Six substituted N-(2-hydroxyphenyl)-2- [(4-methylbenzensulfonyl)amino]acetamides 7-12 have been synthesized from 2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 2-amino-4-chlorophenol, 2-amino-4-tert-butylphenol, 2-amino-4-chloro-5-nitrophenol, and the [(4-methylbenzenesulfonyl) experiments on compounds 7-12 gave evidence for the formation of intra-and intermolecular hydrogen-bonds in solution. The molecular structure of 7 and 12 was determined by X-ray crystallography. The electronic behavior of the intramolecular hydrogen-bonds in these compounds was established by NBO studies.