2-(Arylamino)aryliminophosphoranes as Easily Available and Convenient Starting Materials in the Synthesis of 1,2,3-Benzotriazoles

Abstract

1-Aryl-1,2,3-benzotriazole systems are synthesized in the high-yielding cyclocondensation of 2-(arylamino)aryliminophosphoranes under mild conditions. The reaction concludes the three-step, halogen-free synthetic route starting from simple nitroarenes and arylamines.

Key words

cyclization - condensation - heterocycles - annulation - ylides

• References and Notes

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• 13 Synthesis of 1-Aryl-1,2,3-benzotriazoles 2 – General Procedure Iminophosphorane 1 (1 mmol) was dissolved in AcOH (5 mL), cooled down to 0 °C, and NaNO₂ (1.1 mmol) was added portionwise with stirring. The reaction was stirred until completion (TLC control, usually 5–20 min). The mixture was poured into H₂O, extracted with EtOAc, dried with Na₂SO₄, and the solvent was evaporated. The crude product was purified by column chromatography.
• 14 Analytical Data for Representative Products Compound 2a: white solid; mp 152–154 °C. ¹H NMR (400 MHz, CDCl₃): δ = 1.92 (s, 6 H), 7.21 (d, J = 2.0 Hz, 1 H), 7.25 (s, 1 H), 7.27 (s, 1 H), 7.37–7.42 (m, 2 H), 8.08 (d, J = 8.8 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 17.5, 112.3, 118.3, 127.0, 129.1, 131.1, 132.9, 134.8, 136.3, 142.6, 145.2. MS (EI): m/z (%) = 259 (13), 257 (40), 228 (39), 216 (13), 214 (39), 194 (100), 193 (22). HRMS (EI): m/z calcd for C₁₄H₁₂N₃ ³⁵Cl: 257.0720; found: 257.0730. Compound 2b: pink crystals; mp 136–138 °C. ¹H NMR (500 MHz, CDCl₃):¹⁶ δ = 2.40 (s, 3 H), 7.30 (dd, J = 8.8, 1.8 Hz, 1 H), 7.33–7.36 (m, 2 H), 7.52–7.55 (m, 2 H), 7.65 (d, J = 1.8 Hz, 1 H), 7.98 (d, J = 8.8 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 21.2, 110.2, 121.1, 122.9, 125.5, 130.5, 133.0, 134.0, 134.6, 139.2, 150.0. MS (EI): m/z (%) = 245 (16), 243 (51), 216 (29), 215 (44), 214 (76), 180 (100), 179 (12). HRMS (EI): m/z calcd for C₁₃H₁₀N₃ ³⁵Cl: 243.0563; found: 243.0563. Compound 2c: white solid; mp 92–95 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.84 (s, 6 H), 4.11 (s, 3 H), 6.94–7.01 (m, 2 H), 7.33–7.39 (m, 2 H), 7.45–7.51 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 16.9, 56.9, 101.5, 105.9, 128.8, 130.6, 133.3, 134.9, 135.4, 135.8, 135.9, 151.7. MS (EI): m/z (%) = 289 (51), 288 (29), 287 (100), 258 (24), 246 (37), 245 (23), 224 (78), 218 (16), 217 (10), 216 (51), 209 (39), 201 (21), 181 (52), 180 (39). HRMS (EI): m/z calcd for C₁₅H₁₄N₃O³⁵Cl: 287.0825; found: 287.0828. Compound 2e: yellow solid; mp 110–112 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 3.87 (s, 3 H), 7.19–7.25 (m, 2 H), 7.40–7.44 (m, 1 H), 7.46–7.2 (m, 2 H), 7.76–7.80 (m, 3 H), 7.81–7.86 (m, 2 H), 7.93 (s, 1 H), 8.19–8.25 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 55.6, 108.2, 115.1, 119.9, 124.4, 