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Synlett 2012; 23(15): 2215-2218
DOI: 10.1055/s-0032-1317075
letter
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed One-Pot Synthesis of Functionalized 1,4-Dihydroazete Derivatives from Sulfonyl Azides, Terminal Alkynes, and Tetramethylguanidine

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

Publication History

Received: 20 May 2012

Accepted after revision: 18 July 2012

Publication Date:
17 August 2012 (online)

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Abstract

Ketenimine intermediates generated by the addition of copper acetylides to sulfonyl azides are trapped by tetramethyl­guanidine to afford 1,4-dihydro-N,N-dimethyl-3-aryl(alkyl)-4-­aryl(alkyl)sulfoniminoazet-2-amine derivatives in moderate to good yields.

Key words

1,4-dihydroazete - copper iodide - tetramethyl­guanidine - sulfonyl azide - terminal alkyne - ketenimine
 

  • References and Notes

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  • 21 General Procedure for the Synthesis of Compounds 4
    To a mixture of sulfonyl azide 2, (1.2 mmol), alkyne 1 (1 mmol), and CuI (0.1 mmol), Et3N (1 mmol) in THF (2 mL) was slowly added tetramethylguanidine (1 mmol). The mixture was stirred at r.t. After completion of the reaction [about 12 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. 1,4-Dihydro-N,N-dimethyl-3-phenyl-4-tosyliminoazet-2-amine (4a) Yellow oil; yield 0.27 g (80%). IR (KBr): νmax = 3438, 2923, 1511, 1396, 1270, 1139, 1083 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.38 (3 H, s, Me), 2.80 (6 H, s, NMe2), 3.94 (1 H, s, NH), 7.18 (2 H, t, 3 J = 7.5 Hz, Ar), 7.24 (1 H, t, 3 J = 7.5 Hz, Ar), 7.25–7.28 (4 H, m, Ph), 7.76 (2 H, d, 3 J = 7.9 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 29.7 (Me), 40.5 (NMe2), 88.3 (C), 125.7 (CH), 126.4 (2 CH), 128.1 (2 CH), 128.7 (2 CH), 129.6 (2 CH), 137.5 (C), 141.1 (C), 142.3 (C), 166.1 (C), 169.2 (C). MS (EI): m/z (%) = 341 (2) [M+], 297 (8), 271 (12), 155 (100), 145 (22), 91 (70), 77 (54). Anal. Calcd (%) for C18H19N3O2S (341.00): C, 63.32; H, 5.61; N, 12.31. Found: C, 63.79; H, 5.54; N, 12.38. 1,4-Dihydro-N,N-dimethyl-3-phenyl-4-benzenesulfoniminoazet-2-amine (4b) Yellow oil; yield 0.27 g (82%). IR (KBr): νmax = 3437, 2929, 1520, 1400, 1273, 1142, 1087 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.85 (6 H, s, NMe2), 3.98 (1 H, s, NH), 7.15 (2 H, t, 3 J = 7.5 Hz, Ar), 7.20 (1 H, t, 3 J = 7.5 Hz, Ar), 7.23 (2 H, d, 3 J = 7.5 Hz, Ar), 7.25–7.29 (3 H, m, Ph), 7.78 (2 H, d, 3 J = 7.9 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 40.6 (NMe2), 88.5 (C), 125.6 (CH), 126.5 (2 CH), 128.3 (2 CH), 128.8 (2 CH), 129.7 (2 CH), 137.5 (CH), 140.2 (C), 142.5 (C), 165.7 (C), 170.8 (C). MS (EI): m/z (%) = 327 (3) [M+], 283 (12), 257 (17), 145 (31), 141 (100), 77 (54). Anal. Calcd (%) for C17H17N3O2S (327.05): C, 62.36; H, 5.23; N, 12.83. Found: C, 62.06; H, 5.18; N, 12.75. 