Institute of Fine Organic Chemistry of A. L. Mnjoyan, Scientific Technological Center of Organic and Pharmaceutical Chemistry of National Academy of Science of Republic of Armenia, Ave. Azatutyan 26, Yerevan 0014, Armenia.
Dipartimento di Chimica G. Ciamician, Alma Mater Studiorum-Università di Bologna, Via F. Selmi 2, 40126 Bologna, Italy.
Int J Mol Sci. 2024 Nov 7;25(22):11977. doi: 10.3390/ijms252211977.
Herein we describe the synthesis and rearrangement of 1,3-diamino-2,7-naphthyridines and 1-amino-3-oxo-2,7-naphthyridines. In the case of 1,3-diamino-2,7-naphthyridines, it was found that the rearrangement reaction was influenced by both the substituent at the 7th position of the 2,7-naphthyridine ring and by the nature of the cyclic amine at the 1st position. The influence was mainly steric. The reaction of 1-amino-3-oxo-2,7-naphthyridines with amines was studied for the first time. It was revealed that for these substrates, the rearrangement occurs faster and without any influence of the alkyl and cyclic amine groups. We also observed the nucleophilic addition of the amine to the carbonyl group of the rearranged product with the formation of a Schiff base. The calculation of the ESP charges on these substrates indicates a considerable increase in the positive charge on the cyano group that suffers the nucleophilic attack during the rearrangement process, possibly explaining its increased tendency to react and to have a higher reaction velocity.
在此，我们描述了 1,3-二氨基-2,7-萘啶和 1-氨基-3-氧代-2,7-萘啶的合成和重排反应。对于 1,3-二氨基-2,7-萘啶，发现重排反应受到 2,7-萘啶环第 7 位取代基和第 1 位环状胺的性质的影响。这种影响主要是立体的。我们还首次研究了 1-氨基-3-氧代-2,7-萘啶与胺的反应。结果表明，对于这些底物，重排发生得更快，并且不受烷基和环状胺基团的影响。我们还观察到胺对重排产物的羰基的亲核加成，形成席夫碱。对这些底物的 ESP 电荷的计算表明，在重排过程中遭受亲核攻击的氰基上的正电荷显著增加，这可能解释了其增加的反应趋势和更高的反应速度。
