By H. Fischer (auth.), H. Fischer (eds.)
Free radicals, that are key intermediates in lots of thermal, photochemical and radiation tactics, are vital for a formal figuring out of basic common methods and the winning improvement of natural syntheses. Volume II/18 serves as a complement and extension to volume II/13 and covers fee constants and different kinetic info of loose radical reactions in drinks. Furthermore II/18 includes new chapters on reactions of radicals in excited states and of carbenes, nitrenes and analogues. chosen species in aqueous suggestions for which different compilations can be found have been intentionally passed over as sooner than, and for a similar cause electron move equilibria of natural radicals weren't covered.
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Extra info for Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals
Rate data • a –– C6H5C(CH3)2O • –––– ➝ C6H5COCH3 + CH3 • b –– ➝ C6H5C(CH3)2OH + C6H5C(CH3)2 C6H5C(CH3)2O • + C6H5CH(CH3)2 –––– Phot. and therm. of [C6H5C(CH3)2O]2 and therm. 074 M–1 [C9H11O] 83Bai1 • a –– C6H5C(CH3)2O • –––– ➝ C6H5COCH3 + CH3 • b –– ➝ C6H5C(CH3)2OH + C6H5C(CH3)CH2OOC(CH3)2C6H5 C6H5C(CH3)2O • + [C6H5C(CH3)2O]2 –––– Phot. or therm. 5 Alkoxyl radicals with ten carbon atoms [C10H19O] O OH + (n-C4H9)3 Sn H O a + (n-C4H9)3 Sn O b BrCH2CH2CH(C(CH3)3)CH2CH2C(O)H, initiated by therm. 2 · 106 s –1 PR C6H6 118 ) 92Bec1 117 ) Calculated from the Arrhenius parameters.
Rate data • –– C6H5C(CH3)2O • + c-C6H12 –––– ➝ C6H5C(CH3)2OH + c-C6H11 Laser phot. 04 · 106 M–1 s –1 83Bai1 Laser phot. 35 · 106 M–1 s –1 93Avi1 [C9H11O] C6H5 C (CH3)2 O + abstraction and addition products Laser phot. 64 · 106 M–1 s –1 83Bai1 [C9H11O] 40 ) 40) C6H5 C (CH3)2 O + C6H5 C (CH3)2 OH + Laser phot. 30 · 106 M–1 s –1 [C9H11O] • –– C6H5C(CH3)2O • + CH2 –– CH(CH2)5CH3 –––– ➝ C6H5C(CH3)2OH + CH2 –– CHCH(CH2)4CH3 Laser phot. 59 · 106 M–1 s –1 [C9H11O] 5 ) Time-resolved infrared detection. ) Most probable reaction path.
1 Alkoxyl radicals Radical’s gross formula Reaction Radical generation Method Solvent [C4H9O] T [K] [Ref. p. / add. ref. Rate data • a –– ➝ CH3COCH3 + CH3 (CH3)3CO • –––– • b –– ➝ (CH3)3COH + X –– C6H4 S (CH3)3CO • + X –– C6H4SH –––– Therm. 2 M–1 93Kim1 59 ) 59 ) 59 ) 59 ) 59 ) [C4H9O] a (CH3)3 CO (CH3)3 CO + HO Therm. of DTBP PR [C4H9O] CH3 CO CH3 + OH C6H6 CH3 b (CH3)3 COH + O kb /ka = 803 M–1 393 OH 60 ) 85Lis1 • a –– (CH3)3CO • –––– ➝ CH3COCH3 + CH3 • b –– (CH3)3CO • + C6H5NH2 –––– ➝ (CH3)3COH + C6H5 NH Therm.