The synthetic pathway to 5-carbethoxythieno [3, 2-b] pyrrole has been improved and a new product isolated from its reaction with formaldehyde and dimethylamine. Several 6- substituted 5-carbethoxythieno [3, 2-b] pyrrole Compounds have been hydrolyzed and decarboxylated under mild conditions to afford important intermediates for the preparation of thieno [3, 2-b] pyrrole analogs of natural indole compounds.