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Synthesis 2011(20): 3350-3358  
DOI: 10.1055/s-0030-1260229
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Nikita S. Polonik*, Sergey G. Polonik, Vladimir A. Denisenko, Olga P. Moiseenko
Pacific Institute of Bioorganic Chemistry FEB RAS, Prospect 100 let Vladivostoku 159, 690022 Vladivostok, Russian Federation
Fax: +7(4232)314050; e-Mail: nikpol@piboc.dvo.ru;
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Publication History

Received 22 June 2011
Publication Date:
13 September 2011 (online)

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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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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.