Oxidants Jones

Following oral administration of 50 mg/kg bw 2,3-dibromopropan-l-ol to male Sprague-Dawley rats, two urinary mercapturic acid metabolites were identified as N-acetyl-5 -(2,3-dihydroxypropyl)cysteine and A, W-bis-acetyl-N<5"-(l,3-bis-cysteinyl)-propan-2-ol, respectively. It was inferred that 3-bromo-l,2-propane epoxide is an intermediate in the metabolism of 2,3-dibromopropan-l-ol. In addition, (3-bromolactate was produced, presumably as a result of hydrolysis to the a-bromohydrin and subsequent oxidation (Jones Fakhouri, 1979). Marsden and Casida (1982) identified small amounts of 2-bromoacrylic acid in the urine of rats injected intraperitoneally with 2,3-dibromopropan-l-ol and suggested that this arose by oxidation and dehydrobromi-nation, with 2-bromoacrolein as an unstable intermediate. 

Although nitric oxide has an unpaired electron, it is difficult to detect directly by electron paramagnetic resonance. In addition to the low concenttation of nitric oxide in vivo, the angular momentum of the unpaired electron can couple with the angular momentum of the nitric oxide molecule to obscure the paramagnetic properties of nitric oxide (Jones, 1973). However, nitric oxide can be detected as a complex with heme groups, which has been used to show the... 

All of the usual chromium-based oxidation reagents that have been used for the oxidation of cyclobutanols to cyclobutanones, for example, chromium(VI) oxide (Jones reagent),302 pyri-dinium chlorochromate,304 pyridinium dichromate,307 and chromium(YI) oxide/pyridine (Collins),303 are reported to do so without any serious problems. Alternatively, tetrapropylam-monium perruthenate in the presence of A-methylmorpholine A -oxide. oxalyl chloride in the presence of triethylamine in dimethyl sulfoxide (Swern),158,309,310 or phenyl dichlorophos-phate in the presence of triethylamine and dimethyl sulfoxide in dichloromethane (Pfitzner-Moffatt),308 can be used. The Pfitzner-Moffatt oxidation procedure is found to be more convenient than the Swern oxidation procedure, especially with respect to the strict temperature control that is necessary to achieve good yields in the latter, e.g. oxidation of 1 to give 2.308... 

Related reactions Dess-Martin oxidation, Jones oxidation, Ley oxidation, Oppenauer oxidation, PTitzner-Moffatt oxidation, Swern oxidation ... 

The Collins oxidation, Jones oxidation, and Corey s PCC (pyridinium chlorochromate) and PDC (pyridinium dichromate) oxidations follow a similar pathway. 

In an attempt to prepare carhna oxide from an a-endiynic alcohol, by a similar reaction, it was found that the trans form of the alcohol (LIV) did not cychze, but that the cis form yielded the compound (LV) isomeric with carhna oxide (Jones, i960). 

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