Oxidations miscellaneous substrates

Oxidations of Amines, Amides, Ethers, Sulfides, Phosphines, Arsines, Stibines and Miscellaneous Substrates... 

Substrates DME = dropping mercury electrode FTO = fluorine-doped tin oxide G = graphite GC = glassy carbon GrC = graphic carbon ITO = indium tin oxide-coated glass SC = single crystals SS = stainless steel TCO = transparent conducting oxide VC = vitrious carbon. Miscellaneous ECALE = electrochemical atomic layer epitaxy ED = electrodeposition ML = monolayer RT = room temperature SMD = sequential monolayer deposition V = vacuum. 

Abstract This chapter principally concerns oxidations of organic substrates containing N, O, S, P, As and Sb. Oxidations of amines are covered first, including primary amines to nitriles or amides secondary amines to imines or other products tertiary amines to N-oxides or other prodncts (Section 5.1) and the oxidation of amides (5.2). Oxidation of ethers to esters or lactones follows (5.3), then of sulfides to sulfoxides or sulfones (5.4) and of phosphines, arsine and stibines to their oxides (5.5). A final section (5.6) concerns such miscellaneous oxidations not covered by other sections in the book. 

MISCELLANEOUS REACTIONS OF DIHYDROPYRIDINES Additional tests for net hydride transfers initiated by single-electron transfer include the use of substrates in which such pathways would necessarily involve readily ring-opened cyclopropylmethyl or readily cyclized 5-hexenyl radicals. Products from these radical reactions are not formed in NAD+/ NADH dependent enzymic reductions or oxidations (Maclnnes et al., 1982, 1983 Laurie et al., 1986 Chung and Park, 1982). Such tests have also been applied in non-enzymic reductions. Thus cyclopropane rings in cyclopropyl 2-pyridyl ketones, or imines of formylcyclopropane (van Niel and Pandit, 1983, 1985 Meijer et al., 1984) survive Mg+2 catalysed reduction by BNAH or Hantzsch esters but are opened by treatment with tributylin hydride. 

Miscellaneous. Reagent prepared by the Syntex procedure has been used to oxidize pyridine methanols to the corresponding aldehydes, mercaptans to disulfides, aliphatic a-ketols to a-diketones, and N-phenylhydroxylamine to nitrosobenzene. A suspension of the dioxide in an ethereal solution of the substrate was stirred vigorously for 5-6 hrs. and the oxide was removed, and washed with ether. The filtrate and washings were concentrated under reduced pressure and the product isolated by distillation or crystallization. 

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