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Turkish Journal of Chemistry

DOI

10.3906/kim-1506-28

Abstract

Regio- and stereoselective synthesis are described for convenient preparation of hydroxy- and methoxynaphthalenes starting from naphthalene (\textbf{1}). \textit{cis,cis,trans}-2,3,5,8-Tetrabromo-4-methoxy-1,2,3,4-tetrahydronaphthalen-1-ol (\textbf{6}), \textit{cis,cis,trans}-2,3,5,8-tetrabromo-1,4-dimethoxy-1,2,3,4-tetrahydronaphthalene (\textbf{7}), and \textit{cis,cis,cis}-2,3,5,8-tetrabromo-1,4-dimethoxy-1,2,3,4-tetrahydronaphthalene (\textbf{8}) were obtained with silver-induced substitution of \textit{trans,cis,trans}-1,2,3,4, 5,8-hexabromo-1,2,3,4-tetrahydronaphthalene (\textbf{3}). Base-promoted aromatization of dimethoxides \textbf{7} and \textbf{8} afforded 3,5,8-tribromo-1-methoxynaphthalene (\textbf{9}) and 2,5,8-tribromo-1-methoxynaphthalene (\textbf{10}). The reaction of \textbf{6 }with sodium methoxide formed compounds \textbf{10 }and 3,5,8-tribromonaphthalen-1-ol (\textbf{16}). Bromination of \textbf{9} and\textbf{ 16} with Br$_{2}$ in dichloromethane at room temperature produced 2,3,5,8-tetrabromo-1-methoxynaphthalene (\textbf{14}) and 2,3,4,5,8-pentabromonaphthalen-1-ol (\textbf{18}), respectively, while compound \textbf{10} did not react in the same conditions. Pyridine-induced elimination of hexabromide \textbf{3} afforded 1,4,6\textbf{-}tribromnaphthalene (\textbf{21}) in 99{\%} yield and thermolysis of the hexabromide \textbf{3} gave mainly 1,4,6,7-tetrabromonaphthalene (\textbf{22}). Tetrabromide \textbf{22} was transformed to 1,4,6,7-tetramethoxynaphthalene (\textbf{23}) by copper-assisted nucleophilic substitution reaction.

Keywords

Methoxynaphthalene, silver-induced substitution, base-promoted elimination, hydroxynaphthalene, bromonaphthalene

First Page

332

Last Page

346

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