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Umlagerungen vinyloger Carbonsaeurechloride, XXX. Thermische Umlagerungen von chlor- und organylthiosubstituierten (2Z,4Z)-2,4-Pentadienalen und -onen zu (2Z,4Z)-2,4-Pentadienthiosaeure-S-estern
Roedig, Alfred,Goepfert, Herbert
, p. 3625 - 3633 (2007/10/02)
The pentadienals 2 are prepared by reduction of the corresponding acyl chlorides 1.The ketone 2d is synthesized from 1b with lithium tert-butyl(phenylthio)cuprate.Elimination of methyl chloride and cyclization occurs on treatment of 1a with AlCl3 giving the 2H-thiopyran-2-one 8.In boiling carbontetrachloride the aldehydes 2 rearrange by 1,5-chlorine shift completely and stereospecifically into the thiolates 3.The analogous reaction 2d -> 3d is non stereospecific.As expected, compounds 2 and 3 may be converted into the same 4H-pyran-4-ones 6.The rearrangement 2 -> 3 is accelerated by RS-groups instead of chlorine in the 5-position and decelerated in the 3-position.The substituent influences and the reaction mechanism are discussed.
