l-Proline: An Efficient Organocatalyst for the Synthesis of 5-Substituted 1H-Tetrazoles via [3+2] Cycloaddition of Nitriles and Sodium Azide

Abstract

A simple and efficient route for the synthesis of a series of 5-substituted 1H-tetrazoles using l-proline as a catalyst from structurally diverse organic nitriles and sodium azide is reported. The prominent features of this environmentally benign, cost effective, and high-yielding l-proline-catalyzed protocol includes simple experimental procedure, short reaction time, simple workup, and excellent yields making it a safer and economical alternative to hazardous Lewis acid catalyzed methods. The protocol was successfully applied to a broad range of substrates, including aliphatic and aryl nitriles, organic thiocyanates, and cyanamides.

Keywords

5-substituted 1H-tetrazoles - organic nitriles - thiocyanates - cyanamides - sodium azide - l-proline

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• 34 Typical Procedure for the Synthesis of 5-Substituted 1H-tetrazoles 3, 5, 7 General Procedure for the Synthesis of 5-Aryl/Alkyl 1H-Tetrazoles 3 The mixture of organic nitrile (1 mmol), NaN₃ (1.25 mmol), and l-proline (30 mol%) in DMF (5 mL) was stirred at 110 °C for 1–2 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was allowed to cool to room temperature. The cooled reaction mixture was poured in ice water (15 mL) with stirring. The resulting mixture was acidified with dilute HCl under vigorous stirring. The solid product was filtered under suction and washed with sufficient cold water. The solid was air dried to obtain the pure product. General Procedure for the Synthesis of 5-(Substituted ­Sulfanyl)-1H-tetrazoles 5 The mixture of appropriate thiocyanate (1 mmol), NaN₃ (1.25 mmol), and l-proline (30 mol%) in n-propanol (5 mL) was refluxed for 1–2 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was allowed to cool to room temperature. The cooled reaction mixture was poured in ice water (15 mL) with stirring. The resulting mixture was acidified with dilute HCl under vigorous stirring. The solid product was filtered under suction and washed with sufficient cold water. The solid was air dried to obtain the pure product. General Procedure for the Synthesis of 5-Arylamino-1H-tetrazoles 7 The mixture of organic cyanamide (1 mmol), NaN₃ (1.25 mmol), and l-proline (30 mol%) in DMF (5 mL) was stirred at 110 °C for 1–2 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was allowed to cool to room temperature. The cooled reaction mixture was poured in ice water (15 mL) with stirring. The resulting mixture was acidified with dilute HCl under vigorous stirring. The solid product was filtered under suction and washed with sufficient cold water. The solid was air dried to obtain the pure product. 5-Phenyl-1H-tetrazole (3a, Table 2 Entry 1) Yield 96%, 140.3 mg; white solid; mp 214–216 °C (lit.^6a 215–216 °C). IR (KBr): ν_max = 3207, 3075, 3051, 1610, 1565, 1491, 1466, 688 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 16.8 (br, NH), 8.03–8.01 (m, 2 H), 7.62–7.58 (m, 3 H) ppm. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 155.1, 131.2, 129.5, 126.8, 124.1 ppm. MS (ESI): m/z = 147 [M + H]⁺. 5-(4-Pyridyl)-1H-tetrazole (3j, Table 2, Entry 10) Yield 94%, 138.3 mg; white solid; mp 254–256 °C (lit.²¹ 254–255 °C). IR (KBr): ν_max = 3485, 3264, 3099, 3040, 2966, 1621, 1580, 1450, 1388, 1123, 1096, 1042, 1022, 845, 784 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 16.30 (br s, 1 H), 8.51 (d, J = 7.6 Hz, 2 H), 7.78 (d, J = 7.6 Hz, 2 H) ppm. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 159.1, 149.9, 139.4, 120.9 ppm. MS (ESI): m/z: 148 [M + H]⁺. 5-(Benzylsulfanyl)-1H-tetrazole (5b, Table 3, Entry 2) Yield 93%, 178.8 mg; white solid; mp 133–135 °C (lit.³⁵ 134–135 °C). IR (KBr): ν_max = 3061, 2900, 2812, 2653, 2545, 2490, 1532, 1493, 1454, 1433, 1362, 1318, 1236, 1079, 1037, 980, 776, 704 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 16.45 (br s, 1 H), 7.40–7.38 (m, 2 H), 7.32–7.28 (m, 3 H), 4.50 (s, 2 H) ppm. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 154.2, 137.2, 129.5, 129.1, 128.2, 36.5 ppm. MS (ESI): m/z = 193 [M + H]⁺. 5-(p-Tolyl)amino-1H-tetrazole (7b, Table 4, Entry 2) Yield 86%, 150.7 mg; coffee colored solid; mp 200–202 °C (lit.³⁵ 201–203 °C). IR (KBr): ν_max = 3268, 3210, 3135, 3091, 1626, 1578, 1545, 1470, 1440, 1256, 1134, 1090, 1060, 835, 782, 730, 503 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 15.21 (br s, 1 H), 9.66 (s, 1 H), 7.38 (d, J = 8.4 Hz, 1 H), 7.12 (d, J = 8.4 Hz, 1 H), 2.24 (s, 1 H) ppm. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 155.8, 138.1, 130.2, 124.0, 117.8, 20.3 ppm. MS (ESI): m/z = 176 [M + H]⁺. 5-(4-Chlorophenyl)amino-1H-tetrazole (7d, Table 4, Entry 4) Yield 89%, 174.1 mg; white solid; mp 227–229 °C (lit.³⁵ 226–228 °C). IR (KBr): ν_max = 3268, 3210, 3135, 3091, 1626, 1578, 1545, 1470, 1440, 1256, 1134, 1090, 1060, 835, 782, 730, 503 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 15.43 (br s, 1 H), 9.97 (s, 1 H), 7.56–7.53 (d, J = 11.9 Hz, 1 H), 7.38–7.35 (d, J = 11.9 Hz, 1 H) ppm. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 156.1, 139.8, 129.3, 125.1, 118.7 ppm. MS (ESI): m/z = 196 [M + H]⁺.
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