HKUST-1 was used as a catalyst in the conversion, under mild oxidation conditions, of trans-ferulic acid to vanillin. When catalyst was activated under vacuum, the average reaction yield reached 95%.
Fluorescent Fréchet-type poly(aryl ether) dendrimers that incorporate the 1,3,5-triphenylbenzene as core molecule and 3, 6, 9, or 12 terminal allyl ether groups have been prepared in very good yield by following the Fréchet convergent approach. Regiospecific hydrosylilation reactions on the allyl ether functions with the cobaltabisdicarbollide derivative Cs[1,1′-μ-SiMeH-3,3′-Co(1,2-C2B9H10)2] lead to different generations of Féchet-type polyanionic metallodendrimers decorated with 3, 6, and 9 cobaltabisdicarbollide units. Starting dendrimers exhibit photoluminescence properties at room temperature under ultraviolet irradiation; nevertheless, after functionalization with cobaltabisdicarbollide derivatives, the fluorescence properties are quenched. Products are fully characterized by FTIR, NMR, and UV−vis spectroscopies. For metallodendrimers, the UV−vis absorptions have been a good tool for estimating the experimental number of cobaltabisdicarbollide units peripherally attached to the dendrimeric structure and consequently to corroborate the unified character of the dendrimers. Because of the anionic character of these compounds and the boron-rich content, we actually focus our research on biocompatibility studies and potential applications.
Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.
A new family of polyanionic poly(alkyl aryl-ether) metallodendrimers decorated with four and eight cobaltabisdicarbollide units have been obtained in high yield by the ring-opening reaction of cyclic oxonium [3,3'-Co(8-(C(2)H(4)O)(2)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))] with alkoxides formed by deprotonation of terminal alcohols in the α,α'-bis[3,5-bis(hydroxymehyl)phenoxy]-p-xylene, α,α'-bis[3,5-bis(hydroxymehyl)phenoxy]-m-xylene, α,α'-bis[3,5-bis-[3,5-bis(hydroxymethyl)phenoxy]methylen]phenoxy]-p-xylene, and α,α,'-bis[3,5-bis-[3,5-bis(hydroxymethyl)phenoxy]methylen]phenoxy]-m-xylene dendrimers. The crystal structure of the precursor α,α'-bis[3,5-bis(chloromethyl)phenoxy]-p-xylene is also described. Final products are fully characterized by FTIR, NMR, UV-vis spectroscopies and elemental analysis. For metallodendrimers, the UV-vis absorptions have been a good tool for estimating the experimental number of cobaltabisdicarbollide units peripherally attached to the dendrimeric structure and consequently to corroborate the complete functionalization of the dendrimers.
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