Chlorine Dioxide Oxidation of Cyclohexene.

Chlorine dioxide resistance of different phenolic antioxidants in polyethylene

“…The presence of grafted chlorine onto polymer chains was only revealed by Colins et al [18]. This polymer contained some unsaturation, which in view of the early findings of Lindgren et al [16,17] suggest some reactivity between the polymer and chlorine dioxide. When the antioxidant system has become totally depleted, a fast but strictly surface-confined degradation of polyethylene occurs [10].…”

“…Saturated aliphatic hydrocarbons and aliphatic olefins were reported to be unreactive to chlorine dioxide under typical water conditions [14,15]. Lindgren et al [16,17] reported the presence of oxidative and chlorinated products from the reactions of chlorine dioxide and some olefins, which they suggested to be due to a mechanism whereby the allylic hydrogen is abstracted by chlorine dioxide giving free radical intermediates. The high stability of saturated hydrocarbons towards chlorine dioxide was further supported by data presented by Yu et al [8] on polyethylene pipes exposed to water containing 4.0 ppm chlorine dioxide at 90 C and pH ¼ 6.8: the material beneath the degradation layer showed no detectable IR absorption due to carbonyl, hydroxyl or chlorine groups.…”

Asymmetric sulfoxidation of phenacyl phenyl sulfide using chiral vanadium(IV) complexes

“…The latter is one of the most interesting and accessible oxidants available on a large scale. There are published data [11][12][13][14][15][16][17][18] on the oxidation with chlorine dioxide of amines, phenols, olefins, and carbonyl compounds, while asymmetric oxidation with ClO 2 has not been reported. We previously showed that chlorine dioxide ensures chemoselective oxidation of sulfides to sulfoxides [11,19,20].…”

Chlorine Dioxide as an Electron‐Transfer Oxidant of Olefins. Preliminary Communication

“…In spite of its growing environmental importance, there are only a few studies on the nature of the reaction in H,O between C10, and organic functionalities. Whereas C10, functions as an electron oxidant towards tertiary amines [4] and phenols [5], the reaction with olefins was hitherto viewed to involve free-radical attacks both on the allylic sp3-C-atoms and the olefinic sp2-Catoms [6]. This brings up the interesting question as to whether the reaction mechanism of CIO, varies with the substrate demand.…”

“…These rate constants may be correlated with CT+ [16], with a e value The expected order of reactivity of alkenes on the basis of the allylic-radical mechanism [6] should have been PheHCH, (IV) are about 20 kcal more stable than the respective aliphatic cations. In the alkene series, secondary free radicals are calculated to be 6 kcal more stable than primary radicals, whereas an a-phenyl group is evaluated to increase the stability of the free radical by an additional 13 kcal.…”