Masaharu O-oka

Synthesis of macrocyclic compounds containing the cycloheptatriene and tropylium ion unit

Abstract Crown compounds containing the cycloheptatriene and tropylium ion unit were synthesized from 1,6-dithiocyanatocycloheptatriene.

SYNTHESES OF CYCLOHEPTATRIENES WITH SULFUR FUNCTIONAL GROUPS

Abstract Disodium 1, 6-disulfido-1, 3, 5-cycloheptatriene 3, formed by reduction of 1 with sodium in liq. ammonia, reacts with hydrogen chloride and methyl iodide to give 1, 6-dimercapto-, 4, and 1, 6-bis(methylthio)-1, 3, 5-cycloheptatrienes 5 respectively; however, it is oxidized by bromine to afford cyclic disulfide 6. 1, 6-Diiodo-1, 3, 5-cycloheptatriene 2 is converted to 1, 6-bis(benzylthio)-1, 3, 5-cycloheptatriene 7 by reaction with sodium phenylmethanethiolate, whereas similar reactions with 1-(2-hydroxyethyl)-6-iodo-1, 3, 5-cycloheptatriene 9, obtained from 2 via 1-iodo-6-vinyl-1, 3, 5-cycloheptatriene 8, give 1-benzylthio-6-(2-hydroxyethyl)-1, 3, 5-cycloheptatriene 10. 1-Benzylthio-6-benzylthioethyl-1, 3, 5-cycloheptatriene 11 is synthesized by the reaction from 9 via 1-(2-bromoethyl)-6-iodo-1, 3, 5-cycloheptatriene 10. Attempts to synthesize thiols from 7, 11, and 12 are also described.

Cycloaddition reactions of N-thioacyl dithioimidocarbonates

N-Thioacyl dithioimidocarbonates undergo 1,2- and 1,4-cycloaddition reactions with active olefins, diphenylketen, and diphenyldiazomethane; the products obtained with the latter two reagents differ from those obtained in the reactions with a related conjugated system, thioacylketen thioacetal.