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Reactivity of allylic hydrogen in cyclohexadiene towards OH radicals
Author(s) -
Ohta Tomohiro
Publication year - 1984
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550161204
Subject(s) - chemistry , allylic rearrangement , radical , hydrogen atom abstraction , reaction rate constant , yield (engineering) , benzene , branching (polymer chemistry) , photochemistry , reactivity (psychology) , hydrogen , photoionization , branching fraction , medicinal chemistry , organic chemistry , kinetics , catalysis , materials science , quantum mechanics , atomic physics , metallurgy , ionization , medicine , ion , physics , alternative medicine , pathology
The yield of benzene in the reaction of 1,4‐ and 1,3‐cyclohexadiene with OH radicals in the presence of oxygen was determined using H 2 O 2 and CH 3 ONO as OH radical sources. Both in the H 2 O 2 and the CH 3 ONO systems, the yield of benzene from 1,4‐cyclohexadiene was 15.3% and the yield from 1,3‐cyclohexadiene was 8.9%. On the basis of the obtained yields, the rate constant for allylic hydrogen abstraction per CH in cyclohexadiene was determined to be 3.8 × 10 −12 cm 3 molecule −1 s −1 . The branching ratio of the hydrogen abstraction to overall reaction for 1‐butene and 1‐pentene was estimated to be (25–14)% by applying the obtained rate constants. The result was in good agreement with the branching ratio determined directly by use of the discharge flow photoionization mass spectrometer by Biermann, Harris, and Pitts [4].