124.8, 127.6, 128.0, 129.0, 129.3, 132.8, 139.6, 140.8, 145.0, 159.4. MS (EI): m/z (%) = 301 (20), 273 (45), 259 (22), 258 (100), 231 (14), 230 (68), 228 (10). HRMS (EI): m/z calcd for C₁₉H₁₅N₃O: 301.1215; found: 301.1219. Compound 2f: white solid; mp 116–119 °C. ¹H NMR (500 MHz, DMSO-d ₆): δ = 1.36 (t, J = 7.0 Hz, 3 H), 4.06 (s, 3 H), 4.11 (q, J = 7.0 Hz, 2 H), 6.96 (d, J = 1.5 Hz, 1 H), 7.14–7.17 (m, 2 H), 7.35 (d, J = 1.5 Hz, 1 H), 7.67–7.70 (m, 2 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 15.0, 57.2, 64.1, 102.9, 106.1, 115.9, 125.3, 129.1, 134.6, 134.9, 136.8, 151.8, 159.4. MS (EI): m/z (%) = 305 (39), 304 (21), 303 (82), 248 (53), 247 (49), 246 (100), 240 (58), 232 (37), 218 (37), 212 (87), 211 (12), 204 (51), 203 (26), 188 (20). HRMS (EI): m/z calcd for C₁₅H₁₄N₃O₂ ³⁵Cl: 303.0775; found: 303.0769. Compound 2g: orange solid; mp 123–126 °C. ¹H NMR (500 MHz, DMSO-d ₆): δ = 2.41 (s, 3 H), 7.36-7.41 (m, 1 H), 7.44–7.47 (m, 2 H), 7.70–7.73 (m, 3 H), 8.20–8.23 (m, 1 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 21.1, 97.4 (d, J _CF = 29 Hz), 114.8 (d, J _CF = 27 Hz), 122.0 (d, J _CF = 7 Hz), 123.1, 130.9, 132.7 (d, J _CF = 14 Hz), 134.1, 139.1, 143.1, 162.6 (d, J _CF = 244 Hz). MS (EI): m/z (%) = 227 (48), 199 (50), 198 (100), 184 (25). HRMS (EI): m/z calcd for C₁₃H₁₀N₃F: 227.0859; found: 227.0859. Compound 2h: orange solid; mp 109–111 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.52 (s, 3 H), 7.37–7.42 (m, 3 H), 7.43–7.50 (m, 2 H), 7.61–7.64 (m, 2 H), 7.65–7.69 (m, 3 H), 7.82–7.84 (m, 1 H), 8.15–8.19 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.4, 108.5, 120.5, 123.2, 124.9, 127.9, 128.2, 129.1, 130.6, 133.3, 134.7, 139.1, 140.8, 142.1, 146.0. MS (EI): m/z (%) = 285 (21), 258 (21), 257 (100), 256 (64), 140 (16), 139 (17). HRMS (EI): m/z calcd for C₁₉H₁₅N₃: 285.1266; found: 285.1266. Compound 2i: white solid, mp 155–158 °C. ¹H NMR (500 MHz, DMSO-d ₆): δ = 7.58–7.62 (m, 1 H), 8.02–8.04 (m, 2 H), 8.24–8.29 (m, 1 H), 8.30–8.33 (m, 1 H), 8.84–8.87 (m, 2 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 111.9, 116.3, 121.9, 126.5, 132.3, 135.0, 143.1, 145.3, 152.1. MS (EI): m/z (%) = 232 (31), 230 (68), 204 (46), 203 (20), 202 (91), 167 (48), 140 (53). HRMS (EI): m/z calcd for C₁₁H₇N₄ ³⁵Cl: 230.0359; found: 230.0359. Compound 2j: orange oil. ¹H NMR (500 MHz, CDCl₃): δ = 2.13 (s, 3 H), 7.35–7.44 (m, 4 H), 7.46–7.54 (m, 2 H), 8.08 (d, J = 8.8 Hz, 1 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 17.7, 109.9, 121.0, 125.4, 126.8, 127.1, 130.3, 131.8, 134.5, 134.6, 134.7, 135.3, 144.2. MS (EI): m/z (%) = 245 (20), 243 (43), 217 (19), 216 (36), 215 (40), 214 (74), 200 (21), 180 (100). HRMS (EI): m/z calcd for C₁₃H₁₀N₃ ³⁵Cl: 243.0563; found: 243.0562. Compound 2k: white solid; mp 200–202 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.19–7.25 (m, 1 H), 7.34–7.37 (m, 1 H), 7.57–7.62 (m, 2 H), 7.68–7.72 (m, 2 H), 8.09–8.13 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 96.3 (d, J _CF = 29 Hz), 114.6 (d, J _CF = 26 Hz), 122.1 (d, J _CF = 11 Hz), 124.0, 130.4, 132.7 (d, J _CF = 14 Hz), 134.9, 135.3, 143.5, 163.1 (d, J _CF = 248 Hz). MS (EI): m/z (%) = 247 (24), 219 (47), 185 (15), 184 (100), 158 (13), 157 (11). HRMS (EI): m/z calcd for C₁₂H₇N₃ ³⁵ClF: 247.0313; found: 247.0322. Compound 2l: white solid; mp 224–226 °C. IR (film; CH₂Cl₂): ν_max = 2226 (CN) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.47 (dd, J = 8.8, 2.8 Hz, 1 H), 7.96 (d, J = 2.8 Hz, 1 H), 7.93–7.99 (m, 4 H), 8.11 (d, J= 8.8 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 110.2, 112.7, 117.9, 121.9, 122.7, 125.0, 126.4, 132.5, 134.2, 136.0, 140.1. MS (EI): m/z (%) = 256 (17), 254 (49), 228 (44), 226 (99), 192 (23), 191 (100), 102 (56). HRMS (EI): m/z calcd for C₁₃H₇N₄ ³⁵Cl: 254.0359; found: 254.0358. Compound 2m: white solid, mp 170–172 °C. ¹H NMR (400 MHz, CDCl₃): δ = 3.91 (s, 3 H), 7.09–7.13 (m, 2 H), 7.37 (dd, J = 8.8, 1.6 Hz, 1 H), 7.60–7.64 (m, 2 H), 7.65 (d, J = 1.6 Hz, 1 H), 8.04 (d, J = 8,8 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 55.8, 110.2, 115.2, 121.2, 124.7, 125.5, 129.6, 133.4, 134.6, 144.9, 160.2. MS (EI): m/z (%) = 261 (13), 259 (39), 218 (34), 216 (100), 196 (90), 190 (21), 189 (10), 188 (66), 181 (20), 153 (35). HRMS (EI): m/z calcd for C₁₃H₁₀N₃O³⁵Cl: 259.0512; found: 259.0513. Compound 2n: white solid, mp 135–138 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.36 (d, J = 2 Hz, 1 H), 7.41 (dd, J = 8.8, 2.4 Hz, 1 H), 7.45–7.49 (m, 1 H), 7.54–7.57 (m, 1 H), 7.86 (d, J = 2.4 Hz, 1 H), 8.08 (d, J = 8.8 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 110.3, 121.4, 121.6, 125.8, 129.2, 130.2, 134.1, 134.3, 135.2, 137.5, 144.4 (one signal not visible). MS (EI): m/z (%) = 343 (25), 340 (13), 314 (16), 279 (21), 277 (16), 236 (65), 234 (100), 199 (20), 198 (18), 164 (26). HRMS (EI): m/z calcd for C₁₂H₆N₃ ³⁵Cl₂ ⁷⁹Br: 340.9122; found: 340.9127. Compound 2o: colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 1.93 (s, 6 H), 6.84–6.87 (m, 1 H), 7.17–7.22 (m, 1 H), 7.25–7.27 (m, 2 H), 7.37–7.41 (m, 1 H), 8.10–8.14 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 17.6, 95.5 (d, J _CF = 27 Hz), 114.2 (d, J _CF = 27 Hz), 121.8 (d, J _CF = 11 Hz), 128.9, 130.6, 133.9, 134.4 (d, J _CF = 14 Hz), 136.6, 142.5, 163.0 (d, J _CF = 248 Hz). MS (EI): m/z (%) = 241 (68), 213 (36), 212 (100), 211 (17), 199 (24), 198 (83). HRMS (EI): m/z calcd for C₁₄H₁₂N₃F: 241.1015; found: 241.1013. Compound 2p: white solid; mp 134–137 °C. ¹H NMR (400 MHz, CDCl₃): δ = 3.88 (s, 6 H), 6.59 (t, J = 2.0 Hz, 1 H), 6.88–6.90 (m, 2 H), 7.49 (dd, J = 8.8, 1.6 Hz, 1 H), 7.77 (d, J = 1.6 Hz, 1 H), 8.05 (d, J = 8.8 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 55.9, 100.8, 101.5, 110.6, 121.3, 125.8, 