ISSN:
0009-2940
Keywords:
α1-Cyanodiazonium ions
;
α1-Cyanoalkyl radicals
;
Carbocations, destabilized
;
Substitution, nucleophilic
;
Deamination reactions
;
Diazonium ions
;
Radicals
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Deamination Reaction, 54[1]. - Decomposition of 1-Cyano-1-propanediazonium IonsThe nitrous acid deamination of 2-aminobutanenitrile (9) was studied with regard to product distribution and stereochemistry. The formation of 2-(hydroxyimino)butanenitriles (21, 22; 8 - 28%) indicates the intervention of 1-cyanopropyl radicals (24) that are captured by NO. The polar reactions lead mainly to elimination (10 - 13) and nucleophilic substitution (14 - 16), rearrangement playing a minor role. (R)-9 was prepared from (R)1-2-aminobutanoic acid. The nitrous acid deamination of (R)-9 afforded the cyanohydrin 16 with 81% net inversion. Owing to destabilization of the carbocation 26 by CN, the SN2 route of nucleophilic displacement is preferred over SN1. The influence of CN is shown to be smaller than that of CF3.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260636
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