ISSN:
1573-8353
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract The reaction of O-tosyloximes of acetone, hexafluoroacetone, and mesoxalic acid esters with alkoxyamines leads to the corresponding diazirines, while the reaction of benzophenone O-tosyloxime with methoxyamine gives only benzophenone O-methyloxime. O-Esters of acetoxime were isolated along with 3,3-dimethyldiazirine also in the reaction of O-tosylacetoxime with alkoxyamines. Nucleophilic attack of alkoxyamines on O-tosyloximes of mesoxalates is realized at the carbon atom of not only the C=O bond but also at the carbon atom of the C=O bond, and the latter leads to fragmentation of the O-tosyloxime to give N-alkoxycarbamates, a cyanocarbonate ester, and p-toluenesulfonic acid. In the presence of triethylamine, which blocks the C=N bond, the reaction of the mesoxalate O-tosyloxime proceeds only via the fragmentation pathway. The mechanism of the formation of diazirines in the reaction of O-tosylketoximes with alkoxyamines is discussed.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00503487
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