Electrochemical reduction of nitrobenzyl halides in acetonitrile

Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis

“…This species is a strong reductant ( E 1/2 II/*I = –1.43 V vs SCE), capable of donating an electron to 4-nitrobenzyl bromide ( 17 , E 1/2 red = –1.1 V vs SCE). 34 Thus, while Ru(bpy) 3 2+ must be reduced to its Ru(I) oxidation state before it can transfer an electron to benzyl bromide, the substantially more reducing Cu(dap) 2 + can perform the reduction directly from its photoexcited state. Reduction of 17 induces fragmentation to afford benzyl radical 18 , which may dimerize to give bibenzyl 19 (or, as suggested by Tanaka, undergo a second reduction followed by S N 2 attack on benzyl bromide).…”

Photochromic indigoids. II. Absorption spectra and quantum yields for the photoisomerization of selenoindigo

“…DO rate(H/D ex) = kK [6] = k0bsd61 K = Kw/Ka the mechanism shown in eq 2 demands the presence of 6 + OD-+ 3 + DzO + 6-di + OD- Table I allow a distinction between these two possibilities. These data demonstrate the requirement of added base for exchange and an independence of the calculated second-order rate constant (k,,,,/[NaOD]) on the added deuterioxide concentration.…”

The direct preparation of the esters ofp-nitrobenzylphosphonic acid fromp-nitrobenzyl halides

“…Because of the less negative reduction potential of p-nitrobenzyl bromide, the electron transfer reaction is a very fast process, and the result of this is dimer 6 formation in a very high yield. On the other hand, the reduction potentials for p-nitrobenzyl chloride 1 and p-nitrobenzyl bromide 5 are -0.97 and -0.89 V (Pt/SCE, CH,CN), respectively [28]. Since p-nitrobenzyl chloride and bromide have very similar reduction potentials, one can expect that they should have comparable ability to accept an electron from the p-nitrobenzyl anion.…”