Synthese und Reaktionen des 5-[p-(Dimethylamino)phenyl]-2,2-dimethyl-4-phenyl-3-oxazolins

Synthesis and Reactions of 5-[p-(Dimethylamino)phenyl]-2,2-dimethyl-4-phenyl-3-oxazoline The title compound 8 has been synthesized in a one-pot reaction of 4′-(dimethylamino)benzoin ( 4 ) with 2-propanone and NH₃. The preparation of the intermediate 4 from 3 is the first example of an acid-catalyzed transformation of the stable benzoin 3 into the corresponding less stable benzoin 4 . Structures and yields of various by-products occurring under different reaction conditions during the synthesis of 8 from 4 are given. The O-atom of the 3-oxazoline ring in 8 could be replaced by S from P₂S₅ yielding the 3-thiazoline 14 . Separation of the enantiomers of the racemate 8 could only be performed by transforming them into the trimethylanilinium salts 8b and 8c of (−)- and (+)-10-camphorsulfonic acid, respectively. Solid NaOAc in boiling toluene caused the precipitation of the 10-camphorsulfonic acids from the quaternary ammonium salts as sodium salts and the removing of the third methyl group from the quaternary ammonium salts as AcOMe to give the enantiomers (−)-(5S)- 8 and (+)-(5R)- 8 . Their absolute configurations are deduced from an X-ray analysis of 8b .