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E versus Z Diazeniumdiolation of Acetoacetate-Derived Carbanions

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journal contribution
posted on 07.09.2012, 00:00 by Navamoney Arulsamy, D. Scott Bohle, Carla L. Holman, Inna Perepichka
Nitric oxide adds to methyl acetoacetate in the presence of KOH in methanol at room temperature to form potassium acetylsydnonate N-oxide (K1) with an (E)-diazeniumdiolation and potassium acetate diazenium diolate (K22) from a (Z)-diazeniumdiolation. A study of the reaction with LiOH, NaOH, and NMe4OH and with ethyl acetate substrate reveals that the temperature of the reaction greatly influences the nitric oxide reactivity. At 23 °C, nitric oxide adds to give both E and Z products, whereas at −5 °C the gas reacts almost exclusively to give Z addition. The (Z)-diazeniumdiolation products, namely, the alkali metal and NMe4+ salts of methyl and ethylbutenoate-2-diazeniumdiolate-3-hydroxylate (32– and 42), are isolated in good yields. The alkali metal salts are not amenable for recrystallization because of their ready decomposition in aqueous solutions. However, [NMe4]2[MeC­(O)­C­(N2O2)­CO2Me] is readily recrystallized from a methanol/acetonitrile solvent mixture. The crystals are unambiguously characterized by X-ray crystallography. NMR spectra for all of the 32– and 42– salts reveal the presence of two isomers in aq solutions. But the structure of the NMe4+ salt contains only one of the isomers. Our attempts to cyclize the isolated and purified butenoatediazeniumdiolates from the (Z)-diazeniumdiolation to the E-containing sydnonate products were unsuccessful. TGA/DSC data for all of the products demonstrate the thermal instability of the salts at high temperatures. The salts decompose exothermally possibly with the release of N2O among other gases.