Abstract. 4,5-Benzotropone and 1,2-ethanedithiol gave the expected dithioketal 8 with boron trifluoride etherate in methanol. In contrast, tropone, under similar conditions, gave the bicyclic 1,7-disubstituted cycloheptatrienes 2, 3 and 4 on reaction with, respectively, 1,2-ethanedithiol, 1,3-propanedithiol, and o-benzenedithiol. Related, monocyclic 1,7-difunctionalized cycloheptatrienes 10-13 and 15ad were obtained from sodium thiolates and methoxy-or I-(alky1thio)tropenylium salts in dichloromethane-ethanol at -50°C. 1,7-Bis(aIkylthio)-substituted cycloheptatrienes with unhindered alkylthio groups showed a rapid interconversion of the alkylthio groups at the C( 1) and C (7) carbons (15a s 16).Unsuccesful attempts to obtain tropone dithioketals, which were desired as reaction intermediates, led us to search for and discover simple entries to cycloheptatrienes 1,7-difunctionalized with alkoxy or alkylthio groups. The reactions involve either tropone itself with thiols or tropenylium salts with thiolates. The results are interesting because access to regiospecifically difunctionalized cycloheptatrienes has, so far, proved difficult. In fact, addition of bases to monosubstituted tropenylium ions is known to give a mixture of I ,7-, 2,7-, and 3,7-disubstituted isomeric cycloheptatrienes*. The only exception is the addition of methoxide to methoxytropenyhum ion at low temperature to give tropone dimethylaceta12. In Scheme 1 are reported the new products obtained in medium to low yields, from tropone 1 and dithiols under typical conditions for dithioacetalization of ketones3. The balance of materials consists of intractable red gums. Structures 2 4 , which are consistent with elemental, mass, and UV data, are fully supported by 'H NMR spectra. In fact, for both 2 and 3 we observed a multiplet for H(7) and