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Steric and Electronic Effects on ^(15)N Chemical Shifts of Piperidine and Decahydroquinoline Hydrochlorides

Duthaler, Rudolf O. and Roberts, John D. (1978) Steric and Electronic Effects on ^(15)N Chemical Shifts of Piperidine and Decahydroquinoline Hydrochlorides. Journal of the American Chemical Society, 100 (12). pp. 3882-3889. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20151008-070942817

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Abstract

Natural-abundance ^(15)N NMR chemical shifts of a number of closely related C- and N-methyl-substituted piperidine and decahydroquinoline hydrochlorides have been measured in chloroform and methanol. For each solvent, the ^(15)N shifts of the salts of secondary and tertiary amines give different linear correlations with the ^(13)C shifts of the corresponding carbons of their hydrocarbon analogues. Additive shift parameters as well as protonation-shift parameters for carbon substitution near nitrogen have been determined. Three of the nine parameters have a pronounced solvent dependence. The substituent-shift parameters for hydrochlorides are in general closer to the analogous values for ^(13)C NMR than the corresponding parameters which correlate the I5N shifts of the free amines. The parameters for substitution on @carbons are an exception. The ^(13)C shifts of some of the compounds can be used to elucidate conformational questions.


Item Type:Article
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http://dx.doi.org/10.1021/ja00480a037DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00480a037PublisherArticle
Alternate Title:Steric and electronic effects on nitrogen-15 chemical shifts of piperidine and decahydroquinoline hydrochlorides
Additional Information:© 1978 American Chemical Society. Received August 12, 1977. We wish to thank Professor M. Allen for providing a very useful computer program doing least-squares multilinear regression analysis, and Professor K. L. Williamson for preparing and measuring the shifts of 8-(e)-methyltrans-decahydroquinoline. We are also indebted to Dr. André Gagneux of Ciba-Geigy AG, Basel, who provided a sample of 2-azaadamantane, to Professor Robert T. LaLonde of the College of Environmental Science and Forestry, State University of New York at Syracuse, for the sample of 3-methylquinolizidine, and to Dr. D. K. Dalling of the University of Utah for calculations of ^(13)C chemical shifts of decalins. Supported by the National Science Foundation, and by the Public Health Service, Research Grant GM-11072 from the Division of General Medical Sciences.
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U.S. Public Health Service (USPHS)GM-11072
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Caltech Gates and Crellin Laboratories of Chemistry5647
Issue or Number:12
Record Number:CaltechAUTHORS:20151008-070942817
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151008-070942817
Official Citation:Steric and electronic effects on nitrogen-15 chemical shifts of piperidine and decahydroquinoline hydrochlorides Rudolf O. Duthaler and John D. Roberts Journal of the American Chemical Society 1978 100 (12), 3882-3889 DOI: 10.1021/ja00480a037
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60885
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:08 Oct 2015 18:13
Last Modified:03 Oct 2019 09:01

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