Abstract
A method for the thiolysis of nitriles by applying Lawesson’s
reagent and facilitated by the addition of boron trifluoride-diethyl
ether complex is reported. The method opens an easy access to primary
thioamides. Aromatic, benzylic, and aliphatic nitriles were converted
into the corresponding thioamides in high to quantitative yields
(even in unfavorable cases, e.g., ortho- substituted
benzonitriles). The reaction was performed in 1,2-dimethoxyethane-tetrahydrofuran
or toluene-diethyl ether solvent mixtures at 20-50 ˚C,
and exhibited considerable selectivity in the case of multifunctional
nitrile substrates, such as cyanomethyl N -acetylphenylalaninate,
benzoylacetonitrile, 4-cyanobenzamide, 4-acetyl-benzonitrile,
or pent-3-enenitrile.
Key words
thioamides - nitriles - Lawesson’s
reagent - Lewis acid complex - sulfur-transferring
reagents
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