1,4-Dihydro-N,N-dimethyl-3-phenyl-4-methanesulfoniminoazet-2-amine (4c) Yellow oil; yield 0.20 g (74%). IR (KBr): νmax = 3435, 2925, 1531, 1401, 1271, 1120 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.81 (3 H, s, Me), 2.93 (6 H, s, NMe2), 4.01 (1 H, s, NH), 7.26 (2 H, t, 3 J = 7.4 Hz, Ar), 7.30 (1 H, t, 3 J = 7.4 Hz, Ar), 7.42 (2 H, d, 3 J = 7.4 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 29.2 (Me), 40.4 (NMe2), 87.2 (C), 124.4 (CH), 125.7 (2 CH), 126.4 (2 CH), 140.9 (C), 162.3 (C), 172.5 (C). MS (EI): m/z (%) = 265 (2) [M+], 221 (10), 195 (14), 145 (30), 79 (100), 77 (44). Anal. Calcd (%) for C12H15N3O2S (265.00): C, 54.32; H, 5.70; N, 15.06. Found: C, 54.66; H, 5.64; N, 15.16. 1,4-Dihydro-N,N-dimethyl-3-propyl-4-tosyliminoazet-2-amine (4d) Yellow oil; yield 0.20 g (67%). IR (KBr): νmax = 3436, 2924, 1510, 1397, 1271, 1138, 1084 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.87 (3 H, t, 3 J = 6.9 Hz, Me), 1.57–1.62 (2 H, m, CH2), 2.38 (3 H, s, Me), 2.52 (2 H, t, 3 J = 7.0 Hz, CH2), 2.91 (6 H, s, NMe2), 3.94 (1 H, s, NH), 7.24 (2 H, d, 3 J = 8.0 Hz, Ar), 7.81 (2 H, d, 3 J = 8.0 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 13.8 (Me), 21.4 (CH2), 22.7 (CH2), 29.7 (Me), 40.5 (NMe2), 86.1 (C), 126.5 (2 CH), 128.4 (2 CH), 139.0 (C), 142.0 (C), 166.6 (C), 172.5 (C). MS (EI): m/z (%) = 307 (2) [M+], 263 (14), 197 (14), 155 (100), 111 (28), 91 (55), 77 (44), 43 (22). Anal. Calcd (%) for C15H21N3O2S (307.01): C, 58.61; H, 6.89; N, 13.67. Found: C, 58.89; H, 6.94; N, 13.54. 1,4-Dihydro-N,N-dimethyl-3-propyl-4-benzenesulfoniminoazet-2-amine (4e) Yellow oil; yield 0.17 g (60%). IR (KBr): νmax = 3455, 2925, 1513, 1269, 1142, 1087 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.87 (3 H, t, 3 J = 7.0 Hz, Me), 1.57–1.60 (2 H, m, CH2), 2.51 (2 H, t, 3 J = 7.0 Hz, CH2), 2.89 (6 H, s, NMe2), 3.93 (1 H, s, NH), 7.39 (1 H, t, 3 J = 8.0 Hz, Ar), 7.43 (2 H, t, 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), 21.1 (CH2), 22.8 (CH2), 40.5 (NMe2), 86.1 (C), 124.3 (CH), 125.6 (2 CH), 128.2 (2 CH), 135.7 (C), 162.9 (C), 172.4 (C). MS (EI): m/z (%) = 293 (3) [M+], 249 (13), 223 (8), 141 (100), 111 (18), 77 (34), 43 (35). Anal. Calcd (%) for C14H19N3O2S (293.00): C, 57.31; H, 6.53; N, 14.32. C, 57.16; H, 6.48; N, 14.21. 1,4-Dihydro-N,N-dimethyl-3-propyl-4-methanesulfoniminoazet-2-amine (4f) Yellow oil; yield 0.13 g (57%). IR (KBr): νmax = 3436, 1518, 1269, 1142, 1086 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.86 (3 H, t, 3 J = 6.9 Hz, Me), 1.57–1.61 (2 H, m, CH2), 2.50 (2 H, t, 3 J = 6.9 Hz, CH2), 2.76 (3 H, s, Me), 2.90 (6 H, s, NMe2) 3.92 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 13.8 (Me), 19.1 (CH2), 22.6 (CH2), 29.6 (Me), 40.5 (NMe2), 86.7 (C), 162.9 (C), 172.5 (C). MS (EI): m/z (%) = 231 (2) [M+], 187 (11), 161 (18), 119 (41), 79 (100), 43 (25). Anal. Calcd (%) for C9H17N3O2S (231.02): C, 46.73; H, 7.41; N, 18.17. Found: C, 47.02; H, 7.34; N, 18.08. 