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Synlett 2025; 36(08): 1003-1008
DOI: 10.1055/a-2493-7974
DOI: 10.1055/a-2493-7974
letter
Direct One-Pot Synthesis of Tetrazole Derivatives from Aldehydes under Metal-Free Conditions
This research was supported by IIT Roorkee and DST-FIST [SR/FST/CS-II/ 2018/72(C)] (funding to the Chemistry Department, IIT Roorkee, for the provision of 500 MHz NMR and XRD facilities). R.S. is grateful to the MHRD, IIT Roorkee, for providing a JRF fellowship.
Abstract
A simple and efficient one-pot protocol has been developed for the synthesis of 1H-tetrazole and 1-methyltetrazole derivatives from aldehydes under mild and metal-free conditions using ammonium azide or methyl azide, respectively. A number of tetrazole derivatives were obtained in moderate to high yields (75–92%) in green solvents at a moderate temperature. These reactions presumably proceed through the formation of a nitrile in situ. The mild conditions and the easy workup and purification make this method highly valuable.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2493-7974.
- Supporting Information
Publikationsverlauf
Eingereicht: 24. Oktober 2024
Angenommen nach Revision: 29. November 2024
Accepted Manuscript online:
29. November 2024
Artikel online veröffentlicht:
18. Dezember 2024
© 2024. Thieme. All rights reserved
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- 30 1H-Tetrazoles 2a–z; General Procedure (CAUTION! Sodium azide can explode on heating and is highly toxic. Contact of metal azides with acids liberates highly toxic and explosive hydrazoic acid.) NH4N3 (0.5 mmol) and H2SO4 (0.5 mmol) were added sequentially to a round-bottomed flask containing the appropriate aldehyde (0.5 mmol) in EtOH (1 mL), and the resulting mixture was stirred at r.t. for 10 min. A solution of NaN3 (0.5 mmol) in H2O (1 mL) was then added, and the resulting mixture was stirred for another 2 h at 80 °C. When the starting material had been consumed, the mixture was cooled to r.t. and ice-cold H2O was added to give a solid precipitate. The precipitate was collected and washed with 20% CH2Cl2–hexane to give the pure product. 5-Phenyl-1H-tetrazole (2a) White solid; yield: 67.1 mg (92%); mp 216–218 °C. IR (KBr): 2981, 2908, 2794, 1856, 1608, 1563, 1485, 1466, 1163, 1084, 1056, 993, 726 cm–1. 1H NMR (500 MHz, DMSO-d6): δ = 8.05–7.95 (m, 2 H), 7.61–7.48 (m, 3 H). 13C NMR (126 MHz, DMSO-d6): δ = 160.59, 136.52, 134.70, 132.25, 129.44. Anal. Calcd for C7H6N4: C, 57.53; H, 4.14; N, 38.34. Found: C, 57.48; H, 4.12; N, 38.40. 2-(1H-Tetrazol-5-yl)phenol (2b) White solid; yield: 73.7 mg (91%); mp 220–222 °C. IR (KBr): 3194, 2831, 2563, 1953, 1781, 1617, 1544, 1489, 1465, 1301, 1218, 997, 748 cm–1. 1H NMR (500 MHz, DMSO-d6): δ = 7.95 (dd, J = 7.8, 1.8 Hz, 1 H), 7.37 (ddd, J = 8.7, 7.3, 1.8 Hz, 1 H), 7.04 (dd, J = 8.3, 1.1 Hz, 1 H), 6.96 (td, J = 7.6, 1.1 Hz, 1 H). 13C NMR (126 MHz, DMSO-d6): δ = 160.60, 156.91, 137.93, 134.35, 125.00, 121.63, 115.80. Anal. Calcd for C7H6N4O: C, 51.85; H, 3.73; N, 34.55. Found: C, 51.96; H, 3.71; N, 34.46.