76917-09-4Relevant articles and documents
Photostimulated Reactions of Potassium Diphenylarsenide with Haloarenes by the SRN1 Mechanism
Rossi, Roberto A.,Alonso, Ruben A.,Palacios, Sara M.
, p. 2498 - 2502 (1981)
Photostimulated reactions of haloarenes with potassium diphenylarsenide (3) were studied in liquid ammonia. p-Chloro-, p-bromo-, and p-iodotoluenes gave four products: triphenylarsine, p-tolyldiphenylarsine, di-p-tolylphenylarsine and tri-p-tolylarsine.Similarly, with p-chloro, p-bromo-, and p-iodoanisole as substrates, four arsines were found as products: triphenylarsine, p-anisyldiphenylarsine, di-p-anisylphenylarsine and tri-p-anisylarsine. p-Chlorotoluene and p-bromoanisole are unreactive in the dark, but with 4-chlorobenzophenone there is a dark reaction, which is accelerated by light and inhibited by m-dinitrobenzene and oxygen.Withthe latter substrate, only the straightforward substitution product is formed.These reactions are believed to occur by the SRN1 mechanism, with an exstra feature of reversible coupling of aryl radicals with arside ions, which causes the scrambling of aryl rings.It is suggested that the low-lying ?* MO of the benzophenone moiety prevents C-As bond breaking in the radical anion intermediate in that case.
