Study On The Friedel-Crafts Reaction Of DAA And MDAA And The Fluorescence Property Of Their Derivatives

Dehydroabietic acid (DAA) is one of important renewable resources. It is widely used in many fields such as paint, adhesives, printing ink, papermaking, rubber, food additive, biological product, etc. It is a natural chiral compound with three chiral carbon atoms and a reactive carbo- xyl group. Like some natural drugs, it has a aromatic diterpene structure with three rings. There- fore, DAA might be hopefully modified to some intermediates with better spectral properties or notable anti-bacterial, anti-virus activity or good recognition to metal ions through Friedel-Crafts reaction on the aromatic ring. It is not only meet with the demand of green chemistry but also br- ing about favorable economical and social effects.Part I, the Friedel-Crafts acylation on DAA and methyl dehydroabietic acid (MDAA) was carried out with acetyl chloride, benzoyl chloride or phthalic anhydride as acylating regents, anh- ydrous aluminum chloride as catalyst and with different solvents to compare with, we have got t- hree new compounds. The experiments show that it is better to use tetrachloroethane as solvent to get higher productivity if DAA as substrate, acyl chloride as acylating reagent, while to MDA- A, carbon tetrachloride is better. Studying on the ultraviolet and fluorescence properties of those compounds shows that it is affected by the groups inducted to the aromatic ring but not by the presence of the ring A and B of dehydroabietic acid moiety.Part II, methyl 12-(3-anthracene-2-propen-1-one) dehydroabietic acid and methyl 12-(3-na- phthalene-2-propen-1-one) dehydroabietic acid was synthesized from methyl 12-acetyl dehydro- abietic acid and 9-anthracene formaldehyde, naphthalene formaldehyde by aldol condensation. While reducing of the electron withdrawing group of the former by Wolff reaction and making the ester group hydrolyzed at the same time to give 12-(3-anthracene-2-allyl) dehydroabietic acid. Studying on their fluorescence properties, we find that the fluorescence performance of the latter improves greatly (λex/em=368/433nm) compared to methyl 12-(3-anthracene-2-propen-1-one)d- ehydroabietic acid (λex/em=321/388nm), the maximal wavelength of the fluorescence excitation and emission is bathochromic shifted around 45nm respectively. In addition, we also studied the fluorescence properties of methyl 12-(3-anthracene-2-propen-1-one) dehydroabietic acid in diff- erent solvents and its recognition ability to different kinds of metal ions, it shows that, there is a correlation of the fluorescence properties with the polarity of the solvent: In the polar solvent, the excitation and emission wavelengths are both maximal (λex/em= 321/388nm) and it has a good recognition to Cu²⁺, Fe³⁺, Ni²⁺ , etc. Part III, 12-benzyl dehydroabietyl thioisocyanate was synthesized from methyl 12-benzyl dehydroabietic acid, by hydrolysis, chloride, Curtius reaction to give isocyanate which was hydr- olysied to amine under acidic condition, and with the method of CS2 at last, the maximal excitat- ion wavelength was bathochromic shifted 14nm compared to DDHA-NCS. All the compounds we received were characteried by UV, IR, NMR in this paper. Besides, we studied the influence of different kinds of metal ions to the DMF system of 12-benzyl dehydroabietyl thioisocyanate. It shows that it has a recognition to K⁺,Ba²⁺,Cd²⁺,Zn²⁺, but it is still need to study or explore its reaction condition to chiral amine and its applications in other fields.