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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
Author(s) -
Devendranath Reddy C.,
Mallikarjuna Reddy P.,
Ramasubba Reddy D.,
Nagalakshmamma M.,
Anuradha K.,
Raju C. Naga,
Berlin K. Darrell,
Couch Kevin M.,
Tyagi Sameer
Publication year - 1995
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570320512
Subject(s) - chemistry , methylene , conformational isomerism , nuclear magnetic resonance spectroscopy , sulfide , medicinal chemistry , ring (chemistry) , nmr spectra database , proton nmr , chloride , carbon 13 nmr , chemical shift , stereochemistry , crystallography , spectral line , organic chemistry , molecule , physics , astronomy
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.