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Desaminierungsreaktionen, 54. Zerfall von 1‐Cyan‐1‐propandiazonium‐Ionen
Author(s) -
Bunse Michael,
Kirmse Wolfgang
Publication year - 1993
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19931260636
Subject(s) - chemistry , deamination , nitrous acid , nucleophile , carbocation , medicinal chemistry , cyanohydrin , nucleophilic substitution , stereochemistry , organic chemistry , enzyme , catalysis
Deamination Reaction, 54 [1] . – Decomposition of 1‐Cyano‐1‐propanediazonium Ions The 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 S N 2 route of nucleophilic displacement is preferred over S N 1. The influence of CN is shown to be smaller than that of CF 3 .