133.0, 134.9, 138.2, 145.2, 161.8. MS (EI): m/z (%) = 291 (32), 290 (16), 289 (83), 261 (33), 246 (28), 227 (22), 226 (100), 218 (49), 203 (44), 183 (18). HRMS (EI): m/z calcd for C₁₄H₁₂N₃O₂ ³⁵Cl: 289.0618; found: 289.0623. Compound 2q: white solid; mp 142–144 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.48 (s, 3 H), 7.39–7.44 (m, 2 H), 7.52 (dd, J = 8.8, 1.6 Hz, 1 H), 7.58–7.63 (m, 2 H), 7.88 (d, J = 1.6 Hz, 1 H), 8.00 (d, J = 8.8 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.3, 113.5, 121.5, 122.6, 123.1, 128.1, 130.6, 133.6, 134.2, 139.4, 145.4. MS (EI): m/z (%) = 289 (24), 287 (24), 261 (21), 260 (31), 259 (22), 258 (29), 181 (26), 180 (100), 179 (23), 178 (11). HRMS (EI): m/z calcd for C₁₃H₁₀N₃ ⁷⁹Br: 287.0058; found: 287.0061. Compound 4: white solid; mp 122–124 °C. IR (film; CH₂Cl₂): ν_max = 1531 (NO₂) cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 2.50 (s, 3 H), 4.00 (s, 3 H), 7.11 (s, 1 H), 7.44–7.47 (m, 2 H), 7.57–7.60 (m, 2 H), 8.56 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 21.3, 57.0, 92.2, 118.0, 123.2, 130.7, 133.6, 134.4, 138.9, 139.5, 139.8, 153.3. MS (EI): m/z (%) = 284 (100), 241 (41), 211 (21), 210 (90), 196 (11), 183 (33), 181 (28), 180 (80). HRMS (EI): m/z calcd for C₁₄H₁₂N₄O₃: 284.0909; found: 284.0918. Compound 5: colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 1.93 (s, 6 H), 7.08 (d, J = 9.2 Hz, 1 H), 7.29–7.31 (m, 2 H), 7.43–7.47 (m, 1 H), 8.95 (d, J = 6.4 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 17.6, 98.2 (d, J _CF = 26 Hz), 119.8, 129.2, 131.2, 133.1, 135.6 (d, J _CF = 12 Hz), 136.4, 139.4, 140.2, 155.5. MS (EI): m/z (%) = 286 (86), 241 (15), 228 (13), 213 (34), 212 (100), 211 (70), 210 (38), 209 (21), 185 (21). HRMS (EI): m/z calcd for C₁₄H₁₁N₄O₂F: 286.0866; found: 286.0869. Compound 6: brown oil. IR (film; CH₂Cl₂): ν_max = 2094 (>=N=N), 1713 (C=O stretching) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 0.89–0.94 (m, 3 H), 1.28–1.38 (m, 2 H), 1.57–1.66 (m, 2 H), 3.62–3.66 (m, 2 H), 6.21 (d, J = 1.6 Hz, 1 H), 6.30 (dd, J = 9.6, 1.6 Hz, 1 H), 6.99–7.02 (m, 2 H), 7.05 (d, J = 9.6 Hz, 1 H), 7.30–7.33 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 13.9, 20.3, 29.3, 54.6, 109.5, 113.6, 124.8, 125.0, 129.0, 130.3, 130.7, 144.7, 150.0, 183.1. Compound 7: orange solid; mp 199–200 °C. IR (film; CH₂Cl₂): ν_max = 3253 (NH), 1693 (C=O stretching) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.22 (s, 6 H), 5.45 (s, 1 H), 7.14–7.23 (m, 3 H), 7.28 (s, 1 H), 7.66–7.69 (m, 1 H), 8.41–8.44 (m, 1 H), 8.96–8.98 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 18.1, 102.4, 128.4, 128.6, 129.0, 130.9, 133.3, 134.4, 135.8, 147.0, 147.2, 153.3, 180.4, 182.2. MS: m/z = 279.2 [M + H]. Anal. Calcd (%) for C₁₇H₁₄N₂O₂: C, 73.37; H, 5.07; N, 10.06. Found: C, 73.22; H, 5.26; N, 9.95.
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