Acidity of Cyclic Sulfamates: Study of Substituted 1,2,3-Benzoxathiazole 2,2-Dioxides and Theoretical Investigation of the Effect of Conformation on Acidity

Kenneth K. Andersen, Martin G. Kociolek

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Sulfamate lb, 5-nitro-3-(4-toluenesulfonyl)-l,2,3-benzoxathiazole 2,2- dioxide, was treated with various nucleophiles: imidazole, benzylamine, tert-butylamine, sodium azide, potassium fluoride, pyridine, and sodium hydroxide. The first five attacked the exocyclic (tosyl) sulfur atom. No reaction was observed with the pyridine. The hydroxide ion attacked the endocyclic sulfur atom leading to opening of the benzoxathiazole ring. Several N-unsubstituted cyclic sulfamates, X-3H-1,2,3-benzoxathiazole 2,2-dioxides (2a, X = 5-H; 2b, X = 5-NO2; 2c, X = 5-Me; 2d, X = 5-Br; 2e, X = 5-C1; 2f, X = 6-NO2; 2g, X = 5,6-Cl,Cl) and the naphtho-fused cyclic sulfamate (2h), were prepared by treatment of the respective N-tosyl compounds (la—h) with sodium azide or potassium fluoride. The pKa values for these compounds were determined by potentiometric titraiion in 60% v/v EtOH/ H2O. AHammett plot using om for 2a-e, σP for 2f, and both σm and ap for 2g gave ao = 2.74. Ab initio calculations were done using sulfamic acid as a simple sulfamate model to test the effect of the geometry changes on pKa, The calculations showed that the sulfamate with the ringlike geometry should be 3.6 pKa units moee acidic than the acyclic sulfamate. This overall change was broken down into three factors affecting the pKa. The N-S bond rotation accounted for a change of 0.22 units, O—S bond rotation for 2.03 units, and ring strain for 1.36 units.

Original languageEnglish (US)
Pages (from-to)2003-2007
Number of pages5
JournalJournal of Organic Chemistry
Issue number7
Publication statusPublished - Jan 1 1995


All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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