Synlett 2013; 24(11): 1420-1422
DOI: 10.1055/s-0033-1338747
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Functionalized Azet-2(1H)-imines through [2+2] Cycloaddition of Imines and Ketenimines

Issa Yavari*
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
,
Manijeh Nematpour
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
› Author Affiliations
Further Information

Publication History

Received: 26 February 2013

Accepted after revision: 18 April 2013

Publication Date:
17 May 2013 (online)


Abstract

The reaction between ketenimine intermediates, generated from terminal alkynes and sulfonyl azides, trichloroacetonitrile, and sodium arylsulfinates in N,N-dimethylformamide at room ­temperature affords N-[3-aryl(alkyl)-4-arylazet-2(1H)-ylidene]-arene(alkane)sulfonamides in moderate to good yields.

 
  • References and Notes

  • 1 Durckheimer W, Blumbach J, Lattrell R, Scheunemann KH. Angew. Chem., Int. Ed. Engl. 1985; 24: 180
  • 2 Barrett AG. M, Sturgess MA. Tetrahedron 1988; 44: 5615
  • 4 Davies DE, Storr RC In Comprehensive Heterocyclic Chemistry I . Vol. 7. Katritzky AR, Rees CW. Elsevier; Oxford: 1984: 237
  • 5 General Procedure for the Synthesis of Compounds 7 To a mixture of sulfonyl azide 2 (1.2 mmol), alkyne 1 (1 mmol), and CuI (0.1 mmol), Et3N (1 mmol) in DMF (2 mL) was slowly added 5 (1 mmol) and sodium arylsulfinate 4 (1 mmol) stirred at r.t. under N2 atmosphere. After completion of the reaction [about 6 h; TLC (EtOAc–hexane, 1:5) monitoring], the mixture was diluted with CH2Cl2 (2 mL) and aq NH4Cl solution (3 mL), stirred for 30 min, and the layers were separated. The aqueous layer was extracted with CH2Cl2 (3 × 3 mL), and the combined organic fractions were dried (Na2SO4) and concentrated under reduced pressure. The residue was purified by flash column chromatography [silica gel (230–400 mesh; Merck), hexane–EtOAc, 5:1] to give the product. 4-Methyl-N-[3-Phenyl-4-tosylazet-2(1H)-ylidene]-benzenesulfonamide (7a) Pale yellow powder, mp 120–123 °C; yield 0.38 g (84%). IR (KBr): νmax = 3430, 2921, 1516, 1392, 1275, 1132, 1080 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.47 (3 H, s, Me), 2.48 (3 H, s, Me), 5.07 (1 H, s, NH), 7.26–7.30 (3 H, m, Ph), 7.34–7.40 (4 H, m, Ph), 7.47 (2 H, d, 3 J = 7.9 Hz, Ar), 7.83 (2 H, d, 3 J = 7.7 Hz, Ar), 7.91 (2 H, d, 3 J = 7.9 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 27.2 (Me), 27.3 (Me), 122.5 (C), 127.5 (2 CH), 128.0 (2 CH), 128.7 (2 CH), 129.2 (CH), 130.6 (2 CH), 130.7 (2 CH), 132.5 (2 CH), 135.0 (C), 136.0 (CH), 142.1 (C), 146.7 (C), 147.3 (C), 166.7 (C), 167.3 (C). MS (EI): m/z (%) = 452 (2) [M+], 375 (8), 361 (12), 297 (14), 196 (23), 155 (100), 91 (70), 77 (51). Anal. Calcd (%) for C23H20N2O4S2 (452.09): C, 61.04; H, 4.45; N, 