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- Title
Von der basenkatalysierten Ringöffnung von 2 H-Azirinen zu einer α-Alkylierungsmethode von primären Aminen.
- Authors
Schulthess, Adrian Heinz; Hansen, Hans-Jürgen
- Abstract
From a Base Catalyzed Ring Opening of 2 H-Azirines to an α-Alkylation Method of Primary Amines It is shown that fluorene-9′-spiro-2-(3-phenyl-2 H-azirine) ( 1) on treatment with various alcohols in the presence of the corresponding alkoxide ions yields N-(9′-fluorenyl)benzimidates 2a-d (Scheme 1). 2,2,3-Triphenyl-2 H-azirine ( 3) reacts with methanol in a similar manner (Scheme 2). Benzimidates 2a (Scheme 3), 8 (Scheme 4) and and 10 (Scheme 5) can easily be deprotonated by butyllithium (BuLi) or lithium diisopropylamide (LDA) in tetrahydrofuran (THF) to 1-methoxy-2-aza-allylanions, that can be alkylated, at C(3), exclusively, by various electrophiles ( e.g. R-X(X = I, Br), RCHO or methyl acrylate (see also Scheme 6)). As the acidic hydrolyses (1 N HCl) of benzimidates 9 and 11 leads to the corresponding α-alkylated free amines 15 and 18 ( Scheme 7 and 8), benzoyl derivatives 16 and 19 are obtained from the hydrolysis under basic conditions. On the other hand, it is observed that a catalyzed Chapman rearrangement of 9 and 11 results in the formation of N-benzoyl- N-methyl derivatives 17 and 20 (Scheme 7 and 8). The described reactions offer a simple method for the α-alkylation of activated primary amines.
- Publication
Helvetica Chimica Acta, 1981, Vol 64, Issue 5, p1322
- ISSN
0018-019X
- Publication type
Article
- DOI
10.1002/hlca.19810640509