5659-38-1Relevant academic research and scientific papers
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.
Rearrangements of Vinylogous Acyl Chlorides, XXVI. - Z,E-Isomerizations of S-Alkyl and S-Aryl 2,3,4,5-Tetrachloro-2,4-pentadienethioates via 2H-Pyran Intermediates
Roedig, Alfred,Fleischmann, Klaus
, p. 1960 - 1971 (2007/10/02)
The (Z,Z)-thioates 2 are prepared from the acyl chlorides 1 with thiols and triethylamine in ether or with thiolates in ethanol.They are stable below 100 deg C.At higher temperature the alkyl esters 2a - c and 2h, i lose alkyl chloride and decompose to th
