Synthesis Of Three Series Of Rosinyl Derivatives Containing Heterocycle And Study On The Products' Property

Dehydroabietic acid (DAA) and dehydroabietylamine (DA) are the isomerides of the renewable rosin. They are widely used in the fields of paint, adhesives, printing ink, papermaking, rubber food and drugs, etc. Similar with many natural drugs, there are aromatic-diterpene-three-ring, three chiral carbon atoms and three reactive groups, benzene, carboxyl and amine on their skeleton. Therefore, DAA and DA might be hopefully modified to some multifunctional derivatives, which can be used as high added value products like novel fluorescence derivatization reagents and efficient but low toxic medicines, through constructing aromatic or heteroaromatic ring on the skeleton. It would bring about favorable economical and social effects. Therefore, we start to do the work of building the heterocycle ring on the rosinyl skeleton.(i) In this paper, firstly, from dehydroabietic acid, five novel furazan derivatives were synthesized with fluorescentλex/λem of 280-330/316-436 nm, through five steps, such as esterification, bromination, nitration, and so on. Compared with DAA's methyl ester, the products'maximal excited wavelengths and emission wavelengths were bathochromic red shifted for 35-70/16-36 nm, respectively. The products were tested to be friendly stable with high temperature, and they began to lose the weight at the temperature 170℃. Besides, methyl 12-bromo-13, 14-oxofurazan-deisopropyl-dehydroabietate and methyl 7-oxo-12, 13-furazan-deisopropyl-dehydroabietate effectively inhibitted MDA-MB-231 in 61 and 31.6 percent, respectively, thus they were potential to be exploited for the precursor compounds of anti-cancer.(ii) Then, we obtained a series of N-rosinyl-4-substituted-1, 8-naphthalimides with fluorescentλ_ex/λ_em of 390-490/400-570 nm, using DA as the precursor. In contrast with DAA's methyl ester, their maximal excited wavelengths and emission wavelengths were red shifted for 140-240/100-270 nm. In our study, N-rosinyl-4-amino-1, 8-naphthalimides showed the best capability for detecting Br- anion, better capability for Cl- anion and no capability for I- anion, indicating that the cavity of these compounds was equal to the radius of Br- anion, says 0.114 nm. In our investigation, the products also displayed good incision property to DNA-pbr322, and they were considered to be novel ronyl drugs.(iii) By coupled with glycol, methyl 13-aminodeisopropyldehydroabietate was converted to two quinolines with fluorescentλ_ex/λ_em of 260-265/370-380 nm. Treated with the complex of hydrochloric acid/natrium nitrite and then sodium acetate, methyl 12-amino-dehydroabietate was converted to methyl 12-chloro-dehydroabietate. Its structure was determined by 1H NMR, as well as the single crystal X-ray diffraction method. Both results showed the same structure.(iiii) In addition, in the optimization of reaction condition of N-rosinyl-1, 8-naphthalimides, a water-solvent-routed preparation of a series of N- and N-, 4- substituted 1, 8-naphthalimides under microwave irradiation, that proceeded via efficient and green reaction of 1, 8-naphthalic anhydride derivatives with different amines, was explored. In this method, the reaction completed in mild conditions, required only a few minutes of reaction time, afforded good yields, and the operation was very simple.In summary, in this paper, 30 new compounds were synthesized and characterized by IR, NMR, X-ray diffraction and MS etc. Our study showed that the properties of DAA and DA, such as fluorescence, thermostability can be improved through constructing aromatic or heteroaromatic ring on their skeleton. All that laid the groundwork for further exploitation of multifunctional reagents.