Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2014; 25(14): 1987-1990
DOI: 10.1055/s-0034-1378448
DOI: 10.1055/s-0034-1378448
letter
2-(Arylamino)aryliminophosphoranes as Easily Available and Convenient Starting Materials in the Synthesis of 1,2,3-Benzotriazoles
Further Information
Publication History
Received: 08 May 2014
Accepted after revision: 10 June 2014
Publication Date:
28 July 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201414/lookinside/thumbnails/10.1055-s-0034-1378448-1.jpg)
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.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
-
References and Notes
- 2 Li X, Fu J, Shi W, Luo Y, Zhang X, Zhu H, Yu H. Bull. Korean Chem. Soc. 2013; 34: 2387
- 3 Boido A, Boido CC, Sparatore F. Farmaco 2001; 56: 263
- 4 Kale RR, Prasad V, Mohapatra PP, Tiwari VK. Monatsh. Chem. 2010; 141: 1159
- 5 Piccionello AP, Guarcello A. Curr. Bioact. Compd. 2010; 6: 266
- 6a Znoiko SA, Kambolova AS, Maizlish VE, Shaposhnikov GP, Abramov IG, Filimonov SI. Russ. J. Gen. Chem. 2009; 79: 1735
- 6b Nolan KA, Humphries MP, Barnes J, Doncaster JR, Caraher MC, Tirelli N, Bryce RA, Whitehead RC, Stratford IJ. Bioorg. Med. Chem. 2010; 18: 696
- 6c Fujiwara C, Hagaya M, Kakuta H, Kawata K, Nakayama M, Ohsawa F, Ohta Y, Shinozaki R, Yakushiji N, Yamada Sh, Makishima M, Uno Sh, Tai A, Maehara A, Nakayama M, Oohashi T, Yasui H, Yoshikawa Y. ACS Med. Chem. Lett. 2012; 3: 427
- 6d Barnes J, Bryce RA, Caraher MC, Doncaster JR, Humphries MP, Nolan KA, Stratford IJ, Tirelli N, Barnes J, Doncaster JR, Whitehead RC. Bioorg. Med. Chem. 2010; 18: 696
- 6e Kulagowski JJ, Moody CJ, Rees CW. J. Chem. Soc., Perkin Trans. 1 1985; 2733
- 7a Beletskaya IP, Davydov DV, Moreno-Mañas M. Tetrahedron Lett. 1998; 39: 5617
- 7b Mukhopadhyay C, Tapaswi PK. Synth. Commun. 2012; 42: 2217
- 7c Antilla JC, Barder TE, Baskin JM, Buchwald SL. J. Org. Chem. 2004; 69: 5578
- 7d Alakonda L, Periasamy M. Synthesis 2012; 44: 1063
- 7e Jena AK, Mohapatra S, Panda N, Rout SR. Tetrahedron Lett. 2011; 52: 1924
- 8a Cao W, Chen J, Chen Y, Lin Y, Ma X, Xu D. Tetrahedron 2011; 67: 856
- 8b Chen Y.-L, Sun J.-Q, Wei X, Wong W.-Y, Lee AW. M. J. Org. Chem. 2004; 69: 7190
- 9a Song T, Xu L, Zhao J, Zhao J, Zhu S. Tetrahedron 2011; 67: 910
- 9b Rosevear J, Wilshire JF. K. Aust. J. Chem. 1991; 44: 1097
- 10a Ankati H, Biehl E. Tetrahedron Lett. 2009; 50: 4677
- 10b Moses JE, Zhang F. Org. Lett. 2009; 11: 1587
- 10c Chen Y, Larock RC, Shi F, Waldo JP. Org. Lett. 2008; 10: 2409
- 11 Łukasik E, Wróbel Z. Synlett 2014; 25: 217
- 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): νmax = 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): νmax = 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): νmax = 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): νmax = 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.
- 15a Sundberg RJ, Baxter EW, Pitts WJ, Ahmed-Schofield R, Nishiguchi T. J. Org. Chem. 1988; 53: 5097
- 15b Adam W, Hadjiarapoglou L, Mielke K, Treiber A. Tetrahedron Lett. 1994; 5625
- 16 Mukhopadhyay C, Tapaswi PK, Butcher RJ. Org. Biomol. Chem. 2010; 8: 4720