Asinger reaction

The Asinger-reaction was invented in 1956 by Friedrich Asinger [1]. The Asinger-reaction is a multicomponent reaction and is classified as A-4CR (short for Asinger-4 component reaction):

An α-halogenated carbonyl-component reacts with sodium-hydrogensulfide NaSH and forms in situ a Thiole. The thiole reacts directly with another carbonyl-component and ammonia to form Thiazolines. The reaction works also by using sulphur, an in α–position substitutable ketone, a further carbonyl-component and ammonia under formation of mixtures[1].

The formation of 3-Thiazolines also occurs by using α-thioaldehyde or α-thioketone and ammonia[2].

A simplyfied route of the Asinger-reaction was developed by Degussa. An α-halogenated carbonyl-compound reacts with sodium hydrogensulfide NaSH and creates in situ Thioles, which reacts directly with aldehydes or ketones and ammonia to 3-thiazolines.[3]. The chemical industry developed based on the Asinger-reaction multi stage processes for the production of pharmaceuticals like D-Penicillamine[4] and the aminoacid DL-cysteine[5].

References

  1. ^ a b Friedrich Asinger: Über die gemeinsame Einwirkung von Schwefel und Ammoniak auf Ketone Angewandte Chemie 68 (1956) 413.
  2. ^ Friedrich Asinger and Manfred Thiel: Einfache Synthesen und chemisches Verhalten neuer heterocyclischer Ringsysteme, Angewandte Chemie 70 (1958) 667–683.
  3. ^ Karlheinz Drauz, Hans Günter Koban, Jürgen Martens and Werner Schwarze: Phosphonic and Phosphinic Acid Analogs of Penicillamine, Liebigs Annalen der Chemie 1985, 448-452.
  4. ^ Wolfgang Weigert, Heribert Offermanns and Paul Scherberich : D-Penicillamin - Herstellung und Eigenschaften, Angewandte Chemie 87 (1975) 372-378 ; Angewandte Chemie-International Edition 14 (1975) 330-336.
  5. ^ Jürgen Martens, Heribert Offermanns and Paul Scherberich : Eine einfache Synthese von racemischem Cystein, Angewandte Chemie 93 (1981) 680; Angewandte Chemie-International Edition 20 668 (1981).

Literature