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58249102769
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Such a large difference in the rate constants of reactions of radical-trapping antioxidants with secondary and tertiary peroxyl radicals is unprecedented. Also, the inhibition rate constants were based on the assumption that one molecule of allicin reacts with one chain-carrying peroxyl radical in the autoxidation of each substrate stoichiometric factor: n, 1, an assumption that is invalid on the basis of the actual inhibition periods observed,[5b] which correspond to stoichiometric factors of approximately 0.3
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[5b] which correspond to stoichiometric factors of approximately 0.3.
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12
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0000608914
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Appropriately substituted carbon-centered radicals, such as that derived from HP-136, are an exception; see: J. C. Scaiano, A. Martin, G. P. A. Yap, K. U. Ingold, Org. Lett. 2000, 2, 899.
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Appropriately substituted carbon-centered radicals, such as that derived from HP-136, are an exception; see: J. C. Scaiano, A. Martin, G. P. A. Yap, K. U. Ingold, Org. Lett. 2000, 2, 899.
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15
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58249098342
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For other highly reactive radical-trapping antioxidants, see: M. Wijtmans, D. A. Pratt, L. Valgimigli, G. A. DiLabio, G. F. Pedulli, N. A. Porter, Angew. Chem. 2003, 115, 4506; Angew. Chem. Int. Ed. 2003, 42, 4370;
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For other highly reactive radical-trapping antioxidants, see: M. Wijtmans, D. A. Pratt, L. Valgimigli, G. A. DiLabio, G. F. Pedulli, N. A. Porter, Angew. Chem. 2003, 115, 4506; Angew. Chem. Int. Ed. 2003, 42, 4370;
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58249110344
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[1] In our inhibited autoxidation reactions, the addition of ethyl propiolate to the reaction mixture did not prevent inhibition, presumably since the reaction of 2-propenesulfenic acid with peroxyl radicals is much faster than its addition to ethyl propiolate.
-
[1] In our inhibited autoxidation reactions, the addition of ethyl propiolate to the reaction mixture did not prevent inhibition, presumably since the reaction of 2-propenesulfenic acid with peroxyl radicals is much faster than its addition to ethyl propiolate.
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19
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58249116493
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[10] that sulfenic acids undergo other reactions, such as reaction with oxygen, during autoxidation processes.
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[10] that sulfenic acids undergo other reactions, such as reaction with oxygen, during autoxidation processes.
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21
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15744383667
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See, for example: P. Mulder, H.-G. Korth, D. A. Pratt, G. A. DiLabio, L. Valgimigli, G. F. Pedulli, K. U. Ingold, J. Phys. Chem. A 2005, 109, 2647.
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58249116494
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[16]
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[16]
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58249099905
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-1).
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-1).
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29
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58249114834
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Sulfinic and sulfonic acids, the oxidation products of sulfenic acids, would not be expected to be good peroxyl-radical scavengers, since the lone pair of electrons on the sulfur atom would either be too low in energy (former) or unavailable (latter) for the five-center PCET reaction
-
Sulfinic and sulfonic acids, the oxidation products of sulfenic acids, would not be expected to be good peroxyl-radical scavengers, since the lone pair of electrons on the sulfur atom would either be too low in energy (former) or unavailable (latter) for the five-center PCET reaction.
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