Abstract
Lithium and sodium bis(trimethylsilyl)amides react with fluoro-, bromo-, and chlorobenzenes in THF or toluene to give a mixture of N,N-bis(trimethylsilyl)aniline and N,2-bis(trimethylsilyl)aniline. The latter compound is resulted from 1,3-shift of the trimethylsilyl group from nitrogen to ortho-carbon atom of the benzene ring. Effects of the solvent, halogen, and alkali metal nature as well as the reaction conditions on the ratio of isomers were examined. Reaction of iodobenzene with sodium bis(trimethylsilyl)amide in THF produces N,N-bis(trimethylsilyl)aniline and 2-iodo-N,N-bis(trimethylsilyl)aniline, while in toluene a mixture of three products, two indicated above and N,N-bis(trimethylsilyl)benzylamine, was obtained.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. Bhunia, S. R. Yetra, A. T. Biju, Chem. Soc. Rev., 2012, 41, 3140.
E. M. Carreira, C. M. Gampe, Angew. Chem., Int. Ed., 2012, 51, 3766.
A. V. Dubrovskiy, N. A. Markina, R. C. Larock, Org. Biomol. Chem., 2013, 11, 191.
H. Pellissier, M. Santelli, Tetrahedron, 2003, 59, 701.
A. V. Lis, I. P. Tsyrendorzhieva, A. I. Albanov, V. I. Rakhlin, M. G. Voronkov, Russ. J. Org. Chem. (Engl. Transl.), 2013, 49, 1451 [Zh. Org. Khim., 2013, 49, 1473].
G. Wittig, E. Benz, Chem. Ber., 1959, 92, 1999.
H. Yoshida, T. Minabe, J. Ohshita, A. Kunai, Chem. Commun., 2005, 3454.
H. Heaney, Chem. Rev., 1962, 62, 81.
J. C. Riggs, A. Ramirez, M. E. Cremeens, C. G. Bashore, J. Candler, M. C. Wirtz, J. W. Coe, D. B. Collum, J. Am. Chem. Soc., 2008, 130, 3406.
S. Lee, M. Jørgensen, J. F. Hartwig, Org. Lett., 2001, 3, 2729.
S. Tripathy, R. Leblanc, T. Durst, Org. Lett., 1999, 1, 1973.
J. F. Nobis, L. F. Moormeier, Ind. Eng. Chem., 1954, 46, 539.
K. B. Wiberg, S. Sklenak, W. F. Bailey, J. Org. Chem., 2000, 65, 2014.
E. A. Amonoo-Neizer, R. A. Shaw, D. A. Skovlin, B. C. Smith, Inorg. Synth., 1966, 8, 19.
A. V. Lis, I. P. Tsyrendorzhieva, A. I. Albanov, B. A. Shainyan, V. I. Rakhlin, Russ. J. Org. Chem. (Engl. Transl.), 2015, 51, 335 [Zh. Org. Khim., 2015, 51, 353].
E. W. Abel, D. A. Armitage, J. Chem. Soc., 1964, 1528.
M. J. Barany, R. P. Hammer, R. B. Merrifield, G. Barany, J. Am. Chem. Soc., 2005, 127, 508.
Author information
Authors and Affiliations
Corresponding author
Additional information
Dedicated to Academician of the Russian Academy of Sciences N. S. Zefirov on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2090–2094, September, 2015.
Rights and permissions
About this article
Cite this article
Lis, A.V., Tsyrendorzhieva, I.P., Albanov, A.I. et al. Peculiarities of the reaction of alkali metal bis(trimethylsilyl)amides with halobenzenes. Russ Chem Bull 64, 2090–2094 (2015). https://doi.org/10.1007/s11172-015-1122-0
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-015-1122-0