Aqueous high-temperature chemistry of carbo- and heterocycles .24. First demonstration of specific C-C bond scission of the pyridine ring, reactions of piperidine, pyridine and some of their methyl derivatives in aqueous formic acid

Tn its reactions with the title compounds, formic acid variously acts as a formylating, methylating, and reducing agent. Both pyridine and piperidine are converted in significant amounts into 1-methyl-, 1-ethyl-, 1-propyl- and 1-pentyl-piperidines. Of the N-alkyl groups, isotopic labeling shows that...

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Published inJournal für praktische Chemie, Chemiker-Zeitung Vol. 338; no. 3; pp. 220 - 230
Main Authors Katritzky, AR, Parris, RL, Ignatchenko, ES, Balasubramanian, M, Barcock, RA, Siskin, M
Format Journal Article
LanguageEnglish
Published HEIDELBERG JOHANN AMBROSIUS BARTH VERLAG 01.01.1996
Subjects
Chemistry
Chemistry, Applied
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
CARBOCYCLES
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Summary:Tn its reactions with the title compounds, formic acid variously acts as a formylating, methylating, and reducing agent. Both pyridine and piperidine are converted in significant amounts into 1-methyl-, 1-ethyl-, 1-propyl- and 1-pentyl-piperidines. Of the N-alkyl groups, isotopic labeling shows that only N-methyl derives from the formic acid, while the N-ethyl and N-propyl arise from heterocyclic ring C-C bond scission by retro-vinylogous-bis-aza-Aldol reactions. Detailed analysis of the products for pyridine, piperidine, and their 4-methyl derivatives, reacted separately and mixed, supports mechanisms in which a piperidine adds 1,2 to a pyridinium cation, or to a di- or tetra-hydropyridine, to initiate reaction sequences leading to the product slates found.
ISSN:0941-1216
DOI:10.1002/prac.19963380146