Four-Step Route to Novel Bisflavylium Dications – First Synthesis of Phloroglucinol-Type Derivatives

Abstract

Various bisflavylium dications have been prepared in an efficient four-step manner utilizing the acid-mediated condensation between bis(arylethynylketones) and activated phenols as the key step. Of special note is that phloroglucinol-type bisflavylium salts have been obtained for the first time thanks to this procedure.

Key words

chromophores - condensation - flavylium - phenols - polycations

• References and Notes

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• 21 Resorcinol-Type Dication 6a Yellow powder; yield 95%. IR (KBr): 3380 (OH), 1635 (C=O), 855 (PF) cm^–1. UV/Vis (MeCN–10% 1 N HCl): λ_max (ε) = 262 (15700), 466 (38600 M^–1 cm^–1) nm. ¹H NMR (500 MHz, CD₃CN–1% TFA-d ₁): δ = 2.37 (quin, J = 5.9 Hz, 2 H), 4.40 (t, J = 5.9 Hz, 4 H), 7.23 (m, 4 H), 7.40 (dd, J = 8.8, 2.2 Hz, 2 H), 7.47 (dd, J = 2.2, 0.7 Hz, 2 H), 8.06 (d, J = 8.8 Hz, 2 H), 8.15 (d, J = 8.8 Hz, 2 H), 8.38 (m, 4 H), 8.95 (dd, J = 8.8, 0.7 Hz, 2 H). ¹³C NMR (125 MHz, CD₃CN–1% TFA-d ₁): δ = 29.9, 66.9, 104.3, 114.2, 117.9, 120.7, 122.6, 122.8, 133.9, 134.2, 155.4, 160.5, 168.2, 169.5, 174.0. ESI-MS (positive mode): m/z (%) = 259 (100) [M²⁺]. ESI-HRMS: m/z calcd for C₃₃H₂₆O₆ [M²⁺]: 259.0859; found: 259.0847.
• 22 Phloroglucinol-Type Dication 6g Orange powder; yield 95%. IR (KBr): 3400 (OH), 1635 (C=O), 835 (PF) cm^–1. UV/Vis (45% EtOH–45% MeCN–10% 1 N HCl): λ_max (ε) = 278 (14500), 326 (6200), 416 (sh), 476 (20800 M^–1 cm^–1) nm. ¹H NMR (500 MHz, CD₃CN–1% TFA-d ₁): δ = 2.35 (quin, J = 6.2 Hz, 2 H), 4.38 (t, J = 6.2 Hz, 4 H), 6.72 (d, J = 2.2 Hz, 2 H), 6.96 (dd, J = 2.2, 0.7 Hz, 2 H), 7.19 (m, 4 H), 7.94 (d, J = 8.8 Hz, 2 H), 8.29 (m, 4 H), 9.04 (dd, J = 8.8, 0.7 Hz, 2 H). ¹³C NMR (125 MHz, CD₃CN–1% TFA-d ₁): δ = 29.9, 66.7, 96.9, 104.0, 111.5, 114.2, 117.7, 122.6, 133.2, 150.4, 159.6, 160.1, 167.7, 171.5, 173.2. ESI-MS (positive mode): m/z (%) = 275 (100) [M²⁺]. ESI-HRMS: m/z calcd for C₃₃H₂₆O₈ [M²⁺]: 275.0808; found: 275.0798.