Convenient and Rapid Synthesis of 3-Selenocyanato-4H-chromen-4-ones

Abstract

A sequential one-pot, simple and convenient method is described for the synthesis of 3-selenocyanato-4H-chromen-4-ones by addition, first of DMF-DMA and then of triselenodicyanide as electrophile.

Key words

selenocyanate - chromones - triselenodicyanide - selenium dioxide - malononitrile - electrophile addition - oxidation - rearrangement

• References and Notes

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• 10 3-Selenocyanato-4H-chromen-4-ones 3; General Procedure: A mixture of o-hydroxyacetophenone (1a; 136 mg, 1 mmol, 1 equiv) and dimethylformamide dimethylacetal (120 mg, 1 mmol, 1 equiv) was heated for 2 h at 100 °C. After cooling to 25 °C, a preprepared solution of malononitrile (66 mg, 1 mmol, 1 equiv) and SeO₂ (332 mg, 3 mmol, 3 equiv) in DMSO (1 mL), stirred at 25 °C for 20 min, was added at 25 °C. The reaction mixture was stirred for a further 30 min, then H₂O was added (3 mL). The resulting precipitate was filtered off, washed with H₂O (3 × 10 mL) and dried under a fume hood overnight at 25 °C to give the pure product 3a. 3-Selenocyanato-4H-chromen-4-one (3a): brown solid; yield: 76%; mp 136–137 °C. ¹H NMR (250 MHz, CDCl₃): δ = 8.26 (s, 1 H), 8.20 (dd, J = 8.0, 1.6 Hz, 1 H), 7.79 (dt, J = 8.4, 1.7 Hz, 1 H), 7.56 (dt, J = 8.4 Hz, 1 H), 7.51 (dt, J = 7.1, 1.1 Hz, 1 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 174.3 (CO), 156.7 (C), 153.1 (CH), 135.1 (CH), 126.5 (CH), 125.9 (CH), 122.0 (C), 118.6 (CH), 112.7 (C), 100.0 (CN). HRMS (ESI): m/z [M + H]⁺ calcd for C₁₀H₅NO₂Se: 251.9559; found: 251.9557.
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