ISSN:
0894-3230
Keywords:
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Reactions of morpholine in dimethyl sulphoxide at unsubstituted ring positions of 1,3,5-trinitrobenzene, and phenyl 2,4,6-trinitrophenyl ether, yield anionic σ-adducts via zwitterionic intermediates. Reactions at the 1-position of phenyl 2,4,6-trinitrophenyl ether, phenyl 2,4-dinitronaphthyl ether, and phenyl 2,4-dinitrophenyl ether result in substitution of the phenoxy groups. In both these reaction types proton-transfer is rate-limiting. Comparison of kinetic and equilibrium data with those for corresponding reactions of piperidine shows that rate constants for proton transfer are similar for the two amines, but equilibrium constants for zwitterion formation have lower values for morpholine, the less basic amine. Implications for base catalysis are discussed.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
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