5-(2-hydroxy-4-isopropyl-phenyl)-5,8a-dimethyl-octahydroisoquinolin(4m) after hydrolysis, reduction reaction.A facile and efficient one-step synthesis of novel compound13-chloro-10,11-bis(dimethylamino)-2-isopropyl-4b,7a-dimethyl-12-formyl-7b,5,6,7,7a,8-hexahydro-4bH-dibenzo[de,g]pyrrolo[2,1-a]isoquinoline (5a) was developed via the Vilsmeier-Haack reaction of accessibly compound3a. The stereochemical structure wasconfirmed by NMR, HRMS, elemental analysis and X-ray single-crystal diffractionanalysis. The proposed reaction pathway for the compound synthesis were dicussed.The effects of the synthesized dehydroabietylamine derivatives on the viabilityof HepG2and L02cells were evaluated by MTT method, and the results shown thatall compounds have low inhibitory effect than compound2e. The synthesizedcompounds were evaluated against CCR5/α1B receptor by calcium current screeningmethods. The results showed that12,14,18-tricaffeoylaminodehydroabietane (2j) hasa weaker antagonistic effect on α1B-adrenoceptor at the concentration of10μmol·L-1. Other compounds have no antagonism and exciting effect againstCCR5/α1B receptor. The synthesized compounds were also evaluated against HIV-1reverse ranscriptase activity. The results showed that the compound12,18-di(3,4-dihydroxybenzoyl)-14-nitrodehydroabietane (2f) has a mediumantagonistic effect on α1B adrenoceptor at the concentration of100μmol·L-1.AntiHIV-1reverse ranscriptase activity of other compounds are not obvious.(3) The dehydroabietylamine derivatives including the polyphenols, Schiff bases,N-heterocyclics, O-heterocyclics and others, more than90kinds of derivatives, werestudied of cleavaging Escherichia coli plasmid DNA activity. The study show thatthe phenol derivatives can’t cleavage plasmid DNA, and antioxidants have aprotective effect on plasmid DNA damage, but these compounds in the presence ofmetal ions can produce different degree of cleavaging plasmid DNA. We concludedthat plasmid DNA fractures were not from oxidation, but from hydrolysis ofphosphodiester bond. Cleavaging plasmid DNA of Schiff base is associated with theelectronic and distribution of N=C. These Schiff bases with electron-withdrawinggroups such as F, CF3, Cl have stronger cleavaging DNA activity than the Schiff basewith electron-donating groups such as CH3, OCH3, which means that some form ofelectrical effect cause cleavaging plasmid DNA strand rupture.(4) Schiff bases from condensation between pyridinecarboxaldehydes anddehydroabietylamine showed stronger inhibitory activity aganist HepG2cells and The Schiff bases can also cleavaging plasmid DNA, which manifest the internalrelation among compound structure, anticancer activity aganist HepG2cell andcleavaging DNA. Other kinds of compounds did not reflect the internal relation.
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