94686-17-6Relevant academic research and scientific papers
HYDROGEN ABSTRACTION FROM THE ISOMERIC CYMENES
Sulpizio, A.,Mella, M.,Albini, A.
, p. 7545 - 7552 (2007/10/02)
The irradiation of cerium (IV) ammonium nitrate in the presence of ortho, meta and para cymene yields products from attack at the methyl group (the nitrates - these ones in 55 to 69percent isolated yield-, the nitro derivatives, and the aldehydes) as well as at the isopropyl group (the acetophenones, not obtained from the ortho isomer), with minimal ring nitration.The formation of bibenzyls on irradiation with t-butyl peroxide of the same substrates is also studied.The mechanisms of the reactions with the NO3 radical, a good electron acceptor, and with the alkoxy radical are contrasted and compared with photochemical hydrogen abstraction by n?* and, respectively, ??* excited states.
Photochemical Hydrogen Abstraction from Cymenes
Albini, A.,Sulpizio, A.
, p. 2147 - 2152 (2007/10/02)
The three isomeric cymenes are examined in photochemical reactions involving hydrogen transfer with 1,4-naphthalenedicarbonitrile (NDN), α,α,α-trifluoroacetophenone (TFA), and benzophenone (BP).Selectivity for attack at primary vs tertiary position (P/T) and quantum yield are determined.The reactions are rationalized as involving loose perpendicular complexes yielding a low P/T ratio in the products (with BP n? triplet), a face-to-face charge transfer complex yielding a high P/T (with TFA ??* triplet and also NDN singlet, but only as far as the benzylnaphthalenes 1 and 2 are concerned), and a tighter charge transfer complex yielding again a low P/T in the formation of dibenzomethanocyclooctenes 3, the main products from NDN.The energetic limit of such a directing effect of the conformation of the intermediate complex onto photochemical reactivity is evidenced by the different results obtained with o-cymene.
