ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The occurrence of so-called synchronous 7-centre-fragmentation has been excluded for γ-amino-ketoxime derivatives N—C—C—C—C=N—X. Fragmentation may occur, however, by another route.Reaction rates of the p-toluenesulfonates of (4-quinuclidinyl)-methyl-ketoxime (10b) and (3β-tropanyl)-methyl-ketoxime (14b) in 80% ethanol and the resulting products have been determined. Whereas the latter γ-aminoketoxime underwent quantitative BECKMANN rearrangement to 3β-acetylaminotropane (29), the former yielded 3% fragmentation products besides rearranged 4-acetylamino-quinuclidine (13).A kinetic study reveals that both 10b and 14b react via the rearranged nitrilium ions 12a and 16a, respectively. In the case of the N-(4-quinuclidinyl)-acetonitrilium ion (12a) 5-centre-fragmentation competes with hydration to the amide 13.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19680510116
