Keywords
hydroxyacetone
hydroxyacetone tosylate
alpha-hydroxydithioketals
boron trifluoride diethyl etherate
ethane-1,2- and propane-1,3-dithiols
Abstract
This paper presents the results of studies on the products of hydroxyacetone and hydroxyacetone tosylate dithioketalization with ethane-1,2-dithiol and propane-1,3-dithiol. The process was carried out in an inert gas atmosphere, argon, or in the air atmosphere and with a variable excess of one of the substrates, here the dithiol reagent. The structure elucidation and the reaction mechanism for the formation of the isolated products have been discussed. Structure products were confirmed using 1H NMR and 13C NMR spectroscopy as well as mass spectrometry. The structure of one of the main products, 1,2-bis((2-methyl-1,4-dithian-2-yl)thio)ethane, was confirmed by single-crystal X-ray diffraction analysis. It was obtained with yield up to 62%. The studied dithioketalization process of selected ketones allows for the efficient synthesis of 2-methyl-1,3-dithiolan-2-yl)methanol, (2-methyl-1,3-dithian-2-yl)methanol and 3-((2-methyl-1,4-dithiepan-2-yl)thio)propane-1-thiol with yields of 63%, 66% and 50% respectively. Furthermore, we disclose an alternative synthesis of 5-methyl-2,3-dihydro-1,4-dithiine, a synthetically useful building block.
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