2932-82-3Relevant articles and documents
FTIR and computational studies of gas-phase hydrogen atom abstraction kinetics by t-butoxy radical
Li, Shuping,Fan, Wai Yip
, p. 276 - 280 (2007/10/03)
By using Fourier-Transform Infrared (FTIR) absorption spectroscopy, rate coefficients in the range of 10-16 to 10-14 cm3 molecule-1 s-1 have been determined for the hydrogen atom abstraction reactions of several substrates including halogenated organic compounds and amines by t-butoxy radical generated from the uv photolysis of t-butyl nitrite in the gas phase. Arrhenius parameters for selected reactions have been measured in the temperature range 299-318 K. Transition states and activation barriers for such reactions have been computed with the help of Gaussian 03 software and found to match very well with the experimental values.
Rate Constants for Halogen Atom Transfer from Representative α-Halocarbonyl Compounds to Primary Alkyl Radicals
Curran, Dennis P.,Bosch, Eric,Kaplan, Jere,Newcomb, Martin
, p. 1826 - 1831 (2007/10/02)
Rate constants for halogen atom transfer from diethyl methyliodomalonate (7a), iodoacetonitrile (7b), ethyl 2-methyl-2-iodopropanoate (7c), ethyl iodoacetate (7d), diethyl methylbromomalonate (7e), and ethyl bromoacetate (7f) to simple primary alkyl radicals have been studied by a variety of competition reactions.The Arrhenius functions for halogen atom transfer to the undecyl radical from halides 7d and 7f are log (kI, M-1 s-1) = 10.4 - 4.4/θ and log (kBr, M-1 s-1) = 10.4 - 8.2/θ, respectively.The rate constants for halogen atom transfer to a primaryradical from the series of compounds 7a-7f at 50 deg C are 1.8 x 109, 1.7 x 109, ca. 6 x 108, 2.6 x 107, 1.0 x 106, and 7.0 x 104 M-1 s-1, respectively.The kinetic values are useful for the planning of synthetic methods that incorporate an atom transfer-cyclization process.
Spin Trapping of Radicals Formed during the Decomposition of Aromatic Diazonium Salts by Ultrasound
Rehorek, Detlef,Janzen, Edward G.
, p. 935 - 940 (2007/10/02)
The decomposition of aromatic diazonium compounds ArN2(+)X(-) (Ar = phenyl, 2,5-diethoxy-4-(N-morpholino)phenyl; X =BF4, PF6, B(C6H5)4, SCN, OCN, N3; 1a, 1c-f, 2b-f) by ultrasonic waves has been studied by e.s.r..The spin trapping technique has been shown to be a suitable method for the detection of free radical intermediates.