Studies on 3-Oxoalkanenitriles Novel Rearrangement Reactions Observed in Studies of the Chemistry of 3-Heteroaroyl-3-Oxoalkanenitriles as Novel Routes to 2-Dialkylaminopyridines 英文参考文献.docVIP

Molecules 2012, 17, 897-909; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Studies on 3-Oxoalkanenitriles: Novel Rearrangement Reactions Observed in Studies of the Chemistry of 3-Heteroaroyl-3- Oxoalkanenitriles as Novel Routes to 2-Dialkylaminopyridines Hamad M. Al-Matar 1,*, Khaled D. Khalil 1,2, Mona F. Al-Kanderi 1 and Mohamed H. Elnagdi 1 1 Chemistry Department, Faculty of Science, University of Kuwait, P.O. Box 5969, Safat 13060, Kuwait 2 Chemistry Department, Faculty of Science, Cairo University, Giza 12613, Egypt * Author to whom correspondence should be addressed; E-Mail: h.almatar@.kw. Received: 1 December 2011; in revised form: 16 January 2012 / Accepted: 16 January 2012 / Published: 18 January 2012 Abstract: 3-Aroyl and 3-heteroaroyl substituted 3-oxoalkanenitriles were synthesized by the reactions of activated aromatic and hetero-aromatic substances with cyanoacetic acid in the presence of acetic anhydride. As part of studies focusing on the preparation of cyanoacetyl-1-N-methylbenzimidazole, we observed that reaction of N-methyl-benzimidazole with the cyanoanhydride formed by condensation of cyanoacetic acid with acetic anhydride, leads to the formation of 2-(1,3-diacetyl-2,3-dihydro-1H- benzo[d]-imidazol-2-yl)acetonitrile (5), whose structure was confirmed by X-ray crystallographic analysis. 3-Oxoalkanenitriles 3a,b were observed to undergo condensation reactions with dimethylformamide dimethyl acetal (DMFDMA) to afford the corresponding enamino-nitriles, which react with malononitrile to give 2-dialkylaminopyridines through a pathway involving a new, unexpected rearrangement process. Reactions of 3-oxoalkanenitriles with ethyl acetoacetate were found to afford 2-oxopyran-3-carbonitriles, also occurring via this unexpected rearrangement process. Mechanisms to account f