Institute of Organic Chemistry, University of Lausanne, BCH, CH-1015
Lausanne-Dorigny, Switzerland.
Fax: ++ 41 21 692 3955 ([email protected])
Received: 20 June 1997 / Published: 4 July 1997
Scheme
The amide 2 [1] was prepared by hydrolysis of the nitrile 1 according to the reported procedure [2].
To a cooled (0[infinity]C) solution of 1 (0.68 g, 2.76 mmol) in CH2Cl2 (2 ml) was added successively hydrogen peroxide (30%, 1.29 ml), tetra-(n-butyl)ammonium hydrogen sulfate (187 mg) and an aqueous solution of sodium hydroxide (20%, 1.03 ml). The reaction mixture was allowed to warm to room temperature. Methylenechloride (30 ml) was added after 1 h. The organic layer was separated, washed with brine, dried (Na2SO4) and concentrated in vacuo. The residue (0.25 g) was flash chromatographed (AcOEt/Hexane = 3:1) to afford 370 mg (70%) of 2.
Rf (AcOEt): 0.34.
M. p. 130-131.5 deg.C.
IR (KBr): 3400vs, 3180s, 1668s, 1630vs, 1598s, 1415s, 963s, 912m, 820m.
1H-NMR (CDCl3): 6.38 (br, 1H, NH); 5.89 (dd, J = 3.0, 0.5, 1H, H-5); 5.69 (br, 1H, NH); 5.05 (dd, J = 1.3, 1.0, 1H, H-2), 4.28 (ddd, J = 5.0, 1.3, 0.5, 1H, H-3); 3.98 and 3.71 (2x dq, J = 9.7, 7.0, OCH2Me), 2.89 (qddd, J = 7.0, 5.0, 3.0, 1.0, 1H, H-4); 1.31 (t, J = 7.0, 3H, OCH2CH3); 1.27 (d, J = 7.0, 3H, Me).
13C-NMR (CDCl3): 164.0 (CONH2), 141.7 (C-6), 110.7 (C-5), 99.5 (C-2), 65.5 (OCH2Me), 52.1 (C-3), 32.2 (C-4), 17.8 (Me), 14.9 (OCH2CH3).
CI-MS: 283/281 (M+NH4+, 69/76), 267/265 (M+2, 12/13), 266/264 (M+H+, 100/100), 184 (M-Br, 68), 152/150 (24/23), 138 (100), 124 (12), 122 (9), 111 (189, 99 (19), 88 (26), 83 (15), 77 (27).
Acknowledgment: We thank the Swiss National Foundation for financial support.
References
1. Zhuo, J.-C.; Wyler, H. Helv. Chim. Acta 1995, 78, 151.
2. Cacchi, S.; Misiti, D.; La Torre, F. Synthesis 1980, 243.
Sample Availability: Available from MDPI, 0.1g, MDPI 12540.
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