- The Oxidation of Trimethylamine by OH Radicals in Aqueous Solution, as Studied by Pulse Radiolysis, ESR, and Product Analysis. The Reactions of the Alkylamine Radical Cation, the Aminoalkyl Radical, and the Protonated Aminoalkyl Radical
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Hydroxyl radical reactions with trimethylamine in aqueous solution lead to the formation of the aminoalkyl radical (A(.)) and its conjugated acid (AH(+.)) as well as to the alkylamine radical cation (CH3)3N(+.) (N(+.)).These radicals are transformed into each other by hydrolytic reactions, e.g. Radicals AH(+.) are more acidic (pKa ca. 3.6) than the radicals N(+.) (pKa ca. 8.0).Consequently, N(+.) predominate over AH(+.) under quasi equilibrium conditions (e.g. in the presence of phosphate buffer) and are the only species observed by ESR in acid solutions.Reacting with the protonated amine, OH radicals abstract hydrogen at nitrogen and at carbon with comparable ease.Reaction of OH radicals with the free amine may initially also generate N(+.), beside H-abstraction at carbon.Radicals A(.) absorb more strongly at 260 nm (ε = 3390 dm3mol-1cm-1) than the radical cation N(+.) (ε = 950 dm3mol-1cm-1).Radical A(.) has reducing properties whereas radicals AH(+.) and N(+.) have oxidizing properties and hence can be monitored with p-nitroacetophenone (the reducing radicals), and Fe(CN)6(4-), N,N'-tetramethyl-p-phenylenediamine and 2,2'-azinobis-(3-ethyl-benzthiazoline-6-sulphonate) (the oxidizing radicals).These radicals mainly (>/=85percent) disproportionate, one of the products being formaldehyde. - Keywords: Radiation Chemistry, Amines, Electron Transfer, Hydrogen Abstraction, Reaction Kinetics
- Das, Suresh,Sonntag, Clemens von
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p. 505 - 513
(2007/10/02)
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- CIDNP STUDY OF THE PHOTOCLEAVAGE OF BENZYL DERIVATIVES
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Evidence of the mechanistic pathways involved in the acetone sensitized homolytic photocleavage of benzyltrialkylammonium salts and other benzyl derivatives is obtained by CIDNP.
- Gardini, G. P.,Charlton, J. L.,Bargon, J.
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p. 987 - 990
(2007/10/02)
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