1,4-Dihydro-N,N-dimethyl-3-butyl-4-tosyliminoazet-2-amine (4g) Yellow oil; yield 0.20 g (62%). IR (KBr): νmax = 3452, 2933, 1520, 1401, 1270, 1118 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.85 (3 H, t, 3 J = 6.9 Hz, Me), 1.23–1.27 (2 H, m, CH2), 1.59–1.62 (2 H, m, CH2), 2.40 (3 H, s, Me), 2.50 (2 H, t, 3 J = 7.0 Hz, CH2), 2.85 (6 H, s, NMe2), 3.97 (1 H, s, NH), 7.38 (2 H, d, 3 J = 8.0 Hz, Ar), 7.92 (2 H, d, 3 J = 8.0 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 13.9 (Me), 19.4 (CH2), 22.4 (CH2), 27.3 (CH2), 30.4 (Me), 40.3 (NMe2), 86.6 (C), 125.6 (2 CH), 128.2 (2 CH), 137.7 (C), 141.2 (C), 166.0 (C), 172.5 (C). MS (EI): m/z (%) = 321 (3) [M+], 277 (16), 251 (13), 155 (100), 125 (20), 91 (51), 77 (41), 57 (52). Anal. Calcd (%) for C16H23N3O2S (321.00): C, 59.78; H, 7.21; N, 13.07. Found: C, 59.51; H, 7.27; N, 13.18. 1,4-Dihydro-N,N-dimethyl-3-butyl-4-benzenesulfoniminoazet-2-amine (4h) Yellow oil; yield 0.17 g (57%). IR (KBr): νmax = 3413, 2926, 1517, 1401, 1268, 1141, 1086 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.84 (3 H, t, 3 J = 6.9 Hz, Me), 1.24–1.28 (2 H, m, CH2), 1.59–1.62 (2 H, m, CH2), 2.49 (2 H, t, 3 J = 7.0 Hz, CH2), 2.92 (6 H, s, NMe2), 3.98 (1 H, s, NH), 7.26 (1 H, t, 3 J = 7.9 Hz, Ar), 7.39 (2 H, t, 3 J = 7.9 Hz, Ar), 7.80 (2 H, d, 3 J = 7.9 Hz, Ar). 13C NMR (125.7 MHz, CDCl3): δ = 14.1 (Me), 20.0 (CH2), 22.5 (CH2), 27.3 (CH2), 40.5 (NMe2), 86.4 (C), 125.6 (CH), 128.7 (2 CH), 129.6 (2 CH), 138.6 (C), 167.3 (C), 172.5 (C). MS (EI): m/z (%) = 307 (3) [M+], 263 (12), 237 (10), 141 (100), 125 (29), 77 (35), 57 (50). Anal. Calcd (%) for C15H21N3O2S (307.00): C, 58.61; H, 6.89; N, 13.67. Found: C, 58.86; H, 6.74; N, 13.55. 1,4-Dihydro-N,N-dimethyl-3-butyl-4-methanesulfoniminoazet-2-amine (4i) Yellow oil; yield 0.13 g (53%). IR (KBr): νmax = 3513, 2934, 1521, 1403, 1270, 1118, 1042 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.85 (3 H, t, 3 J = 6.9 Hz, Me), 1.21–1.29 (2 H, m, CH2), 1.62–1.66 (2 H, m, CH2), 2.47 (2 H, t, 3 J = 7.0 Hz, CH2), 2.82 (3 H, s, Me), 2.90 (6 H, s, NMe2), 3.96 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 14.0 (Me), 19.8 (CH2), 22.4 (CH2), 27.3 (CH2), 30.7 (Me), 40.4 (NMe2), 86.2 (C), 166.2 (C), 172.6 (C). MS (EI): m/z (%) = 245 (2) [M+], 201 (12), 175 (10), 125 (39), 79 (100), 57 (46). Anal. Calcd (%) for C10H19N3O2S (245.00): C, 48.95; H, 7.81; N, 17.13. Found: C, 48.76; H, 7.75; N, 17.04
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