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Small-Ring Compounds. XLVII. Reactions of Optically Active Cyclopropylmethylcarbinyl Derivatives

Vogel, Martin and Roberts, John D. (1966) Small-Ring Compounds. XLVII. Reactions of Optically Active Cyclopropylmethylcarbinyl Derivatives. Journal of the American Chemical Society, 88 (10). pp. 2262-2271. ISSN 0002-7863. doi:10.1021/ja00962a033.

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Cyclopropylmethylcarbinylamine and cyclopropylmethylcarbinol were resolved into optical antipodes and their configurations were related. The former was deaminated with aqueous nitrous acid to give the latter with 0-4% net inversion of configuration. Solvolysis of N-methyl-4- alkoxypyridinium salts was investigated as a means of providing a leaving group which would not undergo “internal return.” Solvolysis rates for N-methyl-4-(cyclopropylcarbinyloxy)pyridinium iodide and perchlorate in water and in 80% ethanol and of N-methyl-4-(cyclopropylmethylcarbinyloxy)pyridinium iodide in water were measured. The first-order rate constant for the hydrolysis of N-methyl-4-(cyclopropylmethylcarbinyloxy)pyridinium iodide at 30º was calculated to be 6 x 10^3 times that of N-methyl- 4-(cyclopropyIcarbinyloxy)pyridinium iodide. The hydrolysis of optically active N-methyl4-(cyclopropylmethylcarbinyloxy) pyridinium iodide produced cyclopropylmethylcarbinol with 4.4 ± 1.5% inversion of configuration. The stereochemistry of the deamination of cyclopropylmethylcarbinylamine and of the hydrolysis of Nmethyl-4-(cyclopropylmethylcarbinyloxy)pyridinium iodide and the ratio of rate constants for the cyclopropylmethylcarbinyl and cyclopropylcarbinyl pyridinium salts are discussed with respect to the possible intervention of nonclassical carbonium ion intermediates in these reactions.

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Additional Information:© 1966 American Chemical Society. Received September 27, 1965. Supported in part by the National Science Foundation and the Petroleum Research Fund administered by the American Chemical Society. Grateful acknowledgment is hereby made to the Donors of the Petroleum Research Fund. From the Ph.D. Thesis of M. Vogel, California Institute of Technology, 1961. Presented in part at Sixteenth National Organic Chemistry Symposium of the American Chemical Society, Seattle, Washington, June 15, 1959; National Science Foundation Predoctoral Fellow, 1958-1960.
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American Chemical Society Petroleum Research FundUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
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Caltech Gates and Crellin Laboratories of Chemistry3302
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Official Citation:Small-Ring Compounds. XLVII. Reactions of Optically Active Cyclopropylmethylcarbinyl Derivatives Martin Vogel and John D. Roberts Journal of the American Chemical Society 1966 88 (10), 2262-2271 DOI: 10.1021/ja00962a033
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61119
Deposited By: Ruth Sustaita
Deposited On:15 Oct 2015 17:13
Last Modified:10 Nov 2021 22:44

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