97. Aza-ir-norbornadi&nes [l] par R. Kitzing. R. Fuchs, M. Joyeux et €1. Prinzbach Labratoire de Chimie organique, Universit6 de Lausanne (4 I\-68) Summavy. Several 7-aza-norbornadiene-derivatives have been synthesized. Their UV.-ant1 NMR.-data are reported.Les aza-7-norbornadihnes 2 sont les premiers produits de la voie de synth2se [Z] des aza-3-quadricyclanes substituks 3 ou des azCpines correspondantes 4, selon le schCma suivant :
“True” acyl anions would be desirable as synthetic reagents, but are inaccessible. Only some N,N‐disubstituted carbamoyllithium compounds such as (1), which have presumably ionic, angular structures, are persistent in solution. Further carbonylation of (1) affords interesting secondary products, e.g. hydroxymalonamide (2), N‐Monosubstituted lithium amides such as (3) rearrange to N‐lithioformamides (4) on carbonylation.
“True” acyl anions would be desirable as synthetic reagents, but are inaccessible. Only some N,N‐disubstituted carbamoyllithium compounds such as (1), which have presumably ionic, angular structures, are persistent in solution. Further carbonylation of (1) affords interesting secondary products, e.g. hydroxymalonamide (2), N‐Monosubstituted lithium amides such as (3) rearrange to N‐lithioformamides (4) on carbonylation.
Die COzCH3-und CF3-substituierten 7-Azanorbornadien-Dcrivate 3ai, 9 und 12 wurden synthetisiert. Direkte oder sensibilisierte Lichtanreguiig von 3a-i und 12 fuhrt in guten bis sehr guten Ausbeuten zu den isolierten (14ad, h; i, 20) bzw. nur indirekt (14e-g) nachgewiesenen 3-Azaquadricyclanen. Hingegen ist die Azaquadricyclan-Bildung bei der direkten Belichtung von 9 (X = N02) der Umwandlung aum 6-Aminofulven 19 deutlich untergeordnet. Uber eine thermische 3a + 3it-Spaltung sind die Azepine 15a-i, I und 16h, i zuganglich. Der EinfluB der Nund C-Substituenten auf die Leichtigkeit und Richtung dcr Azaquadri-cyclan+Azepin-Isomerisierulig sowie generell die Grenzen dieser Azepin-Synthese werden diskutiert.
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