106470-71-7Relevant academic research and scientific papers
Carbanions: Electron Transfer vs. Proton Capture. 8. Use of Sterically Protected Aromatic Nitro Compounds as Base-Resistant, One-Electron Oxidants
Guthrie, Robert D.,Hartmann, Christa,Neill, Richard,Nutter, Dale E.
, p. 736 - 740 (1987)
The behavior of two sterically protected nitroarenes, 2,4,6-tri-tert-butylnitrobenzene and 1,1,4,4,5,5,8,8-octamethyl-1,2,3,4,5,6,7,8-octahydro-9-nitroanthracene, was studied in the presence of strong bases.These compounds are resistant to the oxygen-base-promoted reactions observed with nitrobenzene, but they retain the capacity to oxidize carbon bases such as 9-methoxyfluorenide and triphenylmethide ions.Alkyllithium compounds are converted to alkyl radicals but phenyllithium does not react.Unexpectedly, the radical anions formed when these nitro compounds serve as oxidants undergo slow denitration to the corresponding aryl radicals.
Dual Roles for Potassium Hydride in Haloarene Reduction: CSNAr and Single Electron Transfer Reduction via Organic Electron Donors Formed in Benzene
Barham, Joshua P.,Dalton, Samuel E.,Allison, Mark,Nocera, Giuseppe,Young, Allan,John, Matthew P.,McGuire, Thomas,Campos, Sebastien,Tuttle, Tell,Murphy, John A.
supporting information, p. 11510 - 11518 (2018/09/12)
Potassium hydride behaves uniquely and differently than sodium hydride toward aryl halides. Its reactions with a range of haloarenes, including designed 2,6-dialkylhaloarenes, were studied in THF and in benzene. In THF, evidence supports concerted nucleophilic aromatic substitution, CSNAr, and the mechanism originally proposed by Pierre et al. is now validated through DFT studies. In benzene, besides this pathway, strong evidence for single electron transfer chemistry is reported. Experimental observations and DFT studies lead us to propose organic super electron donor generation to initiate BHAS (base-promoted homolytic aromatic substitution) cycles. Organic donor formation originates from deprotonation of benzene by KH; attack on benzene by the resulting phenylpotassium generates phenylcyclohexadienylpotassium that can undergo (i) deprotonation to form an organic super electron donor or (ii) hydride loss to afford biphenyl. Until now, BHAS reactions have been triggered by reaction of a base, MOtBu (M = K, Na), with many different types of organic additive, all containing heteroatoms (N or O or S) that enhance their acidity and place them within range of MOtBu as a base. This paper shows that with the stronger base, KH, even a hydrocarbon (benzene) can be converted into an electron-donating initiator.
