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Mechanism of the Reaction of Amines with 5‐[(Aryl‐ or Alkylamino)hydroxymethylene]‐2,2‐dimethyl‐1,3‐dioxane‐4,6‐diones in the Presence of Chlorotrimethylsilane (Me 3 SiCl)
Author(s) -
Janikowska Karolina,
Makowiec Sławomir,
Rachoń Janusz
Publication year - 2013
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201200326
Subject(s) - chemistry , amine gas treating , nucleophile , medicinal chemistry , aryl , meldrum's acid , reaction mechanism , organic chemistry , stereochemistry , catalysis , alkyl
Addition of chlorotrimethylsilane (Me 3 SiCl) to the mixture of a carbamoyl‐substituted Meldrum 's acid, i.e. , a 5‐[(arylamino)hydroxymethylene]‐2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione of type 1 and a secondary amine as nucleophile strongly accelerated the rate of their reaction. The reason for this phenomenon observed, during our previous research, remained, however, unclear. To elucidate the mechanism of this reaction, we assumed and verified three possible pathways for the action of Me 3 SiCl ( cf. Scheme 2 ): The acceleration of the reaction is caused i ) by formation of a O ‐trimethylsilylated Meldrum 's acid of type 2 , ii ) by the silylated amine 3 , or iii ) by the presence of HCl liberated from Me 3 SiCl. The performed experiments revealed that the faster course of reaction is caused by the formation of N ‐trimethylsilylated amines of type 3 .