INSERTION REACTION OF TRIPHENYLARSINE AND TRIPHENYLANTIMONY WITH TETRAMETHYL-1,2-DIOXETANE - PREPARATION OF 2,2-DIHYDRO-4,4,5,5-TETRAMETHYL-2,2,2-TRIPHENYL-1,3,2-DIOXARSOLANE AND DIOXASTIBOLANE

The reaction of tetramethyl-1,2-dioxetane (1) with several group 5A compounds was investigated. The reaction of 1 with Ph3N and Ph3Bi resulted in catalytic decomposition of 1 to acetone. The reaction of 1 with Ph3As produced the stable arsenic(V) adduct 2,2-dihydro-4,4,5,5-tetramethyl-2,2,2-triphenyl-1,3,2-dioxarsolane (2). The reaction of 1 with Ph3Sb resulted in the formation of a stable antimony(V) adduct, 2,2-dihydro-4,4,5,5-tetra-methyl-2,2,2-triphenyl-1,3,2-dioxastibolane (3), as well as formation of acetone via catalytic decomposition. The relative yield of adduct 3 to acetone increased upon changing the reaction solvent from C6D6 to CDC13. The kinetics was investigated. Ph3Sb was found to be slightly less reactive than Ph3P while Ph3As was found to be least reactive. The results were consistent with a concerted (biphilic) insertion of the group 5A compounds into the peroxy bond of 1. The reaction of 1 with arsines and stibines represents a new, convenient method for the synthesis of cyclic arsenic(V) and antimony(V) compounds. © 1979, American Chemical Society. All rights reserved.