6705-51-7Relevant articles and documents
Reaction of NO3 radicals with 1,3-cyciohexadiene, α-terpinene and α-phellandrene: Kinetics and products
Berndt,Boege,Kind,Rolle
, p. 462 - 469 (2007/10/03)
The gas-phase reaction of NO3 radicals with 1,3-cyclohexadiene, α-terpinene, and α-phellandrene has been studied in a flow system at 298 K in the pressure range 82 rate constants for the primary attack of NO3 were determined with the relative rate method to be (1.08 ± 0.02) 10-11, (1.03±0.06) 10-10, and (5.98±0.20) 10-11, respectively (unit: cm3 molecule-1 s-1). As buffer gas in the product studies served N2 or He as well as O2/N2 mixtures. In the case of 1,3-cyclohexadiene the formation of the corresponding oxirane (7-oxa-bicyclo[4.1.0]hept-2-ene) up to a yield of 90% at P2 and decreased with increasing total pressure. In the case of α-terpinene and α-phellandrene no indication of oxirane formation was found. However, the corresponding aromatic compound (p-cymene) was detected for both terpenes, maximum yield 6% for α-terpinene and 22% for α-phellandrene. For all reaction systems investigated the formation of organic nitrate-compounds was proved by means of long-path FT-IR measurements. In the case of the 1,3-cyclohexadiene degradation with [O2]>5·1015 molecule crn-3 an absorption band was detected in addition assigned to a carbonylic group. There were no indications for a reaction of O2 with the adduct radical (NO3/diene). VCH Verlagsgesellschaft mbH, 1996.
Vapour-phase Chemistry of Arenes. Part 10. Formation of Phenols in Air Oxidation of Benzene, Chlorobenzene, m-Dichlorobenzene, and Benzonitrile in the Presence of Cyclohexa-1,3-diene at ca. 600 K
Mulder, Peter,Louw, Robert
, p. 1135 - 1142 (2007/10/02)
In a flow reactor at 573-623 K, flow time ca. 2 min, vapours of benzene and derivatives, e.g. chlorobenzene and benzonitrile, are not measurably oxidized by air.In the presence of small amounts of cyclohexa-1,3-diene (1), however, substantial conversion of (1) is accompanied by formation of phenols from arenes.The main oxidation product of (1) is benzene, but some phenol, and cyclohex-3-enone (2) is also formed.Conversion of (1) is largely due to hydrogen abstraction by O2, log(A2/l mol-1 s-1)=8.9, E2 ca. 104 kJ mol-1.The resulting cyclohexadienyl radicalgives benzene by disproportionation with O2.Formation of phenol is explained by addition of O2 to cyclohexadienyl radical, followed by rearrangement and reaction with O2.Addition of HO2 to (1) is shown to be the likely first step in forming non-aromatic oxygenated products such as (2).This slow combustion of (1) leads to OH radicals which must be responsible for conversion of arene.Product data, especially isomeric composition of substituted phenols, as well as thermochemical-kinetic analysis indicate that, at ca. 600 K, a mechanistic transition occurs, from addition of OH (prevailing at lower temperatures) to hydrogen abstraction to give aryl radicals, which lead to phenol via ArO2 and ArO.
