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Solvation and metal ion effects on structure and reactivity of phosphoryl compounds. 1. β‐substituted alkylphosphonic esters
Author(s) -
Belciug MarieP.,
Modro Agnes M.,
Modro Tom A.,
Wessels Philippus L.
Publication year - 1992
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610051203
Subject(s) - chemistry , intramolecular force , substituent , reactivity (psychology) , solvation , hydrogen bond , metal , medicinal chemistry , magnesium , chelation , selectivity , acceptor , stereochemistry , ion , organic chemistry , molecule , catalysis , medicine , physics , alternative medicine , pathology , condensed matter physics
NMR spectroscopic and conformational analyses were performed for three β‐substituted β‐phenylethylphosphonic esters, PhCHXCH 2 PO 3 Me 2 (X = OH, OMe, Cl) in five solvents and in acetone containing sodium and magnesium salts. Strong attractive interactions between the phosphoryl group and the oxygen‐containing substituent X were demonstrated, and were shown to involve intramolecular hydrogen bonding, donor‐acceptor O → P effect and the chelation of a metal ion. These effects led to marked selectivity in the population of individual conformations of the phosphonates. The analogous intramolecular effects were found to be much weaker in the corresponding carboxylic ester systems.