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Natural-Abundance Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy. Steric and Electronic Effects on Nitrogen-15 Chemical Shifts of Piperidines and Decahydroquinolines

Duthaler, Rudolf O. and Williamson, Kenneth L. and Giannini, Donald D. and Bearden, William H. and Roberts, John D. (1977) Natural-Abundance Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy. Steric and Electronic Effects on Nitrogen-15 Chemical Shifts of Piperidines and Decahydroquinolines. Journal of the American Chemical Society, 99 (26). pp. 8406-8412. ISSN 0002-7863. doi:10.1021/ja00468a006.

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Natural-abundance ^(15)N-NMR chemical shifts of closely related methyl-substituted piperidines, decahydroquinolines, and their N-methyl derivatives have been measured in cyclohexane and methanol. For both solvents, the secondary amines and two groups of tertiary amines give separate linear correlations with the ^(13)C chemical shifts of their hydrocarbon analogues. Additive shift parameters for carbon substituents near nitrogen, similar to those which correlate ^(13)C chemical shifts, have been determined. Except for the N-alkylation parameters, these parameters are relatively solvent insensitive, at least for cyclohexane and methanol. Nonetheless, ^(15)N chemical-shift comparisons are best made for the same solvent or very similar solvents. A large shift effect results when substituents are changed which are antiperiplanar to the orbital of the unshared electrons of tertiary amines. The use of the additive shift parameters and the general correlation between ^(15)N and ^(13)C shifts with respect to analysis of conformational and structural changes is illustrated using N-methylpiperidine and cis-2,3-dimethylpiperidine as specific examples.

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Additional Information:© 1977 American Chemical Society. Received December 17, 1976. We are indepted to Dr. André Gagneux of Ciba Geigy A. G., Basel who provided a sample of 2-azaadaniantane, to Professor Robert T. LaLonde of the College of Environmental Science and Forestry of the State University of New York at Slracuse for the sample of 3-methylquinolizidine, and to Dr. Donald K. Dalling of the University of Utah for calculations of ^(13)C-chemical shifts of decalins. Supported by the Public Health Service, Research Grants No. GM-10224 and GM 11072, from the Division of General Medical Sciences, and by the National Science Foundation.
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U.S. Public Health Service (USPHS)GM-10224
U.S. Public Health Service (USPHS)GM-11072
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Caltech Gates and Crellin Laboratories of Chemistry5483
Issue or Number:26
Record Number:CaltechAUTHORS:20151008-070944424
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Official Citation:Natural-abundance nitrogen-15 nuclear magnetic resonance spectroscopy. Steric and electronic effects on nitrogen-15 chemical shifts of piperidines and decahydroquinolines Rudolf O. Duthaler, Kenneth L. Williamson, Donald D. Giannini, William H. Bearden, and John D. Roberts Journal of the American Chemical Society 1977 99 (26), 8406-8412 DOI: 10.1021/ja00468a006
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60890
Deposited By: Ruth Sustaita
Deposited On:08 Oct 2015 18:48
Last Modified:10 Nov 2021 22:41

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