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Structure of products from reactions of phosphorus pentachloride with phenyl salicylate and 2‐hydroxybenzophenone; related compounds. p31 N.M.R. and chemical studies
Author(s) -
Pinkus A. G.,
Waldrep P. G.,
Ma S. Y.
Publication year - 1965
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.5570020407
Subject(s) - phosphorus pentachloride , chemistry , triethylamine , phenol , phosphorus , chemical structure , organic chemistry , hydrolysis , medicinal chemistry , chemical shift
The compounds obtained from the reactions of phenyl salicylate and 2‐hydroxybenzo‐phenone with phosphorus pentachloride have been shown to have structures I A and II A, respectively, rather than alternative heterocyclic structures on the basis of the comparison of the P 31 chemical shifts with appropriate reference compounds and additional chemical evidence. Compound I reacts with two equivalents of phenol in the presence of two equivalents of triethylamine to form mainly compound VIII (substitution on phosphorus). Structure VIII is confirmed via P 31 n.m.r. and IR spectra and the fact that partial hydrolysis forms the same compound (VII) that is obtained from the reaction of compound III with phenol (only phosphorus substitution possible). A mechanism with initial reaction of phosphorus pentachloride (as tetrachlorophosphonium ion) on the phenolic hydroxyl is postulated on the basis of the available evidence. The P 31 chemical shifts for compounds XIV A and XV A confirm these structures as heterocyclic in accord with previous chemical evidence. Structure XIV A is of historical importance as one of the first three cyclic structures ever published in the classical paper in which Couper announced his structural theory of organic chemistry.