Abstract
Iodide ion promotes the free radical addition of t-BuHgI to acrylonitrile to form t-BuCH2CH (CN)HgI. A facile reaction of the adduct 1-cyanoalkyl radical with t-BuHgI2-is indicated. Further promotion is observed in the presence of NH4I or PTSA/KI in a reaction now leading directly to t-BuCH2CH2CN. Protonation of the intermediate adduct radical followed by electron transfer from t-BuHgI2-is postulated. With fumaronitrile reaction of the adduct, radical [t-BuCH (CN)C·HCN] with t-BuHgI can be promoted by the addition of acids or bases. In the presence of NH4I or PTSA/KI, the reductive alkylation product is formed, while in the presence of DABCO, oxidative alkylation occurs to yield t-BuC (CN)=CHCN and t-BuC (CN)=C (CN)Bu-t. Protonation of [t-BuCH (CN)C·HCN] increases the ease of reduction while deprotonation yields an easily oxidized radical anion.
Original language | English |
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Pages (from-to) | 5967-5972 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 117 |
Issue number | 22 |
DOIs | |
Publication status | Published - 1995 Jun |
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry