Correction to Base Controlled Polydiazeniumdiolation of 4-Heptanone and a New Water Layer Structure

Arulsamy, Navamoney; Bohle, D. Scott; Chuang, Chuan‐Hung; Moore, Raecca C.

doi:10.1021/jo901288b

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“…Views of the anions are shown in Figure . Although the compounds are unusual and novel, the structures themselves are comparable to previously reported structures of sydnonate N -oxides and diazeniumdiolates. ,,,, On the other hand, the characterization of K 2 3 relies on more indirect spectroscopic data and elemental analysis data. The IR spectrum measured for K 2 3 exhibits a strong absorption at 1342 cm –1 attributable to the (ONNO) sym vibration .…”

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confidence: 72%

E versus Z Diazeniumdiolation of Acetoacetate-Derived Carbanions

et al. 2012

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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 (K(2)2) from a (Z)-diazeniumdiolation. A study of the reaction with LiOH, NaOH, and NMe(4)OH 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 NMe(4)(+) salts of methyl and ethylbutenoate-2-diazeniumdiolate-3-hydroxylate (3(2-) and 4(2-)), are isolated in good yields. The alkali metal salts are not amenable for recrystallization because of their ready decomposition in aqueous solutions. However, [NMe(4)](2)[MeC(O)C(N(2)O(2))CO(2)Me] is readily recrystallized from a methanol/acetonitrile solvent mixture. The crystals are unambiguously characterized by X-ray crystallography. NMR spectra for all of the 3(2-) and 4(2-) salts reveal the presence of two isomers in aq solutions. But the structure of the NMe(4)(+) 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 N(2)O among other gases.

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