Premium
Das Problem der Mononitrierung von Durol
Author(s) -
Hanna S. B.,
Hunziker E.,
Saito T.,
Zollinger H.
Publication year - 1969
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19690520615
Subject(s) - chemistry , nitromethane , durene , nitration , yield (engineering) , acetonitrile , solvent , hydrogen isotope , photochemistry , inorganic chemistry , hydrogen , organic chemistry , catalysis , materials science , metallurgy
In contrast to many previous investigations, reaction conditions were found under which the nitration of durene (nitrating ratio of 1:1) gives predominantly, and in high yield, mononitrodurene rather than the usually formed dinitrodurene (plus unreacted durene). The method consists in nitrating by nitronium phosphorohexafluoride in nitromethane as solvent in presence of two equivalents of water. With mixed acid (HNO 3 + H 2 SO 4 ) in nitromethane and in acetonitrile durene forms also monoand no dinitrodurene; but under most conditions by‐products are formed. Some of the by‐products were identified. Some preliminary mechanistic results are reported: An addition complex of unknown structure is formed rapidly; 3, 6‐dideuterodurene + D 2 O do not show a hydrogen isotope effect; the preferential formation of dinitrodurene under conventional conditions is due to the fact that the reaction occurs at encounter‐controlled rate.