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DOI: 10.1055/s-0030-1260323
Efficient Preparation of ortho-Aminobenzenesulfonamides using Ligand-Free Copper(I)-Catalyzed Amination
Publikationsverlauf
Publikationsdatum:
22. September 2011 (online)
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Abstract
A general and efficient method of copper-catalyzed amination of 2-iodobenzenesulfonamide has been developed under very mild conditions, with good to excellent yields. This method uses inexpensive copper(I) iodide as catalyst, readily available 2-iodobenzenesulfonamides and aliphatic amines as the starting materials, and does not require the use of any ligand system or any expensive supplementary additives.
Key words
2-iodobenzenesulfonamide - copper(I) catalyst - N-arylation - ligand-free - 2-aminobenzenesulfonamides
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References and Notes
Typical Experimental Procedure for the Synthesis of N -Benzyl-2-(propargylamino)benzenesulfonamide (2c): 2-Iodobenzenesulfonamide (300 mg, 1 mmol), K2CO3 (138 mg, 1 mmol) and anhyd DMF (10 mL) were introduced into a dry Schlenk flask under argon. The mixture was cooled to 0 ˚C and degassed under agitation (10 min). Then amine (1.1 mmol) and CuI (19 mg, 0.1 mmol) were introduced successively under argon flux. The mixture was brought to r.t. and left under stirring for 12 h. The reaction mixture was diluted with Et2O, washed with aq NH4Cl and H2O, dried over MgSO4, filtered and concentrated under vacuum. The residue was purified by chromatography on silica gel (petroleum ether-Et2O, 50:50) or by crystallization (petroleum ether-CH2Cl2, 80:20); yield: 79%; white solid; mp 64-66 ˚C. IR (KBr): 1599, 2114, 2963, 3252, 3389 cm-¹. ¹H NMR (200 MHz, CDCl3): δ = 7.79 (dd, J = 7.9, 1.3 Hz, 1 H), 7.47 (td, J = 7.9, 1.3 Hz, 1 H), 7.13-7.26 (m, 5 H), 6.79-6.91 (m, 2 H), 6.06 (t, J = 5.4 Hz, 1 H), 5.25 (t, J = 6.2 Hz, 1 H), 3.94-4.06 (m, 4 H), 2.24 (t, J = 2.4 Hz, 1 H). ¹³C NMR (50 MHz, CDCl3): δ = 144.2, 139.4, 135.7, 134.0, 129.8, 128.2 (2 × C), 127.4 (2 × C), 121.4, 116.9, 112.6, 79.5, 71.4, 46.8, 32.4. MS (EI): m/z = 300 [M] (8), 130 (51), 129 (59), 108, 106 (100), 102 (22), 91 (63). Anal. Calcd for C16H16N2O2S: C, 63.98; H, 5.37; N, 9.33. Found: C, 63.83; H, 5.41; N, 9.35.