ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Nitrone formation from furfural and 5-nitrofurfural with phenylhydroxylamine was studied in water at 25°C and ionic strength 1·0 (KCl). The reaction exhibits general acid catalysis (α = 0·52), specific base catalysis and a pH-independent process. The results are consistent with a mechanism where dehydration of an N,N′-dihydroxy addition intermediate, formed by a rapid pre-equilibrium, is the only rate-determining step over the pH range studied (1-11). In contrast, nitrone formation from p-chlorobenzaldehyde and N-methylhydroxylamine exhibits a clear change of rate-determining step, from dehydration of the addition intermediate to attack of the nucleophile on the aldehyde, with increase in pH. The profile of log k2 (k2 = second-order rate constant) vs pH indicates, by comparison with the corresponding profile for similar reaction, that phenylhydroxylamine exhibits unexpected nucleophilic behaviour in this reaction. The pH-indpendent dehydration process, which has a higher rate constant than that predicted from the Brønsted line for the water catalysis, appears to involve intramolecular catalysis rather than bifunctional catalysis by water.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610030911
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