Synlett 2017; 28(12): 1445-1448
DOI: 10.1055/s-0036-1588989
letter
© Georg Thieme Verlag Stuttgart · New York

Novel Catalytic Three-Component Reaction between a Terminal Alkyne, Sulfonyl Azide, and O-Methyl Oxime

Mehdi Khalaj*a, Majid Ghazanfarpour-Darjania, Forugh Barat-Seftejanib, Azita Nourib
  • aDepartment of Chemistry, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran
  • bDepartment of Chemistry, Shahr-e-Qods Branch, Islamic Azad University, Tehran   Iran   Email: khalaj_mehdi@yahoo.com
Further Information

Publication History

Received: 27 January 2017

Accepted after revision: 08 March 2017

Publication Date:
10 April 2017 (eFirst)

Abstract

O-Methyl oximes have been employed as nucleophiles in reactions with ketenimines derived from sulfonyl azides and terminal alkynes to form N-alkylidene N′-tosylacetimidamide derivatives. The optimized conditions involved the use of CuPF6 and i-Pr2NEt in MeCN at 65 °C. Both O-methyl aldoximes and ketoximes were tolerated under the optimum conditions.

 
  • References and Notes

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  • 24 N-[N-(Arylsulfonyl)imidoyl]benzamides 4a–l; General Procedure i-Pr2NEt (1.0 mL) was slowly added to a stirred solution of the appropriate terminal alkyne (1.0 mmol), sulfonyl azide (1.2 mmol), and CuPF6 (0.10 mmol) in MeCN (3 mL) under N2 at r.t. After 15 min, the appropriate O-methyl oxime (4.0 mmol) was added, and the mixture was stirred in a sealed tube for 18 h (see Table 2) at 65–75 °C. The solvent was removed under vacuum and the residue was treated with B(C6F5)3 (0.3 mmol) and KOH (2.0 mmol) in 4:1 H2O–1,4-dioxane (10 mL) at 75 °C for 6 h. EtOAc (5 mL) and sat. aq NH4Cl (5 mL) were added, the mixture was stirred for an additional 30 min, and the two layers were separated. The aqueous layer was further extracted with EtOAc (3 × 10 mL), and the organic layers were combined, dried (Na2SO4), filtered, and concentrated under vacuum. The residue was purified by chromatography [silica gel, hexane–EtOAc (2:1)] N-(2-Phenyl-N-tosylethanimidoyl)benzamide (4a) Colorless solid; yield: 0.31 g (79%); mp 147–149 °C. IR (KBr): 3241, 1671, 1548, 1510, 1432, 1325, 1110 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 2.47 (s, 3 H, CH3), 3.89 (s, 2 H, CH2), 7.19 (t, 3 J = 6.3 Hz, 1 H, CH), 7.26–7.33 (m, 6 H, 6 CH), 7.43–7.67 (m, 5 H, 5 CH), 7.87 (d, 3 J = 7.6 Hz, 2 H, 2 CH), 10.78 (s, 1 H, NH). 