Vibrational emission of NO2 from the reaction of NO with O3

Vibrational chemiluminescence in the Δν₁ = Δν₃ = ?1 band of NO₂ is observed both in the O + NO and O₃ + NO reactions and shown to be emitted by molecules with up to 11 000 cm^?1 of vibrational energy. Quenching rate constants of NO₂³ are estimated ranging from about 6 × 10^?14 for Ar to about 3 × 10^?12 cm³ s^?1 for NO₂. The ratio of vibrational to electronic emission is 0.06 ± 0.03 for O + NO and 5.3 ± 1.0 for O₃ + NO. It is suggested that vibrationally excited NO₂ is a major product of that channel of the O₃ + NO reaction which forms ground-state NO₂(²A₁) directly.     

Reactions of methyltris(triarylphosphine)cobalt : I. Formation of biaryls

Methyltris(triarylphosphine)cobalt (Ar₃P)₃CoCH₃, decomposes in solutions of THF, benzene or chlorobenzene to yield biaryls. Coupling to biaryls occurs at the ring carbon originally bonded to phosphorus. Mixed biaryls are obtained from crossover reactions of complexes bearing different triarylphosphine ligands and reactions of complexes with free triarylphosphines.     

Syntheses and degradations of fluorinated heterocyclics III. Perfluoroalkyl and perfluoroalkylether-1,3,4-oxadiazoles

2,5-Bis(perfluoro-n-heptyl)-, 2-perfluoroalkylether-5-perfluoro-n-heptyl-, and 2,5-bisperfluoroalkylether-1,3,4-oxadiazoles were synthesized and characterized. 2,5-Bis(perfluoro-n-heptyl)-1,3,4-oxadiazole was thermally and hydrolytically stable at 325°C; however, in the presence of air, degradation took place at 235°C. The perfluoroalkylether analogue exhibited thermal and hydrolytic stability at 325°C; it was found to be unaffected by Jet-A fuel and air at 235°C. At 325°C in air some degradation occured as evidenced by volatiles production, oxygen consumption, and 96% starting material recovery.     

Quantum chemical calculations on thioridazine

Quantum chemical CNDO /2 calculations for the conformational preference of the side chain of thioridazine as a function of angle indicated the crystallographically determined structure gave the lowest energy. There is also a small region of conformational flexibility within the first 90° of rotation of the side chain. This is commensurate with the results which we had obtained previously for our similar calculations for promazine and its Cl and CF₃ derivatives, perazine and its Cl and CF₃ derivatives, and for the hypothetical hitherto unknown N-piperidinopromazine and its Cl and CF₃ derivatives. The conformational profile of thioridazine resembles that of the perazines. The calculated gross atomic populations on the alkyl nitrogen in thioridazine was within the range we had previously found necessary for neuroleptic activity.