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Contents Vol 68(2)

Reactions of Methyl Ketones and (Hetero)arylcarboxamides with N,N-Dimethylacetamide Dimethyl Acetal. A Simple Metal-Free Synthesis of 2,4,6-Trisubstituted Pyridines*

Benjamin Prek A B , Uroš Grošelj A , Marta Kasunič A , Silvo Zupančič C , Jurij Svete A B and Branko Stanovnik A B D
+ Author Affiliations
- Author Affiliations

A Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, PO Box 537, 1000 Ljubljana, Slovenia.

B EN-FIST Center of Excellence, Trg OF 13, 1000 Ljubljana, Slovenia.

C FARMA GRS, Seidlova cesta 70, 8000 Novo mesto, Slovenia.

D Corresponding author. Email: branko.stanovnik@fkkt.uni-lj.si

Australian Journal of Chemistry 68(2) 184-195 https://doi.org/10.1071/CH14349
Submitted: 30 May 2014  Accepted: 19 June 2014   Published: 3 September 2014

Abstract

Two metal-free syntheses of 2,4,6-trisubstituted pyridines 10a–m and 16a–j are described. N,N,6-Trimethyl-4-(substituted)pyridin-2-amines 10 were prepared from aryl or heteroaryl methyl ketones which were transformed with N,N-dimethylacetamide dimethyl acetal (DMADMA) into enaminones 4a–m, followed by treatment with ammonium acetate to give (Z)-3-amino-1-(substituted)but-2-en-1-ones 5a–m. These were treated with DMADMA under microwave irradiation in a closed vessel at 130°C, to give via intermediates 7–9 the final products 10a–m. N2,N2,N4,N4-Tetramethyl-6-(substituted) pyridine-2,4-diamines 16a–j were prepared in a one-pot synthesis from the corresponding carboxamides 11a–j by treatment with an excess of DMADMA in a closed vessel under microwave irradiation to give via intermediates 12a–j to 15a–j the final products 16a–j. X-Ray single crystal diffractometry studies of the enaminones 5c, 5g, 5i, 5j, and 5m and 2,4,6-trisubstituted pyridines 16a, 16b, 16g, 16i, and 16j were consistent with the expected structures.


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