ISSN:
0009-2940
Keywords:
Aminotroponimines, crystal structure
;
N-Alkylidenepropanedinitrile groups, migration of
;
Nucleophilic substitution at C=C bonds
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Tautomerism of N-substituted Aminotroponimines with N-Alkylidenepropanedinitrile Groups - Examples for stable Intermediates of a Nucleophilic Substitution at a C=C BondThe reaction of N,N′-dimethyl-7-iminotroponamine 1a with (1-chloroalkylidene)propanedinitriles such as 5 and 7 gives rise to products with different structures (e. g. 6 and 8). Only with (α-chlorobenzylidene)- and (chloromethylene)propanedinitrile (9a, b) the N-substitution products 10 are formed. According to an X-ray analysis these exist exclusively in the bicyclic form 10B. A rapid migration of the (N-alkylidene)propanedinitrile group between both nitrogen atoms does not take place. Therefore 10B is the stable intermediate of a nucleophilic substitution at a C=C bond.
Notes:
Die Umsetzung des N,N′-Dimethyl-7-iminotroponamins 1a mit (1-Chloralkyliden)propandinitrilen wie 5 und 7 führt zu Produkten mit unterschiedlicher Struktur (z. B. 6 und 8). Lediglich mit (α-Chlorbenzyliden)- und (Chlormethylen)propandinitril (9a, b) entstehen die N-Substitutionsprodukte 10, die laut Röntgenstrukturanalyse in der bicyclischen Struktur 10B vorliegen. Eine schnelle Wanderung der N-Alkylidenpropandinitril-Gruppe zwischen beiden N-Atomen findet nicht statt. 10B ist somit das stabile Zwischenprodukt der nucleophilen Substitution an einer C=C-Bindung.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19891220619
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