Catalysis over zinc-incorporated berlinite (ZnAlPO4) of the methoxycarbonylation of 1,6-hexanediamine with dimethyl carbonate to form dimethylhexane-1,6-dicarbamate

<p>Abstract</p> <p>Background</p> <p>The alkoxycarbonylation of diamines with dialkyl carbonates presents promising route for the synthesis of dicarbamates, one that is potentially 'greener' owing to the lack of a reliance on phosgene. While a few homogeneous catalysts have been reported, no heterogeneous catalyst could be found in the literature for use in the synthesis of dicarbamates from diamines and dialkyl carbonates. Because heterogeneous catalysts are more manageable than homogeneous catalysts as regards separation and recycling, in our study, we hydrothermally synthesized and used pure berlinite (AlPO₄) and zinc-incorporated berlinite (ZnAlPO₄) as heterogeneous catalysts in the production of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine (HDA) and dimethyl carbonate (DMC). The catalysts were characterized by means of XRD, FT-IR and XPS. Various influencing factors, such as the HDA/DMC molar ratio, reaction temperature, reaction time, and ZnAlPO₄/HDA ratio, were investigated systematically.</p> <p>Results</p> <p>The XRD characterization identified a berlinite structure associated with both the AlPO₄and ZnAlPO₄catalysts. The FT-IR result confirmed the incorporation of zinc into the berlinite framework for ZnAlPO₄. The XPS measurement revealed that the zinc ions in the ZnAlPO₄structure possessed a higher binding energy than those in ZnO, and as a result, a greater electron-attracting ability. It was found that ZnAlPO₄catalyzed the formation of dimethylhexane-1,6-dicarbamate from the methoxycarbonylation of HDA with DMC, while no activity was detected on using AlPO₄. Under optimum reaction conditions (i.e. a DMC/HDA molar ratio of 8:1, reaction temperature of 349 K, reaction time of 8 h, and ZnAlPO₄/HDA ratio of 5 (mg/mmol)), a yield of up to 92.5% of dimethylhexane-1,6-dicarbamate (with almost 100% conversion of HDA) was obtained. Based on these results, a possible mechanism for the methoxycarbonylation over ZnAlPO₄was also proposed.</p> <p>Conclusion</p> <p>As a heterogeneous catalyst ZnAlPO₄berlinite is highly active and selective for the methoxycarbonylation of HDA with DMC. We propose that dimethylhexane-1,6-dicarbamate is formed <it>via </it>a catalytic cycle, which involves activation of the DMC by a key active intermediate species, formed from the coordination of the carbonyl oxygen with Zn(II), as well as a reaction intermediate formed from the nucleophilic attack of the amino group on the carbonyl carbon.</p

Palaeotectonic setting of the south-eastern Kédougou-Kéniéba Inlier, West Africa: new insights from igneous trace element geochemistry and U-Pb zircon ages

New U-Pb zircon ages and geochemistry from the eastern Kédougou-Kéniéba Inlier are presented and integrated with published data to generate a revised tectonic framework for the westernmost Birimian terranes. The Falémé Volcanic Belt and Kofi Series are highly prospective, hosting several multi-million ounce gold deposits and a significant iron ore resource, but remain under-researched. It is therefore important to constrain the fundamental geological setting. The igneous rocks of the eastern Kédougou-Kéniéba Inlier are dominantly of high-K calc-alkaline affinity, with fractionated REE patterns and negative Nb-Ta anomalies. The plutonic rocks in the Falémé Belt are dioritic to granodioritic in composition, with moderately fractionated REE patterns and metaluminous A/CNK signatures. Felsic, peraluminous granite stocks, dykes and plutons with fractionated REE patterns and negative Eu, Ti and P anomalies intruded both the Falémé Belt and Kofi Series. Albitisation masks the affinity of some units, although use of the Th-Co diagram shows that prior to albitisation, all igneous units belonged to the high-K calc-alkaline series. New U-Pb age data for the Boboti and Balangouma plutons indicate crystallisation at 2088.5 ± 8.5 Ma and at 2112 ± 13 Ma, respectively. Inherited zircons in the Boboti pluton indicate magmatic activity in the Falémé Belt at 2218 ± 83 Ma coincided with the oldest dated units in the Mako Belt to the West. Systematic changes in Dy/Yb, Sm/La, Nb/Zr, Rb concentration, Eu-anomaly and ɛNdt over ∼200 Ma reveal that the tectonic setting in the KKI evolved from a volcanic island arc environment to an active continental margin. Crustal thickening, as a result of a shift to collisional tectonic setting, combined with magmatic differentiation, led to the generation of peraluminous, granitic melts with a significant crustal component. A small suite of more basic intrusive and extrusive rocks on the eastern margin of the Dialé-Daléma basin are highly metaluminous and display limited LILE enrichment, with normalised HREE values close to unity. The Daléma igneous rocks may have formed in an extensional back arc, related to the arc system

Shape-Selective Fabrication of Zinc Phosphate Hexagonal Bipyramids via a Disodium Phosphate-Assisted Sonochemical Route

Via a simple and facile disodium phosphate-assisted sonochemical route, highly uniform zinc phosphate hexagonal bipyramid crystals were selectively synthesized under ambient conditions. All the facets of hexagonal bipyramids are smooth. The average size (from pole to pole) and the standard deviation were 1.437 mu m and 562 nm, respectively. The concentration of HpO(4)(2-) in the aqueous precursor solution is thought to be a key factor in getting hexagonal bipyramidal morphology. This method is simple, fast, economical, and environmentally benign. It is expected that this sonochemical technique call be readily adopted in realizing other forms of various micro/nanostructured materials