Reaction of Dichloronaphthazarins with Sodium Nitrite as a Route to Natural Pigments Echinamines A and B and Related Aminonaphthazarins

Abstract

A series of 6,7-disubstituted 2-hydroxy-3-nitronaphthazarins were prepared by treatment of 2,3-dichloronaphthazarins with sodium nitrite. Acid-catalyzed hydrolysis of a mixture of two isomeric 6(7)-ethoxy-7(6)-ethyl-substituted 2-hydroxy-3-nitronaph­thazarins followed by chromatographic separation led to the individually precursors of echinamines A and B. Further reduction of nitroquinones using various reducing agents gave echinamines and related 3-amino-2-hydroxynaphthazarins in good yields.

Key words

5,8-dihydroxy-1,4-naphthoquinones - nucleophilic aromatic substitution - natural products - echinamine A - echinamine B - sodium nitrite - dichloronaphthazarins

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35

Ratios of both isomeric products were measured directly from the integration of ^¹H NMR absorptions of the α-hydroxy group protons, which are common to both of the regioisomers.

38

The mixture of regioisomeric 7-ethyl-2,5,8-trihydroxy-6-methoxy-3-nitronaphthalene-1,4-dione and 6-ethyl-2,5,8-trihydroxy-7-methoxy-3-nitronaphthalene-1,4-dione, which was early synthesized in 90% yield (ref. 31), is a preferable starting material for the preparation of echinamines.