SYNTHESIS OF N'-SUBSTITUTED AMIDINES THROUGH THE CLEAVAGE AN OXADIAZOLONE HETEROCYCLE BY EAKLY BASIC NUCLEOPHILES. EFFECT OF THE NATURE OF THE NUCLEOPHILE AND THE OF NUCLEOPHILE/SUBSTRATE MOLAR RATIO

Abstract

The reaction of 1-ethoxycarbonylmethyl-5,5,7,7-tetramethyl-2-oxo-tetrahydroimidazo[1,5-b]oxadiazol-6-oxyl with the weakly basic nucleophiles NaN3, NaCN, KF, KBr, KCl and NaNO2 has been studied. It was shown for the first time that, as in the case of NaOH and MeONa, the reaction occurs with opening of the oxadiazolone ring to form exo-N-substituted  amidines. It was shown that the weakly basic nucleophiles readily react with substrates which contain a substituent sensitive to attack by such nucleophiles as NaOH or MeONa. The effect of the nature of the nucleophiles on the reaction course for opening of the oxadiazolone ring was also studied. It was found that the reactivity of the nucleophiles in DMSO changes in the series F– > CN– > N3–> NO2–> Cl–>Br- and qualitatively correlates with their basicities in this solvent. Examination of the effect of the ratio of the reagents  on the degree of conversion of the starting oxadiazolone has shown that a quantity of nucleophiles less than one equivalent also allowed the cleavage reaction of the oxadiazolone heterocycle to go to completion through just increasing the reaction time. The experimental data obtained lends support to the proposed reaction scheme.

How to Cite
Polienko, Yu. F.; Grigor'yev, I. A.; Voinov, M. A.  Chem. Heterocycl. Compd. 2009, 45, 59. [Khim. Geterotsikl. Soedin. 2009, 71.]

For this article in the English edition see DOI 10.1007/s10593-009-0226-6