Abstract
Data have been summarized of several studies on the separation of isomeric pyrrolizidine alcohols by GLC using liquid polar stationary phases. It was shown that the order of emergence of isomers from the chromatographic column is determined to a significant extent by competition of intermolecular hydrogen bonds formed in the sorbate-sorbent systems and intramolecular hydrogen bonds in the molecules of the same pyrrolizidine alcohols. The preference for one or other type of hydrogen bond depends on the stereochemistry of the pyrrolizidine alcohols. Analysis of the geometric conditions for the formation of intramolecular hydrogen bonds in the investigated compounds in conjunction with chromatographic resolution data enables their configurations to be assigned. The anomalously short retention times of highly strained 5-hydroxyalkyl-3-methylpyrrolizidines are explained by the existence in them of a bicyclic conformation predominantly with a trans linkage and with f avora ble geometric conditions for forming intramolecular hydrogen bonds in them.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
I. M. Skvortsov andL. N. Astakhova, Khim. Geterotsikl. Soedin., 1489 (1987).
H. Rottsche andM. Gofman, in: A. A. Zhukhovitskii (editor), Handbook of Gas Chromatography [Russian translation], Mir, Moscow (1969), p. 176.
H. M. McNair andE. J. Bonnelli, Basic Gas Chromatography, Varian, Walnut Creek, Calif. (1969), 306 pp.
I. M. Skvortsov, Zh. Fiz. Khim., 72, 340 (1998).
C. H. De Puy andP. R. Story, Tetrahedron Lett., 20 (1959).
C. P. Rader, R. L. Young, andH. S. Aaron, J. Org. Chem., 30, 1536 (1965).
H. S. Aaron, G. E. Wicks, andC. P. Rader, J. Org. Chem., 29, 2248 (1964).
H. S. Aaron, C. P. Rader, andG. E. Wicks, J. Org. Chem., 31, 3502 (1966).
O. Cervinka, K. Pelz, andI. Jirkovsky, Collect. Czech. Chem. Commun., 26, 3116 (1961).
I. M. Skvortsov andS. A. Kolesnikov, Khim. Geterotsikl. Soedin., 484 (1976).
I. M. Skvortsov andV. M. Levin, Khim. Geterotsikl. Soedin., 947 (1973).
I. M. Skvortsov, L. N. Astakhova, I. Ya. Evtushenko, E. V. Cheslavskaya, S. N. Kuz'min, andS. P. Voronin, Khim. Geterotsikl. Soedin., 63 (1980). 502
N. I. Shergina, T. V. Kashik, E. N. Kositsina, Z. T. Dmitrieva, andB. A. Trofimov, Izv. Akad. Nauk SSSR. Ser. Khim., 2703 (1969).
K. I. Petrov, M. G. Zaitseva, A. M. Kuliev, M. A. Allakhverdiev, E. Ya. Borisova, andE. M. Cherkasova, Zh. Obshch. Khim., 45, 618 (1975).
M. Tichy, in: I. L. Knunyants (editor), Progress in Organic Chemistry, Vol. 5 [Russian translation], Mir, Moscow (1968), p. 117.
R. Taylor, O. Kennard, andW. Versichel, J. Am. Chem. Soc., 105, 5761 (1983).
W. G. Schneider, J. Chem. Phys., 23, 26 (1955).
K. Nakamoto, M. Margoshes, andR. E. Rundle, J. Am. Chem. Soc., 77, 6480 (1955).
G. C. Pimentel andA. L. McClellan, The Hydrogen Bond, Freeman, San Francisco (1960).
I. M. Skvortsov, Usp. Khim., 48, 481 (1979).
Yu. A. Pentin, I. M. Skvortsov, Tran Suan Khoan', andI. V. Antipova, in: Ya. I. Gerasimov (editor), Spectra and Molecular Structure, Izd. Mosk. Gos. Univ., Moscow (1980), p. 108.
I. M. Skvortsov andI. V. Antipova, Zh. Org. Khim., 15, 868 (1979).
I. M. Skvortsov andJ. A. Elvidge, J. Chem. Soc. (B), 1589 (1968).
I. M. Skvortsov, Dissertation for Doctor of Chemical Sciences, Saratov (1989).
O. A. Subbotin andI. M. Skvortsov, Khim. Geterotsikl. Soedin., 1638 (1985).
I. M. Skvortsov andI. V. Antipova, Khim. Geterotsikl. Soedin., 58 (1979).
I. V. Antipova, V. V. Negrebetskii, andI. M. Skvortsov, Khim. Geterotsikl. Soedin., 39 (1982).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Skvortsov, I.M. Investigations on 1-Azabicyclic Compounds. 25. Stereochemistry, Hydrogen Bonds, and Gas-Liquid Chromatography of Pyrrolizidine Alcohols. Chemistry of Heterocyclic Compounds 39, 493–503 (2003). https://doi.org/10.1023/A:1024769531168
Issue Date:
DOI: https://doi.org/10.1023/A:1024769531168