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DOI: 10.1055/s-2008-1078497
Synthesis, Characterization, and Redox Property of 3-(2-Phenyl-4H-thiochromen-4-ylidene)-3H-chromene-2,4-diones
Publication History
Publication Date:
02 July 2008 (online)
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Abstract
Two 3-(2-phenyl-4H-thiochromen-4-ylidene)-3H-chromene-2,4-dione derivatives were synthesized and evaluated as reversible redox switches. The prepared purple compound 7 and blue compound 13 instantly changed to colorless when treated with sodium borohydride in methanol. The corresponding reduced 9 and 14 can be reverted to their original colors via DDQ oxidation or by air. While no fluorescence of the N,N-dimethylamino-substituted 13 was detected prior to reduction, the reduced 14 emitted blue fluorescence in methanol with a quantum yield value of 0.19.
Key words
heterocycles - oxidation - reduction - sulfur - conjugation compounds
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
Crystallographic data (excluding structure factors) of compound 8 have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC-665160. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif or by emailing data_request@ccdc.cam.ac.uk or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 (1223)336033.
7Procedure for the Preparation of 13 To a solution of 12 (500 mg, 2.06 mmol) in DCE (10 mL) was added 4-hydroxy-7-N,N-dimethylaminocoumarin (423 mg, 2.06 mmol) and a catalytic amount of PTSA. After the mixture was stirred at 50 ˚C for 6 h, H2O (5 mL) was added to the mixture and the product was extracted twice with CH2Cl2. The combined organic extracts were dried over anhyd MgSO4, filtered, and concentrated. The resulting crude product was purified by column chromatography (EtOAc-hexane, 7:15) to give a blue solid with a 35% yield; mp 258-259 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 9.62 (s, 1 H), 8.34 (dd, J = 8.4, 1.2 Hz, 1 H), 7.98 (d, J = 8.7 Hz, 1 H), 7.90 (dd, J = 8.1, 1.2 Hz, 1 H), 7.87-7.84 (m, 2 H), 7.74 (ddd, J = 8.1, 7.2, 1.2 Hz, 1 H), 7.63-7.52 (m, 4 H), 6.60 (dd, J = 9.0, 2.4 Hz, 1 H), 6.42 (d, J = 2.4 Hz, 1 H), 3.09 (s, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 176.9, 165.1, 164.2, 156.48, 156.47, 155.9, 154.5, 139.1, 136.2, 134.9, 132.2, 131.8, 129.8, 129.7, 128.2, 128.0, 127.8, 126.6, 110.7, 108.4, 108.1, 97.3, 40.2. IR (KBr): ν = 1674, 1615, 1488, 1205 cm-¹. HRMS (EI): m/z calcd for C26H19NSO3: 425.1086; found: 425.1081 [M+].