AbstractReplacement of C‐4 with a hetero substituent (NR,O,S) in the 1‐vinyl‐3,4‐dihydronaphthalene system has provided a new type of diene for participation in the McCormack cycloaddition reaction with P(III) halides. The tricyclic phospholene oxides so obtained are the first to bear an additional heteroatom in the ring system. 1,2‐Dihydro‐7‐methoxy‐1‐(p‐toluenesulfonyl)‐4‐vinylquinoline is a stable solid that reacts with methylphosphonous dichloride to give, after hydrolysis of the cycloadduct, the 1,2,4,5‐tetrahydro‐1H‐phospholo‐[2,3‐c]quinoline ring system. The dihydroquinoline moiety was aromatized by detosylation with potassium t‐butoxide. The tendency of 4‐vinyl‐2H‐benzopyran to dimerize was a serious complication in its use, and the cycloaddition with methylphosphonous dichloride proceeded only in low yield. The product, a 2,3,3a,4‐tetra‐hydrobenzo[3,2‐d]pyran derivative, was a stable, easily purified and characterized substance. 4‐Vinyl‐2H‐benzo[b]thiopyran was more stable than the pyran, but the phospholo derivative from reaction with methylphosphonous dichloride was more difficult to purify. All products were characterized by 13C‐nmr spectroscopy.