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Thiocyanations VI: Iron‐catalyzed thiocyanations of unsaturated acids and esters
Author(s) -
Maxwell R. J.,
Silbert L. S.
Publication year - 1978
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/bf02667274
Subject(s) - chemistry , adduct , catalysis , double bond , yield (engineering) , organic chemistry , medicinal chemistry , polymer chemistry , metallurgy , materials science
The effect of iron catalyst and the advantages of its use in thiocyanogen additions to a series of unsaturated acids and esters were studied. In the absence of catalyst, the deactivation effect of the carboxylic group on the double bond is observed up to and including the Δ 5 position, conversions to products are low, and the products in some cases are not the anticipated dithiocyanate adducts. These normally unreactive double bonds are induced to react with thiocyanogen by iron catalyst. Furthermore, for the catalyzed reactions of Δ 2 and Δ 3 acids and esters, the esters are found to be more reactive than the acids, although both produce trace to low yields of adducts. Single isolated bonds located in any position beyond Δ 3 , including terminal, are thiocyanated rapidly and in high yield in the presence of iron catlyst. Methyl linoleate and methyl linolenate form ca. 80% of the tetrathiocyanate and hexathiocyanate adducts, respectively.