Untersuchungen über Umlagerungen. III

Abstract

Unter der allmiihlig ziemlich angewachsenen Zahl sogenaqnter Umlagerungsreactionen , von denen weitaus die meisten eich durch Abspaltung gewisser Atomgruppen und Wiederanlagerung derselben in anderer Anordnung erkliiren, befinden sich einige, welche dem chemischen Verstiindniss znr Stunde noch vollig unroghglich sind.Dies gilt wohl von keiner Umsetzung in hoherem Maase, als von der von L i n n e m a n n und v. Z o t t a g ) beschriebeoen Umwandlung des n o r m a l e n B u t y l a m i n s in p r i m a r e n I s o b u t y l a l k o h o l durch salpetrige Siiure, welche nach der Oleichung verlaofen 8011:

Formation of heterocyclic N-nitrosamines from the reaction of nitrite and selected primary diamines and amino acids

“…As shown in Table V, yields in solution at 100°were extremely low, but in the low moisture system at 160°, 1% of the nitrosamine was obtained. The identification of DBNA as a reaction product confirms the finding of Meyer et al (1877) who reported DBNA, in addition to butylene and butanol, as reaction products of butylamine and nitrite. The mechanism of DBNA formation involves dimerization rather than cyclization and represents nitrosamine formation from a primary monoamine.…”

“…Several investigations have presented evidence, however, that some primary amines may produce nitrosamines when allowed to react with nitrite under certain conditions. Early studies by von Linnemann (1872) demonstrated that dipropylnitrosamine (DPNA) was a product of the propylamine-nitrite reaction and Meyer et al (1877) determined that dibutylnitrosamine (DBNA) was a product of the butylamine-nitrite reaction. Adamson and Kenner (1934) also found dialkylnitrosamines resulted from the action of nitrite on various primary aliphatic amines.…”