REACTION OF TRITHIAZYL TRICHLORIDE WITH ACTIVE METHYLENE-COMPOUNDS

Activated allylic compounds react with trithiazyl trichloride, (NSCl), , to give 1,2,5-thiadiazoles 1 and isothiazoles 2. An allylic 2-substi tuent normally prevents formation of an aromatic 1,2,5-thiadiazole, an d isothiazole formation becomes the major pathway. Simple allylic comp ounds are not very reactive towards (NSCl)(3) but a terminal electron withdrawing group (CO2Et) enhances the reactivity. With unsymmetrical allylic compounds, isothiazole formation is regiospecific placing the more electron withdrawing group adjacent to the ring sulfur. 1,3-Diket ones give 3-acyl-1,2,5-thiadiazoles; unsymmetrical 1,3-diketones give these thiadiazoles regiospecifically, explicable by cyclisation of an intermediate onto the more reactive carbonyl group. 1,4-Diketones give 3,4-diacyl-1,2,5-thiadiazoles; thus 1,2-dibenzoyl-ethane, -ethene and -ethyne all give 3,4-dibenzoylthiadiazole (40-44%). Many of these tri thiazyl trichloride reactions provide attractive one-step routes to 1, 2,5-thiadiazoles and isothiazoles.