2396-02-3Relevant articles and documents
Magnetic Field Effects on the Photodissociation Reaction of Triarylphosphine in Nonviscous Homogeneous Solutions
Sakaguchi, Yoshio,Hayashi, Hisaharu
, p. 3421 - 3429 (2007/10/03)
The magnetic field effects (MFEs) on the photodecomposition reactions of triphenylphosphine and its halogen and methyl derivatives are investigated in fluid solutions. The yield of diarylphosphinyl radicals decreased with increasing magnetic field from 0.1 to 5 T but was stationary below 0.1 T and above 5 T. The MFE becomes larger by the substitution of halogen atoms and the 3- or 4-methyl group. In cyclohexane, the yields of the escaped diarylphosphinyl radicals at 1 T are reduced to 0.69, 0.55, 0.59, and 0.56 of those at 0 T for triphenylphosphine and its tris(4-chloro), tris(3-methyl), and tris(4-methyl) derivatives, respectively. This magnetic field dependence was ascribed to originate from the deactivation process of the excited triplet state, which is a variant of the d-type triplet mechanism originally proposed by Steiner. The interaction between the closely lying nπ* and ππ* states makes their solvent dependence complicated.
p-benzyne
Marquardt, Ralph,Balster, Andreas,Sander, Wolfram,Kraka, Elfi,Cremer, Dieter,Radziszewski, J. George
, p. 955 - 958 (2007/10/03)
A noble gas matrix at low temperature was used to investigate the photochemical behavior of diacetyl terephthaloyl diperoxide and dipropionyl terephthaloyl diperoxide as well as 1,4-diiodobenzene. All three photoreactions formed small quantities of a compound with IR absorption bands at 725 and 980 cm-1, which disappeared when the matrix was annealed. These bands correspond to the most intense of the calculated bands (B3LYP) for 1,4-didehydrobenzene (p-benzyne) (1). That decomposition of the peroxides in fact leads to 1 is confirmed by vapor-phase pyrolysis experiments in which (Z)-2 was obtained in high yield.
Homogenous Gas-Phase Formation and Destruction of Anthranil from o-Nitrotoluene Decomposition
He, Y. Z.,Cui, J. P.,Mallard, W. G.,Tsang, W.
, p. 3754 - 3759 (2007/10/02)
Dilute quantities of o-nitrotoluene and anthranil have been pyrolyzed in comparative rate single pulse shock tube experiments.Rather than C-NO2 bond cleavage and NO2 isomerization found as major channels in p-nitrotoluene decomposition, we demonstrate that the important pathway for pyrolysis involves the formation of anthranil with the following overall rate expression: k(o-nitrotoluene -> anthranil) = 1.2 x 1013 exp(-26020/T)/s.The anthranil that is formed is very unstable under our conditions; the rate expression for disappearence has been found to be the following: k(anthranil)d = 3.7 x 1015 exp(-25800/T)/s.Arguments are presented that suggest that the first rate expression is representative of a retroene reaction and the second expression is for the breaking of the N-O bond in anthranil.These conclusions emphasize the difference in results from shock tube and laser pyrolysis experiments.Their implications on the initiation reactions in the decomposition of nitroaromatic explosives are discussed.