Efficient [WO4]2–-Catalyzed Chemical Fixation of Carbon Dioxide with 2-Aminobenzonitriles to Quinazoline-2,4(1H,3H)-diones

Abstract

A simple monomeric tungstate, TBA(2)[WO(4)] (I, TBA = tetra-n-butylammonium), could act as an efficient homogeneous catalyst for chemical fixation of CO(2) with 2-aminobenzonitriles to quinazoline-2,4(1H,3H)-diones. Various kinds of structurally diverse 2-aminobenzonitriles could be converted into the corresponding quinazoline-2,4(1H,3H)-diones in high yields at atmospheric pressure of CO(2). Reactions of inactive 2-amino-4-chlorobenzonitrile and 2-amino-5-nitrobenzonitrile at 2 MPa of CO(2) also selectively proceeded. The present system was applicable to a g-scale reaction of 2-amino-5-fluorobenzonitrile (10 mmol scale) with CO(2) and 1.69 g of analytically pure quinazoline-2,4(1H,3H)-dione could be isolated. In this case, the turnover number reached up to 938 and the value was the highest among those reported for base-mediated systems so far. NMR spectroscopies showed formation of the corresponding carbamic acid through the simultaneous activation of both 2-aminobenzonitirile and CO(2) by I. Kinetic and computational studies revealed that I plays an important role in conversion of the carbamic acid into the product.