A facile synthesis and spectral (ir, 1 H, 13 C, 31 P nmr) studies of 2,10‐dichloro‐6‐aryloxy‐12 H ‐dibenzo[ d,g ][1,3,2]dioxaphosphocin 6‐sulfides

The synthesis of new 2,10‐dichloro‐6‐aryloxy‐12 H ‐dibenzo[ d,g ][1,3,2]dioxaphosphocin 6‐sulfides 4 was achieved in two steps with high yields from the simple materials 5,5′‐dichloro‐2,2′‐dihydroxydiphenyl‐methane (1) and thiophosphoryl chloride (2) which produced the key intermediate 2,6,10‐trichloro‐12 H ‐dibenzo[ d,g ][1,3,2]dioxaphosphocin 6‐sulfide (3) . Treatment of 3 with substituted phenols under phase transfer catalytic (PTC) conditions led to members of 4 . Long range coupling [ 5 J (P,H) = 3.6 Hz] was observed between phosphorus and one of the bridged methylene protons in 4 . A 13 C nmr analysis revealed 2 J (P,O,C) , 3 J (P,O,C) 4 J(P,O,C) and 5 J(P,O,C) couplings. All 31 P nmr chemical shifts for thirteen members of these new heterocycles are reported for the first time. The nmr data are not totally definitive to confirm a boat‐chair as the major conformer for the central eight‐membered dioxaphosphocin ring, but such a conformer is tentatively suggested as favored.