Halogenation of dibenz[a,c]anthracene (1) by NBS in CCl(4) affords the products of 9- and 10-monobromination in the ratio of 9:1. The reaction is accelerated by iodine, and HBr effects rearrangement of 9-bromo product to the sterically less crowded 10-bromo isomer. The mechanism is proposed to involve reversible addition of Br(2), followed by elimination of HBr. Reaction of NCS with 1 in CCl(4) requires addition of HCl and affords exclusively 9-chlorination. The different reactivities of NBS and NCS are ascribed to the relative amounts of free halogen produced (due to differences in N-X bond strengths involving Br and Cl), and the different sizes of the halogens. Under similar conditions, NCS chlorinates 9-bromoanthracene (2a) to afford 9,10-dichloroanthracene and 9-bromo-10-chloroanthracene in the ratio of 65:35. This reaction ostensibly occurs by addition of Cl(2) to 2a, followed by preferential loss of HBr rather than HCl. 9-Methylanthracene (3) affords exclusively 9-(bromomethyl)anthracene with NBS in the absence of iodine, but mainly (67%) 9-bromo-10-methylanthracene in the presence of iodine. Chlorination of 3 with NCS in the presence of HCl also affords mostly (65%) nuclear halogenation. Nuclear bromination of anthracene, 9-methylanthracene, and dibenz[a, c]anthracene by NBS in the absence of added HBr is accelerated by iodine. This effect is probably due to an increase in the amount of bromine produced from NBS in the presence of iodine.

Alkoxyamine 3 undergoes thermolysis only on heating to over 150°C, ∆H q ) 34.3 ( 1.6 kcal/mol and ∆S q ) 0.8 ( 3.7 eu. The initially formed nitroxyl (6) and R-phenethyl radicals (5) mainly disproportionate to styrene plus diethylhydroxylamine (2) but they also recombine to starting material and undergo a new reaction, disproportionation to ethylbenzene plus nitrone (12). The latter reacts with the styrene product to yield oxazolidines 8 and 9. The competition between attack of 5, generated from azo-R-phenylethane (1), on 2 versus styrene allowed us to calculate a rate constant at 120°C of 5 × 10 3 M -1 s -1 for H • transfer from diethylhydroxylamine to 5.

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Photolysis of azoazoxyalkane 9 and thermolysis of β-azoxyperester 13 afford β-azoxy radicals 1 and 14, respectively. One reaction pathway of these radicals is cyclization to azoxy oxygen to form cyclic hydrazyl radicals 2 and 16 that fragment to a ketone or aldehyde plus hydrazonyl radical 3. The analogous hydrazyl radical 6 need not be invoked in the case of γ-azoxy radical 5, which instead undergoes a rare solution phase β-scission to lose ethylene. Surprisingly, the same β-scission was found in the 3,3-dimethyl-4-pentenyl radical (34), a hydrocarbon analogue of 5.