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Dimethyl N-Aryl phosphoramidates : structural effects on bonding and solvolytic reactivity

Bibliography: p. 84-86. / The acid catalysed hydrolysis of a number of ring alkyl substituted dimethyl N-aryl phosphoramidates, (MeO)2P(0)NHAr, has been studied by measuring the rates of hyd~olysis with the aid of a UV spectrophotometer. These rates have been correlated with the pKa values of the corresponding ani I inium iOhs and the slope of this reactivitybasicity relationship for phosphoramidate with ortho substituents (6 = 0~85) is found to differ from that for substrates with meta and para substituents (S = 0,36). Determination of the thermodynamic parameters indicates that the entropy of activation is approximately constant for the substrates studied and the strongly negative values ~ -I -I (~S = 155,4 - 17,5 J mole K ) are consistent with an A2 type mechanism.

Identiferoai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:uct/oai:localhost:11427/13518
Date January 1981
CreatorsRijkmans, Bloys Peter
ContributorsModro, Tom A
PublisherUniversity of Cape Town, Faculty of Science, Department of Chemistry
Source SetsSouth African National ETD Portal
LanguageEnglish
Detected LanguageEnglish
TypeMaster Thesis, Masters, MSc
Formatapplication/pdf

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