Russian Journal of Organic Chemistry

, Volume 52, Issue 8, pp 1112–1117 | Cite as

Reaction of N-phenyltriflamide with 1,2-dibromoethane and propargyl bromide. Unexpected cleavage of С–С and С–N bonds

Article

Abstract

Reaction of N-phenyltriflamide with 1,2-dibromoethane under basic conditions in DMSO unexpectedly results in N-methyl-N-phenyltriflamide and 1,3-diphenylurea. The presumed reaction mechanism includes the formation of unstable intermediate disubstitution product TfN(Ph)CH2CH2N(Ph)Tf that suffers the the С–С bond cleavage resulting in TfN(Me)Ph and N,N′-methanediylbis(N-phenyltriflamide). The latter reacts with K2CO3 releasing two molecules of potassium triflinate and after hydrolysis of diphenylcarbodiimide PhN=C=NPh gives 1,3-diphenylurea. With propargyl bromide, N-phenyltriflamide affords N-propargyl-Nphenyltriflamide in high yield. The bromination of the latter results in a mixture of Z,E-isomers of N-(2,3-dibromoprop-2-en-1-yl)-N-phenyltriflamide which undergo dehydrobromination giving first N-(3-bromopropanedienyl)-N-phenyltriflamide and then the products of the C–N bond cleavage: N-phenyltriflamide and 3,3-dimethoxyprop-1-yne.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Yagupolskii, L.M., Popov, V.I., Pavlenko, N.V., Maletina, I.I., Mironova, A.A., and Gavrilova, R.Yu., Zh. Org. Khim., 1986, vol. 22, p. 2169.Google Scholar
  2. 2.
    Zhu, S.Z. and Chen, Q.I., Chem. Commun., 1991, p. 732.Google Scholar
  3. 3.
    Zhu, S.Z., Lee, A.W., Zhu, Y.H., Chen, X.M., Dai, J.N., and Yuan, X.W., J. Fluor. Chem., 1993, vol. 60, p. 283.CrossRefGoogle Scholar
  4. 4.
    Zhu, S.Z. and Jin, X.L., J. Fluor. Chem., 1995, vol. 72, p. 19.CrossRefGoogle Scholar
  5. 5.
    Shainyan, B.A. and Tolstikova, L.L., Russ. J. Org. Chem., 2005, vol. 41, p. 984.CrossRefGoogle Scholar
  6. 6.
    Shainyan, B.A. and Sterkhova, I.V., Russ. J. Org. Chem., 2010, vol. 46, p. 1743.CrossRefGoogle Scholar
  7. 7.
    Shainyan, B.A. and Ushakova, I.V., Russ. J. Org. Chem., 2012, vol. 48, p. 141.CrossRefGoogle Scholar
  8. 8.
    Ushakova, I.V. and Shainyan, B.A., Russ. J. Org. Chem., 2013, vol. 49, p. 924.CrossRefGoogle Scholar
  9. 9.
    Shainyan, B.A. and Ushakova, I.V., Russ. J. Org. Chem., 2014, vol. 50, p. 1093.CrossRefGoogle Scholar
  10. 10.
    Shainyan, B.A. and Danilevich, Yu.S., Russ. J. Org. Chem., 2013, vol. 49, p. 922.CrossRefGoogle Scholar
  11. 11.
    Shainyan, B.A. and Danilevich, Yu.S., Russ. J. Org. Chem., 2013, vol. 49, p. 1112.CrossRefGoogle Scholar
  12. 12.
    Shainyan, B.A., Chipanina, N.N., Oznobikhina, L.P., and Danilevich, Yu.S., J. Phys. Org. Chem., 2013, vol. 26, p. 653.CrossRefGoogle Scholar
  13. 13.
    Shainyan, B.A. and Danilevich, Yu.S., Russ. J. Org. Chem., 2014, vol. 50, p. 747.CrossRefGoogle Scholar
  14. 14.
    Shainyan, B.A. and Ushakova, I.V., Russ. J. Org. Chem., 2014, vol. 50, p. 1835.CrossRefGoogle Scholar
  15. 15.
    Shainyan, B.A. and Danilevich, Yu.S., Russ. J. Org. Chem., 2015, vol. 51, p. 601.CrossRefGoogle Scholar
  16. 16.
    Shainyan, B.A., Ushakova, I.V., and Danilevich, Yu.S., Russ. J. Org. Chem., 2015, vol. 51, p. 931.CrossRefGoogle Scholar
  17. 17.
    Shainyan, B.A. and Ushakova, I.V., Russ. J. Org. Chem., 2016, vol. 52, p. 192.CrossRefGoogle Scholar
  18. 18.
    Zhang, W., Liu, N., Schienebeck, C.M., Zhou, X., Izhar, I.I., Guzei, I.A., and Tang, W., Chem. Sci., 2013, vol. 4, p. 2652.CrossRefGoogle Scholar
  19. 19.
    Montaña, Á.M., Fernández, D., Pagès, R., Filippou, A.C., and Kociok-Köhn, G., Tetrahedron, 2000, vol. 56, p. 425.CrossRefGoogle Scholar
  20. 20.
    Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, O., Foresman, J.B., Ortiz, J.V., Cioslowski, J., and Fox, D.J., Gaussian 09, Revision A.01, Gaussian, Inc., Wallingford, CT, 2009.Google Scholar

Copyright information

© Pleiades Publishing, Ltd. 2016

Authors and Affiliations

  1. 1.Favorskii Irkutsk Institute of Chemistry, Siberian BranchRussian Academy of SciencesIrkutskRussia

Personalised recommendations