Abstract
The Stevens rearrangement of ammonium salts containing 2-alkenyl, 2-alkynyl, or benzyl groups along with 2-propynyloxy or tert-butoxycarbonylmethyl was studied. Under the action of a suspension of sodium phenolate in benzene the salts containing a 2-propynyloxycarbonylmethyl group form 2-propynyl esters of 2-dialkylamino-4-pentenoic acids, whereas with sodium methylate as the basic reagent, rearrangement is preceded by an almost complete transesterification. The salts containing a tert-butoxycarbonylmethyl group undergo almost no transesterification under the action of sodium methylate. The tert-butyl fragment in the ester group of the salt with a benzyl group exerts a fairly strong effect on the regiochemistry of the rearrangement and on the prototropic isomerization of the 3,2-Stevens rearrangement of the salts with 2-butynyl or 3-phenyl-2-propynyl groups.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
Stevens, T.S., Snedden, W.W., Stiller, E.T., and Thomson, T., J. Chem. Soc., 1930, no. 2, p. 2119.
Paton, J.M., Pauson, P.L., and Stevens, T.S., J. Chem. Soc. C, 1969, no. 16, p. 2130.
Kocharyan, S.T., Ogandzhanyan, S.M., Razina, T.L., and Babayan, A.T., Arm. Khim. Zh., 1977, vol. 3, no.12, p. 977.
Eryshev, B.Ya., Yatsenko, B.P., Smirnova, T.A., Kutepov, D.F., and Brysin, Yu., Zh. Prikl. Khim., 1978, vol. 51, no.14, p. 953.
Organic Syntheses, Ann. vols. 20–25, 1940–1945. Translated under the title Sintezy organicheskih preparatov, Kazanskii, B.A., Ed., Moscow: Inostrannaya literatura, 1952, vol. 3, p. 124.
Bader, A.R., Cummings, L.O., and Vogel, H.A., J. Am. Chem. Soc., 1951, vol. 73, no.9, p. 4195.
Kocharyan, S.T., Voskanyan, V.S., Grigoryan, V.V., Panosyan, G.A., and Babayan, A.T., Arm. Khim. Zh., 1985, vol. 38, no.1, p. 37.
Kocharyan, S.T., Ogandzhanyan, S.M., and Babayan, A.T., Arm. Khim. Zh., 1976, vol. 29, no.5, p. 409.
Babayan, A.T., Kocharyan, S.T., and Ogandzhanyan, S.M., Arm. Khim. Zh., 1976, vol. 3, no.12, p. 401.
Author information
Authors and Affiliations
Additional information
Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1321–1326.
Original Russian Text Copyright © 2004 by Babakhanyan, Ovakimyan, Grigoryan, Kocharyan.
Rights and permissions
About this article
Cite this article
Babakhanyan, A.B., Ovakimyan, S.A., Grigoryan, V.V. et al. Stevens rearrangement of ammonium salts containing 2-propynyloxy or tert-butoxycarbonylmethyl groups. Russ J Gen Chem 74, 1221–1226 (2004). https://doi.org/10.1007/s11176-005-0143-z
Received:
Issue Date:
DOI: https://doi.org/10.1007/s11176-005-0143-z