Synthesis of a Heavy-Atom-Free BODIPY and its Photooxygenation of 1-Naphthol to 1,4-Naphthoquinone

Abstract

By using 1,5,6,7-dihydro-4H-indol-4-one, a carbonyl group was introduced onto a BODIPY photosensitizer. The resulting heavy-atom-free BODIPY is a highly effective producer of singlet oxygen with a calculated quantum yield (Φ_Δ) of 0.68, compared with that of methylene blue (Φ_Δ = 0.57). Photooxygenation of 1-naphthol to 1,4-naphthoquinone was achieved by using this heavy-atom-free BODIPY catalyst in the presence of white-light irradiation under air atmosphere. Our work demonstrated a practical example of the design of a heavy-atom-free BODIPY, capable of efficient singlet-oxygen generation, with a potential in photocatalysis.

Key words

BODIPY dyes - organophotocatalysis - difluoroboradiazaindacene - photooxygenation - photocatalysts

Publication History

Received: 27 February 2023

Accepted after revision: 26 April 2023

Accepted Manuscript online:
26 April 2023

Article published online:
26 May 2023

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• 9 Carbonyl-BDP Under N₂, p-anisaldehyde (0.11 mL, 0.89 mmol) was added to 1,5,6,7-tetrahydro-4H-indol-4-one (300 mg, 2.21 mmol) in DCE (20 mL), and the mixture was stirred for 10 min. A drop of F₃CCO₂H was then added at rt, and the mixture was stirred at 70 °C for 2 h. DDQ (503.8 mg, 2.21 mmol) was added, and the resulting mixture was again stirred for 2 h at 70 °C. The mixture was then washed with H₂O (3 × 100 mL), and the aqueous solution was extracted with CH₂Cl₂ (2 × 50 mL). The organic layers were dried (MgSO₄), filtered, and concentrated. Et₃N (0.5 mL, 3.63 mmol) was added to the resulting mixture in DCE (40 mL), and the mixture was stirred for 10 min. BF₃·Et₂O (1.0 mL, 7.26 mmol) was then added, and the mixture was stirred for a further 2 h. The mixture was then washed with H₂O (3 × 100 mL), and the organic layers were dried (MgSO₄), filtered, and concentrated. The crude product was purified by column chromatography [silica gel, CH₂Cl₂–hexane (6∶1)] to give a dark-pink solid; yield: 15.6 mg (13%). ¹H NMR (400 MHz, CDCl₃): δ = 7.77 (s, 2 H), 7.57 (d, ³ J = 8.8 Hz, 2 H), 7.09 (t, ³ J =8.8 Hz, 2 H), 3.944 (s, 3 H), 3.31 (t, ³ J = 6.4 Hz, 4 H), 2.35 (t, ³ J = 7.6 Hz, 4 H), 2.21 (t, ³ J = 7.6 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 183.8, 163.1, 137.5, 132.9, 130.1, 130.1, 129.8, 128.3, 114.7, 114.2, 55.5, 32.1, 27.3, 22.8. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₄H₂₂BF₂N₂O₃: 435.16861; found: 435.16848.