Arsinous acid esters pyrolysis

The pyrolysis of organoarsenic compounds containing the arsenyl moiety has some limited preparative applications [arsenyl (As=0) by analogy with phosphoryl (P=0)]. The compounds are based on the arsonic acid RAs(0)(0H)2, the arsinic acid R2As(0)0H and the arsine oxide R3As=0 structures. The acids are in interesting contrast with the phosphorus series. The phosphonic and phosphinic esters are prepared from the phosphorus(III) precursors via the Arbuzov synthesis. This synthetic route fails with the arsenic analogues, and further, if an alkyl halide or a salt is added in the pyrolysis of arsonic or arsinic acid esters a retro-Arbuzov reaction takes place . ... 

The esters of arsinic acid are more thermally labile, often resinifying on distillation. However, catalysed pyrolyses using alkyl halides, salts or mineral acids afford useful yields ca 50%) of arsenic(III) esters . The mechanism is considered to involve the pyrolysis of an alkoxyarsonium salt 7 is formed with the catalyst. 

It has already been noted that the esters of arsinous and arsonous acids disproportionate of heating. The formation of As(OR)3 in the pyrolysis of arsonic acid derivatives is thought to be the product of the secondary disproportionation reaction of the primary product RAs(OR)2-... 

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