45702-21-4Relevant academic research and scientific papers
Selective N-oxidation of aromatic amines to nitroso derivatives using a molybdenum acetylide oxo-peroxo complex as catalyst
Biradar, Ankush V.,Kotbagi, Trupti V.,Dongare, Mohan K.,Umbarkar, Shubhangi B.
, p. 3616 - 3619 (2008)
The molybdenum acetylide oxo-peroxo complex obtained in situ by the treatment of the corresponding molybdenum acetylide carbonyl complex, CpMo(CO)3(C{triple bond, long}CPh); Cp = η5-C5H5 with H2O2, has been used as an efficient catalyst for selective N-oxidation of primary amines to nitroso derivatives. Excellent amine conversion (up to 100%) and very high selectivity for nitroso compounds (99%) have been obtained using 30% hydrogen peroxide as an oxidant. The oxo peroxo Mo(VI) complex has also been found to be very active for the oxidation of various substituted primary aromatic amines with electron donating as well as electron withdrawing substituents on the aromatic ring.
Kinetics and Thermochemistry of the Reversible Combination Reactions of the Allyl and Benzyl Radicals with NO
Boyd, A.A.,Noziere, B.,Lesclaux, R.
, p. 10815 - 10823 (2007/10/02)
The equilibrium kinetics of the reversible additions of NO to the benzyl (C6H5CH2) and allyl (CH2CHCH2) radicals have been studied at atmospheric pressure and over the temperature range 400 1/k-1 and k3/k-3) for the forward and reverse processes: C6H5CH2 + NO + N2 C6H5CH2NO + N2 (reactions 1, -1) and CH2CHCH2 + NO +N2 CH2CHCH2NO + N2 (reactions 3, -3).Thermodynamic treatment of the data by both second law and third law methods of analysis yielded values for the enthalpy and entropy of reaction 1 and 3 which were self consistent and hence the following average values: reaction 1, ΔH0298 = -123 +/- 5 kJ mol-1 (thus ΔH00 = -117 +/- 6 kJ mol-1 and ΔH0f298(C6H5CH2-NO) = 176 +/- 7 kJ mol-1, ΔS0298 = -159 +/- 9 J K-1 mol-1); reaction 3, ΔH0298 = -110 +/- 5 kJ mol-1 (thus ΔH00 = -105 +/- 4 kJ mol-1 and ΔH0f298(CH2CHCH2NO) = 148 +/- 8 kJ mol-1 ΔS0298 = -154 +/- 9 kJ mol-1).The bond dissociation energies for these adducts (= -ΔH0298) are compared and discussed in relation to those for other alkyl nitrosos.Also as part of the study, some measurements of the rate coefficients for the benzyl and ally association reactions with NO (reactions 1 and 3) and their radical self-recombinations (reaction 4, C6H5CH2 + C6H5CH2, and reaction 5, CH2CHCH2 + CH2CHCH2) were made under similar experimental conditions, yielding (in units 1E-11 cm3 molecule-1 s-1): k1(415, 443, 466 K) = 0.91 +/- 0.08, 0.81 +/- 0.05, and 0.62 +/- 0.09, k3(403 K) = 0.71 +/- 0.04, k4(435-519 K) = 2.9 +/- 0.3, k5(403-540 K) = 2.6 +/- 0.2.