13C NMR (125.7 MHz, CDCl3): δ = 21.5 (CH3), 44.9 (CH2), 126.5 (2 CH), 126.8 (CH), 127.4 (2 CH), 128.1 (2 CH), 128.4 (2 CH), 129.4 (2 CH), 130.1 (2 CH), 133.7 (CH), 134.1 (C), 135.1 (C), 140.3 (C), 142.5 (C), 159.1 (CH), 169.3 (C). MS: m/z (%) = 392 (M+, 5), 271 (13), 140 (17), 104 (23), 91 (100), 77 (492), 64 (40). Anal. Calcd for C22H20N2O3S (392.47): C, 67.33; H, 5.14; N, 7.14; S, 8.17. Found: C, 67.61; H, 5.37; N, 7.22; S, 8.13. N-[2-Phenyl-N-(phenylsulfonyl)ethanimidoyl]benzamide (4b) Colorless solid; yield: 0.29 g (76%); mp 140–142 °C. IR (KBr): 3256, 1662, 1541, 1522, 1417, 1331, 1124 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.87 (s, 2 H, CH2), 7.19–7.31 (m, 5 H, 5 CH), 7.51–7.64 (m, 5 H, 5 CH), 7.71–7.78 (m, 3 H, 3 CH), 7.89 (d, 3 J = 6.9 Hz, 2 H, 2 CH), 10.71 (s, 1 H, NH). 13C NMR (125.7 MHz, CDCl3): δ = 45.1 (CH2), 123.3 (CH), 124.9 (2 CH), 126.5 (2 CH), 128.7 (2 CH), 129.1 (2 CH), 129.9 (2 CH), 131.5 (2 CH), 133.6 (CH), 133.9 (C), 134.5 (CH), 136.1 (C), 145.7 (C), 159.4 (C), 170.1 (C). MS: m/z (%) = 378 (M+, 1), 273 (11), 156 (34), 121 (21), 91 (100), 77 (63), 64 (41). Anal. Calcd for C21H18N2O3S (378.45): C, 66.65; H, 4.79; N, 7.40; S, 8.47. Found: C, 66.83; H, 4.91; N, 7.53; S, 8.59. 4-Methoxy-N-[2-phenyl-N-(phenylsulfonyl)ethanimidoyl]benzamide (4c) Colorless solid; yield: 0.37 g (90%); mp 170–172 °C. IR (KBr): 3240, 1658, 1560, 1532, 1428, 1320, 1140 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.85 (s, 2 H, CH2), 3.89 (s, 3 H, OCH3), 6.95 (app. d, 3 J = 7.5 Hz, 2 H, 2 CH), 7.19–7.27 (m, 5 H, 5 CH), 7.69–7.76 (m, 5 H, 5 CH), 7.84 (app. d, 3 J = 7.5 Hz, 2 H, 2 CH), 10.68 (s, 1 H, NH). 13C NMR (125.7 MHz, CDCl3): δ = 46.2 (CH2), 57.1 (OCH3), 115.1 (2 CH), 125.2 (2 CH), 126.1 (CH), 126.8 (2 CH), 127.1 (C), 129.1 (2 CH), 130.4 (2 CH), 131.2 (2 CH), 134.0 (CH), 136.7 (C), 147.1 (C), 158.1 (C), 161.8 (C), 169.5 (C). MS: m/z (%) = 408 (M+, 1), 268 (11), 258 (17), 150 (57), 91 (100), 77 (67), 64 (35). Anal. Calcd for C22H20N2O4S (408.47): C, 64.69; H, 4.94; N, 6.86; S, 7.85. Found: C, 64.86; H, 5.31; N, 6.93; S, 7.91. 4-Bromo-N-[2-phenyl-N-(tosyl)ethanimidoyl]benzamide (4g) Colorless solid; yield: 0.37 g (79%); mp 181–183 °C. IR (KBr): 3236, 1657, 1549, 1532, 1420, 1317, 1140 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 2.41 (s, 3 H, CH3), 3.82 (s, 2 H, CH2), 7.20–7.31 (m, 7 H, 7 CH), 7.51 (d, 3 J = 7.7 Hz, 2 H, 2 CH), 7.76 (d, 3 J = 7.8 Hz, 2 H, 2 CH), 7.91 (d, 3 J = 7.8 Hz, 2 H, 2 CH), 10.76 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 23.9 (CH3), 44.0 (CH2), 125.5 (C), 125.9 (2 CH), 126.1 (CH), 127.5 (2 CH), 128.2 (2 CH), 128.9 (2 CH), 130.3 (2 CH), 132.7 (2 CH), 133.5 (C), 134.9 (C), 140.3 (C), 141.7 (C), 159.2 (C), 169.3 (C). MS: m/z (%) = 473 [M + 2]+ (6), 471 (M+, 6), 272 (13), 197 (57), 182 (68), 171 (39), 91 (100). Anal. Calcd for C22H19BrN2O3S (471.37): C, 56.06; H, 4.06; N, 5.94; Br, 