Reaction of tert-alkoxyl and alkyl radicals with styrene studied by the nitroxide radical-trapping technique
Nakamura, T; Busfield, WK; Jenkins, ID; Rizzardo, E; Thang, SH; Suyama, S
| HERO ID | 4854473 |
|---|---|
| In Press | No |
| Year | 1997 |
| Title | Reaction of tert-alkoxyl and alkyl radicals with styrene studied by the nitroxide radical-trapping technique |
| Authors | Nakamura, T; Busfield, WK; Jenkins, ID; Rizzardo, E; Thang, SH; Suyama, S |
| Journal | Journal of Organic Chemistry |
| Volume | 62 |
| Issue | 16 |
| Page Numbers | 5578-5582 |
| Abstract | The reactions of tert-alkyl peroxypivalates 1 (R = methyl, ethyl, and n-propyl) with styrene in the presence of the free-radical scavenger (1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindol-2-yl)oxyl (2) have been studied at 60 degrees C, tert-Butyl and tert-alkoxyl radicals (tert-butoxyl, tert-pentyloxyl, and tert-hexyloxyl radicals) were generated from the thermolysis of 1, and the derivative alkyl radicals (methyl, ethyl, n-propyl, and 4-hydroxy-4-methylpentyl radicals) were formed by subsequent unimolecular reactions (beta-scission and 1,5-H shift) of the corresponding tert-alkoxyl radicals. The extent of the unimolecular reactions of the tert-alkoxyl radicals (versus addition to styrene) and the relative reactivity of alkyl radicals toward addition to styrene were obtained fi om the competitive addition/trapping reactions. The absolute rate constants for the addition of tert-butyl, ethyl, methyl, and n-propyl radicals to styrene at 60 degrees C were estimated to be (7.4, 4.7, 5, and 5.4) x 10(5) M-1 s(-1), respectively. |
| Doi | 10.1021/jo9707489 |
| Wosid | WOS:A1997XP91100047 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |