A number of 4,5‐dihydrobenzo[e]imidazo[2,1‐c][1,4,2]diazaphosphinine derivatives were prepared by the direct phosphorylation of 1‐(4‐Chlorophenylcarboxamido)‐2‐(1H‐1‐imidazolyl)‐5‐trifluoromethylbenzene in basic medium with phosphorus(III) bromide and dibromophenylphosphine. The tricyclic compounds 6a, 6b, and 9 having a trivalent phosphorus atom undergo the diazaphosphinine ring opening upon treatment with secondary amines in the presence of sulfur. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:84–92, 2002; DOI 10.1002/hc.10000