Reactivity studies of phosphoric amides and esters

The effect of protonation and Lewis acid-base interaction on the ¹H n.m.r. chemical shifts of the ester and amide bonds in selected phosphoramidates (RO)₂P(O)NR'₂ was investigated. The results are interpreted in terms of the interaction of the phosphoryl oxygen atom with Lewis acids and oxygen/nitrogen diprotonation in trifluoromethanesulphonic acid. Intramolecular nucleophilic displacement of the halide ion from secondary β-chloroethyl-substituted phosphoramidates X₂P(O)NHCH₂CH₂Cl, diamidates (RO) (MeNH)P(O)NHCH₂CH₂Cl and β-chloroethyl phosphates Y(MeO)P(O)OCH₂CH₂Cl, was studied under conditions of electrophilic (Ag+) and basic (NaH) catalysis. 1,3-Substitution by the nitrogen atom of the phosphdramidates, yielding ethylenimine derivatives was found to be the preferred reaction-pathway; the alternative 1,5-reaction involving the amide nittogen or phosphoryl oxygen atoms was not observed. No intramolecular nucleophilic displacement occurred in the β-chloroethyl phosphate esters.

Grantor dc:publisher.institution

Department of Chemistry

Year dc:date.issued

1984

Author dc:creator

• Davidowitz, Bette

Advisor dc:contributor.advisor

• Modro, Tomasz A

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/11427/22276

OAI identifier oai:identifier

oai:open.uct.ac.za:11427/22276