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Acid-catalyzed aci-nitro tautomerism epimerization of α, ω-bis-hydroxymethyl-α, ω-dinitroalkanes

✍ Scribed by H. Feuer; A.T. Nielsen


Publisher
Elsevier Science
Year
1963
Tongue
French
Weight
712 KB
Volume
19
Category
Article
ISSN
0040-4020

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✦ Synopsis


The low-melting isomers of 2,5-dinitro-1,6•hexanedlOl (IB) and 2,6-dinitro-l,7heptanediol (lIB) undergo facile acid-catalyzed epimerization to form the respective highmelting isomers (IA and IIA) in water or in aprotic solvents. The dimethyl ether and bisphenylurethan derivatives of IB are not epimerized by acid catalysts under the same conditions. The rate of the isomerization, IB -t lA, has been determined in N hydrochloric acid at 60°and compared with rates of other acid-catalyzed reactions occurring in this medium. The rates of tautomerization to the nitro form, of the mono and bis-nitronic acids derived from I, have been measured and found to be very rapid relative to the isomerization reaction. Mechanisms for the epimerization and related acid-catalyzed reactions of nitroalkanes are presented and discussed.