Abstract
According to the spectrophotometric data, the lithium 1-(2-methoxyphenyl)-3,3-diphenylpropyne derivative in diethyl ether exists as contact ion pairs, while in THF, according to the spectrophotometric and13C NMR data, solvent-separated ion pairs are predominantly formed. According to the13C NMR data, the carbanion in the solventseparated ion pairs has a structure close to the propargylic type. The regioselectivity of reactions of the lithium derivative with ethyl halides in diethyl ether, THF, and hexamethyphosphoramide, with benzyl chloride in the first two solvents, and with methanol in THF were studied. The protonation with methanol proceeds exclusively at the allenylic center (C-1) while the ethylation and especially benzylation proceed predominantly at the propargylic center (C-3). The selectivity of ethylation of the propargylic center of both solvent-separated ion pairs in THF and contact ion pairs in diethyl ether increases as the hardness of the ethylating agent increases, and in the case of the same ethyl halide, the selectivity increases from the solvent-separated ion pairs to the contact ion pairs. The spectral data obtained and the data on changes in the regioselectivity do not allow one to believe that the contact ion pairs of the lithium derivative in ether exhibit the intramolecular coordination of the lithium cation to the methoxy group, which might lead to the allenylic structure of contact ion pairs of this derivative.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
J. Klein, inThe Chemistry of The Carbon-Carbon Triple Bond, Ed. S. Patai, Wiley, New York, 1978, Part 1, 343.
J.-L. Moreau, inThe Chemistry of Ketenes, Allenes and Related Compounds, Ed., S. Patai, Wiley, New York, 1980, Part 1, 363.
J.F. Bielmann and J.-B. Ducep,Org. React., 1982, 27, 1.
R. Epsztein, inComprehensive Carbanion Chemistry, Eds. E. Buncel, T. Durst, Elsevier, Amsterdam, 1984, Part B, 107.
H. Jamamoto, inComprehensive Organic Synthesis, Eds. B. M. Trost, I. Fleming, Pergamon Press, Oxford, 1991, Vol. 2, 81.
P. I. Dem'yanov, I. M. Shtyrkov, V. S. Petrosyan, and O. A. Reutov,Vestn. Mosk. Gos. Univ., Ser. Khim. [Bull. Moscow State Univ., Div. Chem. Sci.], 1988,29, 384 (in Russian).
P. I. Dem'yanov, I. M. Shtyrkov, G. V. Fyodorova, and V. S. Petrosyan,Pure Appl. Chem., 1990,62, 681.
I. Smid, inIon and Ion Pairs in Organic Reactions, Ed. M. Szwarc, Wiley, New York, 1972, Vol.1.
Ion and Ion Pairs in Organic Reactions, Ed. M. Szwarc, Wiley, New York, 1974, Vol.2, 566 p.
A. A. Solov'yanov and I. P. Beletskaya,Usp. Khim., 1978,47, 819 [Russ. Chem. Rev., 1978,47 (Engl. Transl.)].
P. I. Dem'yanov, I. M. Shtyrkov, V. S. Petrosyan, and O. A. Reutov,Vestn. Mosk. Gos. Univ., Ser. Khim. [Rull. Moscow State Univ., Div. Chem. Sci.], 1988,29, 203 (in Russian).
P. I. Dem'yanov, I. M. Shtyrkov, D. P. Krut'ko, V. S. Petrosyan, and O. A. Reutov,Metalloorg. Khim., 1988,1, 1048 [Organomet. Chem. USSR, 1988,1 (Engl. Transl.)].
P. I. Dem'yanov, I. M. Shtyrkov, D. P. Krut'ko, M. V. Vener, and V. S. Petrosyan,J. Organomet. Chem., 1992,438, 265.
P. Dem'yanov, G. Boche, M. Marsch, K. Harms, G. Fyodorova, and V. Petrosyan,Liebigs Ann., 1995, 457.
D. H. O'Brien, inComprehensive Carbanion Chemistry, Eds. E. Buncel and T. Durst, Elsevier, Amsterdam, 1980, Vol.5 271.
P. I. Dem'yanov, I. M. Shtyrkov, D. P. Krut'ko, V. S. Petrosyan, and O. A. Reutov,Metalloorg. Khim., 1988,1, 1033 [Organomet. Chem. USSR, 1988,1 (Engl. Transl.)].
P. I. Dem'yanov, I. B. Fedot'eva, V. S. Petrosyan, and O. A. Reutov,vestn. Mosk. Gos. Univ., Ser. Khim. [Bull. Moscow State Univ., Div. Chem. Sci.], 1984,25, 467 (in Russian).
H. J. Reich and J. E. Holladay,J. Am. Chem. Soc., 1995,117, 8470.
C. Lambert, P. v. R. Schleyer, and E.-U. Würthwein,J. Org. Chem., 1993,58, 6377.
I. M. Shtyrkov, P. I. Dem'yanov, and V. S. Petrosyan,Metallorg. Khim., 1992,5, 1348 [Organomet. Chem. USSR, 1992,5 (Engl. Transl.)].
T. V. Talalaeva and K. A. Kocheshkov,Metody elementoorgaicheskoi khimii. Litii, natrii, kalii, rubidii, tsezii [Methods of Organoelement Chemistry, Lithium, Sodium, Potassium, Rubidium, and Cesium], Nauka, Moscow, 1971, Vol.2, 724 (in Russian).
P. I. Dem'yanov, I. B. Fedot'eva, E. V. Babaev, V. S. Petrosyan, and O. A. Reutov,Dokl. Akad. Nauk SSSR, 1983,268, 1403 [Dokl. Chem., 1983 (Engl. Transl.)].
P. I. Dem'yanov, I. B. Fedot'eva, V. S. Petrosyan, and O. A. Reutov,Vestn. Mosk. Gos. Univ., Ser. Khim. [Bull. Moscow State Univ., Div. Chem. Sci.], 1984,25, 297 (in Russian).
P. I. Dem'yanov, G. V. Fedorova, V. S. Petrosyan, and O. A. Reutov,Metalloorg. Khim., 1989,2, 620 [Organomet. Chem. USSR, 1989,2 (Engl. Transl.)].
P. H. Plesch,High Vacuum Techniques for Chemical Syntheses and Measurements, Cambridge University Press, Cambridge, 1989, 167 pp.
I. B. Fedot'eva,Ph. D. (Chem.), Thesis, Moscow State University, Moscow, 1984, 184 pp. (in Russian).
S. M. Neumann and J. K. Kochi,J. Org. Chem., 1975,40, 599.
H. C. Brown and R. L. Sharp,J. Am. Chem. Soc., 1968,90, 2915.
H.-J. Becher, inHandbuch der Preparativen Anorganischen Chemie, Dritte Auflage, Herausgegeben von G. Brauer, Verdinand Enke Verlag, Stuttgart, 1978, Band2.
B. E. Maryanoff, D. F. McComsey, and S. O. Nortey,J. Org. Chem., 1981,46, 355.
E. S. Petrov,D. Sc. (Chem.) Thesis, L. Ya. Karpov Physicochemical Institute, Moscow, 1977, 266 pp. (in Russian).
Author information
Authors and Affiliations
Additional information
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2043–2051, November, 1997.
Rights and permissions
About this article
Cite this article
Dem'yanov, P.I., Krut'ko, D.P., Borzov, M.V. et al. State in solution, structure, and regioselectivity of reactions of the lithium 1-(2-methoxyphenyl)-3,3-diphenylpropyne derivative. Russ Chem Bull 46, 1939–1947 (1997). https://doi.org/10.1007/BF02503791
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF02503791