16.95; S, 6.80. Found: C, 56.34; H, 4.37; N, 6.11; Br, 17.21; S, 6.97. N-(N-Tosylpentanimidoyl)benzamide (4j) Colorless solid; yield: 0.25 g (70%); mp 132–134 °C. IR (KBr): 3261, 1657, 1561, 1437, 1352, 1109 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 0.79 (t, 3 J = 7.1 Hz, 3 H, CH3), 1.45–1.67 (m, 4 H, 2 CH2), 2.29 (s, 3 H, CH3), 2.68 (t, 3 J = 6.3 Hz, 2 H, CH2), 7.29 (d, 3 J = 6.7 Hz, 2 H, 2 CH), 7.43 (d, 3 J = 6.7 Hz, 2 H, 2 CH), 7.56–7.62 (m, 3 H, 3 CH), 8.05 (d, 3 J = 6.9 Hz, 2 H, 2 CH), 10.67 (s, 1 H, NH). 13C NMR (125.7 MHz, CDCl3): δ = 5.9 (CH3), 20.5 (CH2), 24.5 (CH2), 24.8 (CH3), 27.2 (CH2), 126.4 (2 CH), 127.1 (2 CH), 129.5 (2 CH), 131.4 (2 CH), 133.8 (CH), 135.8 (C), 141.1 (C), 143.6 (C), 160.3 (C), 168.3 (C). MS: m/z (%) = 358 (M+, 1), 238 (16), 171 (39), 155 (68), 105 (100), 77 (79). Anal. Calcd for C19H22N2O3S (358.46): C, 63.66; H, 6.19; N, 7.82; S, 8.94. Found: C, 63.85; H, 6.34; N, 7.98; S, 9.17. N-(N-Tosylhexanimidoyl)benzamide (4k) Colorless solid; yield: 0.26 g (71%); mp 138–140 °C. IR (KBr): 3273, 1663, 1543, 1458, 1337, 1129 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 0.83 (t, 3 J = 6.9 Hz, 3 H, CH3), 1.37–1.65 (m, 6 H, 3 CH2), 2.32 (s, 3 H, CH3), 2.61 (t, 3 J = 7.6 Hz, 2 H, CH2), 7.27 (d, 3 J = 6.9 Hz, 2 H, 2 CH), 7.49 (d, 3 J = 6.9 Hz, 2 H, 2 CH), 7.60–7.65 (m, 3 H, 3 CH), 8.02 (d, 3 J = 6.5 Hz, 2 H, 2 CH), 10.62 (s, 1 H, NH). 13C NMR (125.7 MHz, CDCl3): δ = 13.2 (CH3), 22.1 (CH2), 22.8 (CH2), 24.0 (CH2), 24.7 (CH3), 33.5 (CH2), 126.2 (2 CH), 128.0 (2 CH), 129.3 (2 CH), 131.1 (2 CH), 133.0 (CH), 134.1 (C), 141.2 (C), 143.6 (C), 159.5 (C), 168.2 (C). MS: m/z (%) = 372 (M+, 1), 252 (16), 172 (59), 120 (68), 105 (100), 77 (60). Anal. Calcd for C20H24N2O3S (372.48): C, 64.49; H, 6.49; N, 7.52; S, 8.61. Found: C, 64.63; H, 6.49; N, 7.76; S, 8.81. N-[N-Tosyl-2-(trimethylsilyl)ethanimidoyl]benzamide (4l) Colorless solid; yield: 0.25 g (65%); mp 121–123 °C. IR (KBr): 3258, 1654, 1561, 1448, 1337, 1106 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 0.08 (s, 9 H, 3 Me), 1.83 (m, 2 H, CH2), 2.36 (s, 3 H, CH3), 7.26 (d, 3 J = 7.2 Hz, 2 H, 2 CH), 7.45 (t, 3 J = 6.5 Hz, 2 H, 2 CH), 7.58–7.63 (m, 3 H, 3 CH), 8.03 (d, 3 J = 7.0 Hz, 2 H, 2 CH), 10.69 (s, 1 H, NH). 13C NMR (125.7 MHz, CDCl3): δ = 0.62 (3 Me), 23.9 (CH3), 29.2 (CH2), 126.1 (2 CH), 127.4 (2 CH), 128.5 (2 CH), 129.8 (2 CH), 130.1 (CH), 134.5 (C), 140.1 (C), 142.7 (C), 157.3 (C), 168.1 (C). MS: m/z (%) = 388 (M+, 1), 268 (12), 171 (38), 120 (58), 105 (100), 77 (60). Anal. Calcd for C19H24N2O3SSi (388.56): C, 58.73; H, 6.23; N, 7.21; Si, 7.23; S, 8.25. Found: C, 58.95; H, 6.51; N, 7.32; Si, 7.26; S, 8.34.