6.19. Found: C, 61.49; H, 4.52; N, 6.28. N-[3-Phenyl-4-tosylazet-2(1H)-ylidene]benzene-sulfonamide (7b) Pale yellow powder, mp 111–113 °C; yield 0.35 g (80%). IR (KBr): νmax = 3437, 2939, 1528, 1400, 1271, 1140, 1084 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.48 (3 H, s, Me), 5.08 (1 H, s, NH), 7.29–7.36 (3 H, m, Ph), 7.40 (2 H, d, 3 J = 7.7 Hz, Ar), 7.48 (2 H, d, 3 J = 7.7 Hz, Ar), 7.62 (2 H, t, 3 J = 7.9 Hz, Ar), 7.75 (1 H, t, 3 J = 7.9 Hz, Ar), 7.91 (2 H, d, 3 J = 7.6 Hz, Ar), 8.03 (2 H, d, 3 J = 7.9 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 28.2 (Me), 122.6 (C), 127.4 (2 CH), 127.5 (2 CH), 128.7 (2 CH), 129.2 (CH), 130.2 (2 CH), 130.7 (2 CH), 132.5 (2 CH), 135.7 (CH), 136.2 (C), 142.1 (C), 144.8 (C), 147.3 (C), 165.1 (C), 168.8 (C). MS (EI): m/z (%) = 438 (3) [M+], 361 (11), 283 (13), 256 (15), 155 (76), 141 (100), 91 (34), 77 (44). Anal. Calcd (%) for C22H18N2O4S2 (438.07): C, 60.26; H, 4.14; N, 6.39. Found: C, 60.06; H, 4.18; N, 6.45. N-[3-Phenyl-4-tosylazet-2(1H)-ylidene]methane-sulfonamide (7c) Pale yellow powder, mp 98–100 °C; yield 0.28 g (74%). IR (KBr): νmax = 3425, 2945, 1541, 1401, 1279, 1126 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.47 (3 H, s, Me), 3.65 (3 H, s, Me), 5.08 (1 H, s, NH), 7.29–7.34 (3 H, m, Ph), 7.40 (2 H, d, 3 J = 7.7 Hz, Ar), 7.49 (2 H, d, 3 J = 7.8 Hz, Ar), 7.91 (2 H, d, 3 J = 7.8 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 26.2 (Me), 33.0 (Me), 122.5 (C), 127.5 (2 CH), 128.8 (2 CH), 129.3 (CH), 130.7 (2 CH), 132.5 (2 CH), 135.0 (C), 142.1 (C), 147.4 (C), 162.8 (C), 167.1 (C). MS (EI): m/z (%) = 376 (M+, 2), 299 (10), 256 (14), 221 (12), 155 (40), 78 (100), 77 (44). Anal. Calcd (%) for C17H16N2O4S2 (376.06): C, 54.24; H, 4.28; N, 7.44. Found: C, 54.66; H, 4.34; N, 7.56. 4-Methyl-N-[3-phenyl-4-(phenylsulfonyl)azet-2(1H)-ylidene]benzenesulfonamide (7d) Pale yellow powder, mp 129–132 °C; yield 0.34 g (78%). IR (KBr): νmax = 3436, 2925, 1512, 1397, 1278, 1131, 1082 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.48 (3 H, s, Me), 5.08 (1 H, s, NH), 7.29-7.36 (3 H, m, Ph), 7.40 (2 H, d, 3 J = 7.7 Hz, Ar), 7.49 (2 H, d, 3 J = 7.6 Hz, Ar), 7.62 (2 H, t, 3 J = 7.7 Hz, Ar), 7.75 (1 H, t, 3 J = 7.7 Hz, Ar), 7.91 (2 H, d, 3 J = 7.9 Hz, Ar), 8.05 (2 H, d, 3 J = 7.9 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 32.2 (Me), 122.6 (C), 127.4 (2 CH), 127.5 (2 CH), 128.7 (2 CH), 129.2 (CH), 130.1 (2 CH), 130.7 (2 CH), 132.6 (2 CH), 135.7 (C), 136.0 (CH), 142.1 (C), 144.8 (C), 147.3 (C), 164.8 (C), 167.7 (C). MS (EI): m/z (%) = 438 (2) [M+], 361 (14), 347 (13), 283 (16), 196 (14), 155 (100), 141 (68), 91 (55), 77 (44). Anal. Calcd (%) for C22H18N2O4S2 (438.07): C, 60.26; H, 4.14; N, 6.39. Found: C, 60.69; H, 4.21; N, 6.44. N-[3-Phenyl-4-(phenylsulfonyl)azet-2(1H)-ylidene]-benzenesulfonamide (7e) Pale yellow powder, mp 114–117 °C; yield 0.31 g (73%). IR (KBr): νmax = 3450, 2922, 1511, 1264, 1140, 1082 cm–1. 