Diploquinones A and B, Two New Phytotoxic Tetrasubstituted 1,4-Naphthoquinones from Diplodia mutila, a Causal Agent of Grapevine Trunk Disease

Two new phytotoxic tetrasubstituted 1,4-naphthoquinones, named diploquinones A and B, were isolated together with vanillic acid from Diplodia mutila (DAR78993), a grapevine pathogen involved in Botryosphaeria dieback in Australia. Diploquinones A and B were characterized as 6,7-dihydroxy-2-methoxy-5-methylnaphthalene-1,4-dione and 3,5,7-trihydroxy-2-methoxynaphthalene-1,4-dione using spectroscopic methods (essentially 1D and 2D 1H and 13C NMR and HR ESIMS). The already known vanillic acid was isolated for the first time as fungal phytotoxin and as metabolite of D. mutila. The three compounds were assayed on detached grapevine leaves ( Vitis vinifera cv. Shiraz) at concentrations of 10-3 M and 2.5 × 10-3 M. Vanillic acid showed the highest phytotoxic effect on grapevine leaves irrespective of the tested concentration, while diploquinones A and B showed varying degrees of toxicity.