Terence Alan Hicks

Novel immunosuppressive butenamides

2-[4-(1,1-Dimethylethyl)phenyl]thiophene 12 was carboxylated using butyllithium and carbon dioxide to give 5-[4-(1,1-dimethylethyl)phenyl]thiophene-2-carboxylic acid 13. Conversion of the acid 13 using diphenyl phosphazidate and triethylamine gave 5-[4-(1,1-dimethylethyl)phenyl]thiophene-2-carbonyl azide 14, which was rearranged in toluene at 110 °C with loss of nitrogen to give the isocyanate 15; this in turn was treated with sodium 1-cyanoprop-1-ene 2-oxide 16 in tetrahydrofuran to give 2-cyano-N-{5-[4-(1,1-dimethylethyl)phenyl]thiophen-2-yl}-3-hydroxybut-2-enamide 17. Analogous chemistry has been utilised to synthesize both phenylheteroarylbutenamides and phenylbutenamides which display immunosuppressive activity towards proliferating concanavalin A-stimulated T-lymphocytes.

Heteroarene-fused benzodiazepines. Part 1. Synthesis of thieno-[2,3-b][1,5]-, -[3,2-b][1,5]-, and -[3,4-b][1,5]-benzodiazepinones

The synthesis of the 4H-thieno-[2,3-b][1,5]-, -[3,2-b][1,5]-, and -[3,4-b][1,5]-benzodiazepinone ring systems is described. Sodium methylsulphinylmethanide was used for the intramolecular cyclisation of the intermediate amino-esters (5), (9), and (14). However, attempted cyclisation of ethyl 2-(2-amino-4-fluoroanilino)-5-ethyl-thiophen-3-carboxylate (5b) with sodium hydride at a higher temperature caused rearrangement to a benzimidazolone (12).