Various 4-and 4, 5-substituted 2, 7-di-tert-butylthiepins such as 4-ethoxycarbonyl-(6), 4- formyl-(7), 4-hydroxymethyl-(8), 4-methyl-(12), 4-methy1-5-hydroxymethy1-(13), and 4, 5- dimethyl derivatives (16), and so on, were synthesized by functional group transformation and some of their properties were examined.