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Thiocyanations: I. Elucidation of olefin thiocyanations: Product distribution, mechanism and a rationale of thiocyanogen value
Author(s) -
Silbert L. S.,
Russell J. R.,
Showell J. S.
Publication year - 1973
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/bf02641821
Subject(s) - chemistry , adduct , allylic rearrangement , isothiocyanate , allyl isothiocyanate , acetic acid , olefin fiber , yield (engineering) , organic chemistry , catalysis , materials science , metallurgy
Abstract Thiocyanogen adds to monoolefins ( cis ‐9‐octadecene, trans ‐9‐octadecene and methyl oleate) in acetic acid solution to yield α,β‐dithiocyanate, α‐thiocyanato‐β‐isothiocyanate, α‐thiocyanato‐β‐acetate and α‐bromo‐β‐thiocyanate adducts. A trace amount of a substitution product indicated to be an allylic isothiocyanate was detected in the reaction products from the trans ‐9‐octadecene and methyl oleate reactions. Formation of the mixed adducts does not affect the stoichiometry of thiocyanogen addition to monoolefins but is responsible for the nonquantitative formation of dithiocyanate adducts obtained in preparative work. A mechanism accounting for the products and stereochemistry is proposed. A clearer understanding of the reactions underlying determinations of the thiocyanogen value of polyolefins is provided on the basis of the available current evidences.