14522-82-8Relevant articles and documents
Oxidation of alkylarenes by nitrate catalyzed by polyoxophosphomolybdates: Synthetic applications and mechanistic insights
Khenkin, Alexander M.,Neumann, Ronny
, p. 6356 - 6362 (2007/10/03)
Alkylarenes were catalytically and selectively oxidized to the corresponding benzylic acetates and carbonyl products by nitrate salts in acetic acid in the presence of Keggin type molybdenum-based heteropolyacids, H3+xPVxMo12-xO40 (x = 0-2). H 5PV2Mo10O40 was especially effective. For methylarenes there was no over-oxidation to the carboxylic acid contrary to what was observed for nitric acid as oxidant. The conversion to the aldehyde/ketone could be increased by the addition of water to the reaction mixture. As evidenced by IR and 15N NMR spectroscopy, initially the nitrate salt reacted with H5PV2Mo10O 40 to yield a NVO2+[H 4PV2Mo10O40] intermediate. In an electron-transfer reaction, the proposed NVO2 +[H4PV2Mo10O40] complex reacts with the alkylarene substrate to yield a radical-cation-based donor-acceptor intermediate, NIVO2[H4PV 2Mo10O40]-ArCH2R+.. Concurrent proton transfer yields an alkylarene radical, ArCHR., and NO2. Alternatively, it is possible that the NVO 2+[H4PV2Mo10O 40] complex abstracts a hydrogen atom from alkylarene substrate to directly yield ArCHR. and NO2. The electron transfer-proton transfer and hydrogen abstraction scenarios are supported by the correlation of the reaction rate with the ionization potential and the bond dissociation energy at the benzylic positions of the alkylarene, respectively, the high kinetic isotope effect determined for substrates deuterated at the benzylic position, and the reaction order in the catalyst. Product selectivity in the oxidation of phenylcyclopropane tends to support the electron transfer-proton transfer pathway. The ArCHR. and NO2 radical species undergo heterocoupling to yield a benzylic nitrite, which undergoes hydrolysis or acetolysis and subsequent reactions to yield benzylic acetates and corresponding aldehydes or ketones as final products.
Protonitronium dication (NO2H2+)1
Olah, George A.,Rasul, Golam,Aniszfeld, Robert,Surya Prakash
, p. 5608 - 5609 (2007/10/02)
Protonitronium dication (1, NO2M2+), the assumed superelectrophile responsible for the nitration of deactivated aromatics as well as alkanes with nitronium salts in superacidic media, was found to be a minimum at both HF/6-31G* and MP2/6-31G** levels of ab initio calculations. IGLO *15N NMR chemical shift as well as infrared frequencies were also calculated for 1. Attempts to experimentally observe 1 under superacidic conditions by 15N NMR and FT-IR (Raman) spectroscopy were so far unsuccessful, due to the expected low equilibrium concentration of 1 in the studied systems.
15N NMR spectroscopic investigation of nitrous and nitric acids in sulfuric acid solutions of varying acidities
Prakash, G. K. Surya,Heiliger, Ludger,Olah, George A.
, p. 4965 - 4968 (2008/10/08)
Both nitrous and nitric acids were studied in sulfuric acid solutions of varying acid strengths by 15N NMR spectroscopy. The study gives new insights into the nature of intermediates present at different acid strengths. Furthermore, we have also discovered a novel redox reaction between NO2+ and NO+ ions involving the intermediacy of their respective acids. A mechanism is proposed to explain the observed results.
