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Title: Amination of the pyridinium cations in betaines. Synthesis of substituted pyrimido(5,6-c)-1'-azaquinolizine and its dihydro analogs

Abstract

The pyridinium cations within betaines can be aminated under mild conditions with aqueous ammonia, ultimately undergoing cyclization to a new tricyclic system: 4-substituted-3,5-dioxopyrimido(5,6-c)-1'-azaquinolizine. Intermediates in the reaction are 4-substituted-3,5-dioxo-2,2-dihydropyrimido(5,6-c)-6H-1'-quinolizines. Formation of the methylene group is coupled with transfer of an atom of hydrogen or deuterium from the ..cap alpha..-carbon of the dihydropyridine in compound II to the carbon atom of the azomethine group. The NMR spectrum is represented by the methylene proton signal (3.96 ppm) and by the multiplets of the pyridine and phenyl protons centered at 7.63 and 6.38 ppm respectively. Upon chloranil oxidation, and upfield shift of the pyridine protons is observed: the ..cap alpha..-proton forms a doublet (10.05 ppm, J= 6 Hz), the ..beta..-protons form a doublet and a triplet with centers at 8.57 (J = 8 Hz) and 8.22 (J = 7 Hz) ppm respectively, and the ..gamma..-proton forms a triplet at 8.8 (J = 7 Hz) ppm.

Authors:
;
Publication Date:
Research Org.:
Institute of Physical Organic Chemistry and Coal Chemistry, Donetsk (USSR)
OSTI Identifier:
7005042
Resource Type:
Journal Article
Journal Name:
Chem. Heterocycl. Compd. (Engl. Transl.); (United States)
Additional Journal Information:
Journal Volume: 23:5; Other Information: Translated from Khim. Geterotsikl. Soedin.; 23: No. 5, 677-680(May 1987)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; PYRIDINIUM COMPOUNDS; AMINATION; DEHYDROCYCLIZATION; PYRIMIDINES; NMR SPECTRA; SYNTHESIS; QUINOLINES; AMMONIA; BETAINE; CHEMICAL SHIFT; COUPLING CONSTANTS; DEUTERIUM; HYDROGEN TRANSFER; ISOMERIZATION; ISOTOPIC EXCHANGE; J-J COUPLING; MULTIPLETS; REACTION INTERMEDIATES; AMINES; AMINO ACIDS; AMMONIUM COMPOUNDS; AROMATICS; AZAARENES; AZINES; CARBOXYLIC ACIDS; CHEMICAL REACTIONS; COUPLING; DRUGS; HETEROCYCLIC COMPOUNDS; HYDRIDES; HYDROGEN COMPOUNDS; HYDROGEN ISOTOPES; INTERMEDIATE COUPLING; ISOTOPES; LIGHT NUCLEI; LIPOTROPIC FACTORS; NITROGEN COMPOUNDS; NITROGEN HYDRIDES; NUCLEI; ODD-ODD NUCLEI; ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PYRIDINES; QUATERNARY COMPOUNDS; SPECTRA; STABLE ISOTOPES; 400201* - Chemical & Physicochemical Properties; 640302 - Atomic, Molecular & Chemical Physics- Atomic & Molecular Properties & Theory

Citation Formats

Kochkanyan, R O, and Lukanyuk, S S. Amination of the pyridinium cations in betaines. Synthesis of substituted pyrimido(5,6-c)-1'-azaquinolizine and its dihydro analogs. United States: N. p., 1987. Web. doi:10.1007/BF00476389.
Kochkanyan, R O, & Lukanyuk, S S. Amination of the pyridinium cations in betaines. Synthesis of substituted pyrimido(5,6-c)-1'-azaquinolizine and its dihydro analogs. United States. https://doi.org/10.1007/BF00476389
Kochkanyan, R O, and Lukanyuk, S S. 1987. "Amination of the pyridinium cations in betaines. Synthesis of substituted pyrimido(5,6-c)-1'-azaquinolizine and its dihydro analogs". United States. https://doi.org/10.1007/BF00476389.
@article{osti_7005042,
title = {Amination of the pyridinium cations in betaines. Synthesis of substituted pyrimido(5,6-c)-1'-azaquinolizine and its dihydro analogs},
author = {Kochkanyan, R O and Lukanyuk, S S},
abstractNote = {The pyridinium cations within betaines can be aminated under mild conditions with aqueous ammonia, ultimately undergoing cyclization to a new tricyclic system: 4-substituted-3,5-dioxopyrimido(5,6-c)-1'-azaquinolizine. Intermediates in the reaction are 4-substituted-3,5-dioxo-2,2-dihydropyrimido(5,6-c)-6H-1'-quinolizines. Formation of the methylene group is coupled with transfer of an atom of hydrogen or deuterium from the ..cap alpha..-carbon of the dihydropyridine in compound II to the carbon atom of the azomethine group. The NMR spectrum is represented by the methylene proton signal (3.96 ppm) and by the multiplets of the pyridine and phenyl protons centered at 7.63 and 6.38 ppm respectively. Upon chloranil oxidation, and upfield shift of the pyridine protons is observed: the ..cap alpha..-proton forms a doublet (10.05 ppm, J= 6 Hz), the ..beta..-protons form a doublet and a triplet with centers at 8.57 (J = 8 Hz) and 8.22 (J = 7 Hz) ppm respectively, and the ..gamma..-proton forms a triplet at 8.8 (J = 7 Hz) ppm.},
doi = {10.1007/BF00476389},
url = {https://www.osti.gov/biblio/7005042}, journal = {Chem. Heterocycl. Compd. (Engl. Transl.); (United States)},
number = ,
volume = 23:5,
place = {United States},
year = {Sun Nov 01 00:00:00 EST 1987},
month = {Sun Nov 01 00:00:00 EST 1987}
}