Oxidation of bis(2-hydroxy-1-naphthyl)methane and similar bisnaphthols with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. Structure and synthesis of novel products

Abstract

Oxidation of bis(2-hydroxy-1-naphthyl)methane (4a) with 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) has been shown to give the novel compounds, cis-and trans-dispiro(naphtha1ene-1,2'(1'H)-naphtho[2,1-b)pyran-3',1 "-naphthalene}-2(1 H),2"(1 "H)-dione (1 2a) and (13a) together with the quinone methide dimer (6a) and the spiroketone (5a). Compounds (12a) and (13a) were characterised on the basis of their spectral properties and the structures were finally confirmed by an Xray crystal structure analysis of (1 2a). Hydrogenation of compounds (I 2a) and (1 3a) has been shown t o give the dihydroxy compound (14) via CC bond cleavage. An alternative synthesis of the dispironaphthalenones (12a) and (13a) was achieved by oxidation of the dihydroxy compound (14), prepared by an independent method. The generality of the oxidation of bisnaphthols of type (4a) to give novel products of the type (1 2a) and (13a) has been shown by studying the oxidation of the variously substituted bisnaphthols (4b-d,f) with DDQ. A mechanism has been proposed invoking the intermediacy of the quinol ethers (22) and (24).

Cyclohexadienone Ketals and Quinols: Four Building Blocks Potentially Useful for Enantioselective Synthesis

“…Upon exposure to DDQ, 137 proceeds to the spirocycle 138 in 61% yield. Kasturi has also utilized DDQ for the preparation of 2,4-cyclohexadienones from 1-(2-hydroxybenzyl)-2-naphthols, and there are reports that K 3 Fe(CN) 6 80 and KOBr 81 are equally effective with these substrates.

35 DDQ oxidation leading to a spiro o -quinol derivative.

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Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst

“…Several reagents have been used to oxidize bis(2-hydroxy-1-naphthyl)methanes as a subunit of calix[n]arene to the corresponding spirodienones. These include phenyltrimethylammonium tribromide (PTMATB) 47 , 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) 48 , N -chloro reagents 49 , Ph 3 Bi 50 and nanoparticle-supported TEMPO 51 (2,2,6,6-tetramethylpiperidine-oxyl).…”

Aerobic Copper Catalytic Oxidation of Methylene and Arylidenebisnaphthols: A Green and Efficient Synthesis of Spironaphthalenones

“…Depending on the conditions, the reaction proved to be stereoselective,,, or lead to a mixture of diastereoisomers ,,. Moreover, the reaction conditions are very often stoichiometric and only more recently catalytic conditions were reported.…”