Nitroxydes—LXXVI

Discovery and Exploitation of AZADO: The Highly Active Catalyst for Alcohol Oxidation

“…32) We prepared Nor-AZADO in 5 steps from acetonedicarboxylic acid (38), glutaraldehyde (39), and benzylamine (40), with slight modification of a previous method 43) (Chart 13).…”

“…31,32) (It is important to note that AZADO-type nitroxyl radial is protected by the Bredt rule 33,34) from a destructive disproportionation to give the corresponding nitrone and hydroxylamine.) However, no study has been reported regarding AZADO since then.…”

Ferromagnetic interactions in a crystalline nitroxide biradical: 1,3,5,7-tetramethyl-2,6-diazaadamantane N,N′-dioxyl

“…The temperature ( T ) dependence of the static magnetic susceptibility (x) of pure organic free radicals in the solid state1 generally follows the Curie-Weiss law2 with a negative Weiss constant ( 8 ) indicating independent spins or predominant antiferromagnetic interactions in the solid. Positive Weiss constants are not common.…”

Alkyl group stabilization of monoolefin radical cations. ESR, ENDOR, and cyclic voltammetry study

“…The flattening of the sixmembered rings, which accompanies the removal of the bridging C(6) methylene group on going from 1+* to 4+*, increases slightly both coupling constants of equatorial and axial 7-protons (Table a At a Pt electrode; solvent acetonitrile containing 0.1 M tetran-butylammonium perchlorate; vs. SCE;scan rate 20-200 mV/s unless otherwise indicated. b \E°' -£'°'(l,lt)] 23.06; a positive entry means it is thermodynamically more difficult to remove an electron than from 1. c No reduction peak observed, even at 10-V/s scan rate. EpOK = 1.73 V at 200-mV/s scan rate, corresponding to A(AG ) >9 kcal/mol (see text).…”