101145-03-3Relevant articles and documents
Singlet vs Triplet Reactivity of Photogenerated α,n-Didehydrotoluenes
Pedroli, Chiara,Ravelli, Davide,Protti, Stefano,Albini, Angelo,Fagnoni, Maurizio
supporting information, p. 6592 - 6603 (2017/07/15)
The reactivity of α,n-didehydrotoluenes (DHTs) in protic media (organic/aqueous mixtures) was explored by means of a combined computational and experimental approach. These intermediates were generated via a photoinduced double elimination process occurring in (chlorobenzyl)trimethylsilanes and led to the formation of a varied products distribution, depending on the isomer tested. Irradiation of ortho- and para-derivatives resulted, respectively, in the formation of triplet α,2- and α,4-DHTs, whose diradical reactivity led to both radical and polar products. On the other hand, irradiation of the meta-precursor led to the singlet α,3-DHT isomer. The latter showed a marked preference for the formation of polar products and this was rationalized, as supported by computational evidence, via the involvement of a zwitterionic species arising through interaction of the nucleophilic solvent with the benzylic position of the DHT.
Preparation and Reactions of Dianions from the Cresols
Bates, Robert B.,Siahaan, Teruna J.
, p. 1432 - 1434 (2007/10/02)
With n-BuLi/KO-t-Bu, protons are removed from the hydroxyl and methyl groups of cresols 5 to give dianions 6 in yields of 85percent (ortho), 95percent (meta), and 42percent (para).These dianions react with alkyl halides, Me3SiCl, Bu3SnCl, CO2, and oxidizing agents at carbon only and with dialkyl sulfates at both carbon and oxygen.Thus phenol derivatives bearing primary alkyl groups can be prepared from the corresponding methylphenols via dianions 6.