1H NMR (500 MHz, CDCl3): δ = 5.06 (1 H, s, NH), 7.31–7.36 (5 H, m, Ph), 7.51–7.53 (3 H, m, Ph), 7.59 (2 H, t, 3 J = 7.7 Hz, Ar), 7.72 (1 H, t, 3 J = 7.7 Hz, Ar), 7.98 (2 H, d, 3 J = 7.9 Hz, Ar), 8.05 (2 H, d, 3 J = 7.9 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 122.6 (C), 127.4 (2 CH), 127.9 (2 CH), 128.8 (2 CH), 129.3 (CH), 130.2 (2 CH), 130.7 (CH), 132.6 (2 CH), 135.3 (CH), 135.7 (2 CH), 139.0 (C), 142.2 (C), 144.8 (C), 166.4 (C), 168.3 (C). MS (EI): m/z (%) = 424 (3) [M+], 347 (13), 283 (8), 242 (10), 182 (21), 141 (100), 77 (34). Anal. Calcd (%) for C21H16N2O4S2 (424.06): C, 59.42; H, 3.80; N, 6.60. Found: C, 59.69; H, 3.84; N, 6.57. N-[3-Phenyl-4-(phenylsulfonyl)azet-2(1H)-ylidene]-methanesulfonamide (7f) Pale yellow powder, mp 90–93 °C; yield 0.25 g (70%). IR (KBr): νmax = 3439, 1513, 1269, 1145, 1086 cm–1. 1H NMR (500 MHz, CDCl3): δ = 3.60 (3 H, s, Me), 5.08 (1 H, s, NH), 7.29–7.36 (3 H, m, Ph), 7.47 (2 H, d, 3 J = 7.7 Hz, Ar), 7.63 (2 H, t, 3 J = 7.8 Hz, Ar), 7.74 (1 H, t, 3 J = 7.8 Hz, Ar), 8.04 (2 H, d, 3 J = 7.8 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 33.0 (Me), 122.5 (C), 127.4 (2 CH), 128.8 (2 CH), 129.3 (CH), 130.2 (2 CH), 132.6 (2 CH), 135.7 (CH), 142.3 (C), 147.8 (C), 164.6 (C), 167.4 (C). MS (EI): m/z (%) = 362 (2) [M+], 285 (11), 242 (18), 221 (21), 141 (54), 78 (100), 77 (25). Anal. Calcd (%) for C16H14N2O4S2 (362.04): C, 53.02; H, 3.89; N, 7.73. Found: C, 53.41.; H, 3.94; N, 7.80. N-[3-Butyl-4-tosylazet-2(1H)-ylidene]-4-methylbenzene-sulfonamide (7g) Yellow oil; yield 0.29 g (67%). IR (KBr): νmax = 3452, 2932, 1525, 1461, 1278, 1118 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.91 (3 H, t, 3 J = 6.9 Hz, Me), 1.28–1.45 (2 H, m, CH2), 1.47–1.53 (2 H, m, CH2), 2.18 (2 H, t, 3 J = 7.0 Hz, CH2), 2.43 (3 H, s, Me), 2.48 (3 H, s, Me), 5.10 (1 H, s, NH), 7.39–7.41 (4 H, m, Ph), 7.83 (2 H, d, 3 J = 8.0 Hz, Ar), 7.91 (2 H, d, 3 J = 8.0 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 13.9 (Me), 18.5 (CH2), 22.1 (CH2), 22.2 (CH2), 31.0 (Me), 32.3 (Me), 122.2 (C), 127.5 (2 CH), 128.0 (2 CH), 130.6 (2 CH), 130.7 (2 CH), 132.3 (C), 136.0 (C), 144.3 (C), 146.6 (C), 162.6 (C), 166.2 (C). MS (EI): m/z (%) = 432 (2) [M+], 375 (16), 341 (13), 277 (21), 196 (31), 155 (100), 91 (51), 77 (41), 57 (52). Anal. Calcd (%) for C21H24N2O4S2 (432.12): C, 58.31; H, 5.59; N, 6.48. Found: C, 58.71; H, 5.65; N, 6.55. N-[3-Butyl-4-tosylazet-2(1H)-ylidene]benzene-sulfonamide (7h) Yellow oil; yield 0.25 g (60%). IR (KBr): νmax = 3411, 2924, 1518, 1471, 1298, 1145, 1086 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.90 (3 H, t, 3 J = 6.9 Hz, Me), 1.39–1.45 (2 H, m, CH2), 1.48–1.53 (2 H, m, CH2), 2.17 (2 H, t, 3 J = 7.0 Hz, CH2), 2.48 (3 H, s, Me), 5.09 (1 H, s, NH), 7.39 (2 H, d, 3 J = 7.8 Hz, Ar), 7.62 (2 H, t, 3 J = 7.8 Hz, Ar), 7.76 (1 H, t, 3 J = 7.8 Hz, Ar), 7.91 (2 H, d, 3 J = 8.0 Hz, Ar), 8.05 (2 H, d, 3 J = 8.0 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 14.0 (Me), 18.5 (CH2), 22.1 (CH2), 22.5 (CH2), 31.0 (Me), 122.4 (C), 127.4 (2 CH), 127.5 (2 CH), 130.1 (2 CH), 130.7 (2 CH), 135.7 (CH), 142.1 (C), 144.8 (C), 147.2 (C), 164.9 (C), 167.6 (C). MS (EI): m/z (%) = 418 (2) [M+], 361 (10), 341 (16), 277 (32), 155 (34), 141 (100), 91 (49), 77 (35), 57 (50). Anal. Calcd (%) for C20H22N2O4S2 (418.10): C, 57.39; H, 5.30; N, 6.69. Found: C, 57.76; H, 5.44; N, 6.75. N-[3-Butyl-4-tosylazet-2(1H)-ylidene]methane-sulfonamide (7i) Yellow oil; yield 0.21 g (58%). IR (KBr): νmax = 3513, 2934, 1524, 1408, 1279, 1118, 1044 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.91 (3 H, t, 3 J = 6.9 Hz, Me), 1.38–1.43 (2 H, m, CH2), 1.47–1.51 (2 H, m, CH2), 2.17 (2 H, t, 3 J = 7.0 Hz, CH2), 2.48 (3 H, s, Me), 3.66 (3 H, s, Me), 5.07 (1 H, s, NH), 7.39 (2 H, d, 3 J = 7.9 Hz, Ar), 7.91 (2 H, d, 3 J = 7.9 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 13.9 (Me), 18.5 (CH2), 22.1 (CH2), 22.3 (CH2), 31.0 (Me), 33.0 (Me), 122.6 (C), 127.5 (2 CH), 130.7 (2 CH), 142.1 (C), 147.3 (C), 162.2 (C), 167.5 (C). MS (EI): m/z (%) = 356 (2) [M+], 277 (12), 236 (10), 155 (39), 91 (45), 78 (100), 57 (46). Anal. Calcd (%) for C15H20N2O4S2 (356.46): C, 50.54; H, 5.66; N, 17.86. Found: C, 50.76; H, 5.74; N, 18.01.
  • 6 Whiting M, Fokin VV. Angew. Chem. Int. Ed. 2006; 45: 3157
  • 7 Xu X, Cheng D, Li J, Guo H, Yan J. Org. Lett. 2007; 9: 1585
  • 8 Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 2596
  • 9 Wang J, Wang J, Zhu Y, Lu P, Wang Y. Chem. Commun. 2011; 47: 3275
  • 10 Cui SL, Wang J, Wang YG. Tetrahedron 2008; 64: 487
  • 11 Yavari I, Nematpour M. Synlett 2012; 23: 2215
  • 12 Yavari I, Nematpour M, Yavari S, Sadeghizadeh F. Tetrahedron Lett. 2012; 53: 1889
  • 13 Yavari I, Nematpour M, Ghazanfarpour-Darjani M. Tetrahedron Lett. 2012; 53: 942
  • 14 Yavari I, Nematpour M. Mol. Diversity 2012; 16: 651
  • 15 Recently, Sharpless and co-workers established anhydrous conditions with CuI in CHCl3/2,6-lutidine at 0 °C to prevent intermediate 9 from decomposing and provide selective formation of the desired 1-sulfonyltriazoles. See: Yoo EJ, Ahlquist M, Kim SH, Bae I, Fokin VV, Sharpless KB, Chang S. Angew. Chem. Int. Ed. 2007; 46: 1730
  • 16 Cassidy MP, Raushel J, Fokin VV. Angew. Chem. Int. Ed. 2006; 45: 3154
  • 17 Lu P, Wang Y. Synlett 2010; 165
  • 18 Yao W, Pan L, Zhang Y, Wang G, Wang X, Ma C. Angew. Chem. Int. Ed. 2010; 49: 9210