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Synlett
DOI: 10.1055/a-2661-4038
DOI: 10.1055/a-2661-4038
Letter
Special Issue dedicated to Prof. S. Chandrasekaran on his 80th birthday
Oxidative Halogenation of Sydnones Mediated by KX–Oxone System under Mild Conditions
Abstract
A direct, straightforward, and convenient approach for the synthesis of halogenated sydnones using the potassium halide (KX)–Oxone system via oxidative halogenation is developed. Highlights of the strategy include readily available chemicals, mild reaction conditions, short reaction time, excellent yields, and aqueous medium. Additionally, the scale-up reaction of the present halogenation indicated the practical feasibility on a higher scale under mild conditions.
Publikationsverlauf
Eingereicht: 02. Juni 2025
Angenommen nach Revision: 20. Juli 2025
Accepted Manuscript online:
20. Juli 2025
Artikel online veröffentlicht:
06. August 2025
© 2025. Thieme. All rights reserved.
Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
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- 22 General experimental procedure for the preparation of halogenated sydnones: To a 25-mL RB flask was added sydnone 1 (1.0 equiv 0.56 mmol), KX (1.1 equiv), oxone (1.1 equiv), and aq. acetonitrile (1:1, 2.0 mL). The reaction mixture was stirred at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was quenched with water and extracted with dichloromethane (DCM). The combined organic layer was washed with water, saturated brine solution, and dried over sodium sulphate. The organic layer was concentrated under reduced pressure to obtain the crude product. The crude product was then washed with hexane to obtain the respective halogenated sydnone 2. 4-Bromo-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate (2a): Off-white solid; Yield-96% (140 mg); m.p. 103–105 °C; R f = (0.7 in 20% EtOAc/PET); 1H NMR (400 MHz, DMSO-d 6) δ = 7.83–7.81 (m, 2H), 7.80–7.77 (m, 1H), 7.76–7.72 (m, 2H); 13C NMR (101 MHz, DMSO- d 6) δ = 165.3, 133.8, 132.7, 130.1, 125.5, 86.4; HRMS (ESI): m/z calcd for C8H5BrN2O2 [M+H] 240.9534, found 240.9538. 4-Bromo-3-(p-tolyl)-1,2,3-oxadiazol-3-ium-5-olate (2b): Off-white solid; Yield-98% (142 mg); m.p. 135–137 °C; R f = (0.7 in 20% EtOAc/PET); 1H NMR (400 MHz, DMSO-d 6) δ = 7.67 (d, J = 8.6 Hz, 2H), 7.51 (d, J = 8.1 Hz, 2H), 2.43 (s, 3H); 13C NMR (101 MHz, DMSO-d 6) δ = 165.4, 143.0, 131.3, 130.4, 125.2, 86.3, 20.9; HRMS (ESI): m/z calcd for C9H7BrN2O2 [M+H] 254.9691, found 254.9693. 4-Chloro-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate (2o): Brown solid; Yield-95% (116 mg); m.p. 107–109 °C; R f = (0.7 in 20% EtOAc/PET); 1H NMR (400 MHz, DMSO-d 6) δ = 7.85–7.82 (m, 2H), 7.80–7.76 (m, 1H), 7.76–7.71 (m, 2H); 13C NMR (101 MHz, DMSO-d6) δ = 163.4, 132.8, 130.1, 125.3, 99.2; HRMS (ESI): m/z calcd for C8H5ClN2O2 [M+H] 197.0040, found 197.0042. 4-Chloro-3-(p-tolyl)-1,2,3-oxadiazol-3-ium-5-olate (2p): Pale brown solid; Yield-97% (116 mg); m.p. 124–126 °C; R f = (0.7 in 20% EtOAc/PET); 1H NMR (400 MHz, DMSO-d 6) δ = 7.75–7.69 (m, 2H), 7.53 (d, J = 8.1 Hz, 2H), 2.44 (s, 3H); 13C NMR (101 MHz, DMSO-d 6) δ = 163.4, 143.1, 130.4, 130.3, 125.0, 99.1, 20.9; HRMS (ESI): m/z calcd for C9H7ClN2O2 [M+H] 211.0196, found 211.0199. 4-Iodo-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate (2w): Off-white solid; Yield-97% (172 mg); m.p. 172–174 °C; R f = (0.7 in 20% EtOAc/PET); 1H NMR (400 MHz, DMSO-d 6) δ = 7.74–7.70 (m, 3H), 7.69–7.65 (m, 2H); 13C NMR (101 MHz, DMSO- d 6) δ = 168.9, 135.3, 132.4, 129.9, 125.7, 57.8; HRMS (ESI): m/z calcd for C8H5IN2O2 [M+H] 288.9396, found 288.9398. 4-Iodo-3-(p-tolyl)-1,2,3-oxadiazol-3-ium-5-olate (2x): Off-white solid; Yield-98% (164 mg); m.p. 164–166 °C; R f = (0.7 in 20% EtOAc/PET); 1H NMR (400 MHz, DMSO-d 6) δ = 7.53 (d, J = 8.3 Hz, 2H), 7.40 (d, J = 8.1 Hz, 2H), 2.33 (s, 3H); 13C NMR (101 MHz, DMSO-d6) δ = 169.0, 142.7, 132.9, 130.3, 125.4, 57.7, 20.9; HRMS (ESI): m/z calcd for C9H7IN2O2 [M+H] 302.9552, found 302.9557.