A Streamlined Synthesis for 2,7-Diformyl-1,8-naphthalenediol

Abstract

2,7-Diformyl-1,8-naphthalenediol, an extension of the numerously used precursor 2,6-diformylphenol for the synthesis of various ligand systems, has been synthesized by a double Directed ortho Metalation reaction.

Key words

aldehydes - lithiation - Directed ortho Metalation - formylation

References

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12

CCDC 220283 (2) and CCDC 220284 (3) contain the supplementary crystallographic data of these structures. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html [or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax:[phone]; e-mail:[e-mail]].

13

2,7-Diformyl-1,8-bis(methoxymethoxy)naphthalene ( 3). A solution of 2 (2.00 g, 8.06 mmol) in Et₂O (90 mL) was added dropwise over a period of 3 h to a solution of n-BuLi (2.5 M, 9.67 mL, 24 mmol) and TMEDA (3.63 mL, 24 mmol) in Et₂O (10 mL) at 0 °C. After stirring the reaction mixture for 5 h at r.t., DMF (3.76 mL, 24.17 mmol) was added at 0 °C and the resulting mixture stirred for another 4 h at r.t. After addition of water (40 mL) and stirring for 1 h at r.t., the pH of the reaction solution was raised to 7-8 by addition of dilute HCl. Standard workup and column chromatography gave 1.62 g (66%) of 3 as a brownish yellow solid.