Dithiirane or thiosulfine intermediates in the reaction of acetyl diaroylchloromethyl disulfides with secondary amines? |
| |
Authors: | W Franek |
| |
Institution: | (1) Institut für Organische Chemie, Universität Wien, A-1090 Vienna, Austria |
| |
Abstract: | Summary Since 1979,Senning's acetyl dibenzoylchloromethyl disulfide has been known as one of the first thiosulfine/dithiirane precursors. Its reactions with an excess of morpholine fulfill three advantageous conditions at once: thiosulfine or dithiirane species are intercepted by intermolecular additions, without heating, and without rearrangements. In the present work, reactions between a series of new acetyl diaroylchloromethyl disulfides ((4-X-C6H4-CO)2-CCl-SSCOCH3;X=F, Cl, Br, CH3, and CH3O) and an excess of morpholine are studied. As dominating products, 2-(4-morpholinyldithio)-1,3-diaryl-1,3-propanediones are obtained. The reactions are complete within several seconds. In order to obtain high yields of interception products, the mixtures have to be worked up within a few minutes. From the observation of high reaction rates at room temperature, a new reaction mechanism is deduced that involves the initial formation of dithiirane species (alone or before thiosulfine species).Dedicated to Prof.Peter K. Claus on the occasion of his 60th birthday |
| |
Keywords: | Acetyl diaroylchloromethyl disulfides Dithiiranes Morpholine Reactive intermediates Thiosulfines |
本文献已被 SpringerLink 等数据库收录! |
|