Zr-MOF-808@MCM-41 catalyzed phosgene-free synthesis of polyurethane precursorsElectronic supplementary information (ESI) available. See DOI: 10.1039/c8cy02235f

In this work, a catalytic method is presented for the synthesis of aromatic carbamates from aromatic amines using dimethyl carbonate instead of phosgene as a green and safe reaction process. Microcrystalline Zr-MOF-808 is reported as an active and efficient heterogeneous catalyst for the selective carbamoylation of anilines and industrially relevant aromatic diamines, under mild reaction conditions with near quantitative yields. We have accomplished the selective growth of well-dispersed Zr-MOF-808 nanocrystals within the mesoporous material MCM-41. A superior catalytic performance of the Zr-MOF-808@MCM-41 is demonstrated that together with increased stability stands out as an advantageous heterogeneous catalyst for polyurethane production. In situ FTIR studies have allowed a better understanding of the reaction pathway at the molecular level when the active MOF catalyst is present. Zr-MOF-808@MCM-41 exhibited high catalytic activity, selectivity and stability for the synthesis of aromatic carbamates from aromatic amines and dimethyl carbonate.