N-Alkylation of Primary Aromatic Amines Using Alkylhalide and Triethylamine

알킬할라이드와 Triethylamine을 이용한 일급 아로미틱 아민의 N-알킬레이션

  • 김주희 (덕성여자대학교 약학대학) ;
  • 박명숙 (덕성여자대학교 약학대학)
  • Published : 2005.01.01

Abstract

Synthetic method for the selective N-monoalkylation of anilines using alkyl halides and triethylamine under room temperature was described. The corresponding N-alkyl anilines were obtained in good yields with minor quantities of dialkylated products. Anilines 2a-m and 3a-m were identified using NMR and IR. A series of 2a-m and 3a-m has been synthesized from aniline, toluidines, ethylanilines, aminoacetophenones, phenetidines. Formation of anilines was undertaken with dropping of alkylhalides at room temperature in methanol (or ethanol) for 3 hours~5 days. Selectivity on the monoalkylation was relatively high. Synthetic ratio of monoalkylated and dialkylated product was 94 : 6 in case of maximum monoalkylation.

Keywords

References

  1. Shivarkar, A. B., Gupte, S. P. and Chaudhari, R. V. : Selective synthesis of N,N-dimethyl aniline derivatives using dimethyl carbonate as a methylating agent and onium salt as a catalyst . Journal of Molecular Catalysis A: Chemical 226, 49 (2004) https://doi.org/10.1016/j.molcata.2004.09.025
  2. Nishamol, K., Rahna, K. S. and Sugunan, S. : Selective alkylation of aniline to N-methyl aniline using chromium manganese ferrospinels. Journal of Molecular Catalysis A: Chemical 209, 89 (2004) https://doi.org/10.1016/j.molcata.2003.07.014
  3. Elangovan, S. P., Kannan, C., Arabindoo, B. and Murugesan, V. : Aniline methylation over AFI and AEL type molecular sieves. Applied Catalysis A: General 174, 213 (1998) https://doi.org/10.1016/S0926-860X(98)00189-6
  4. Hayat, S., Rahman, A., Choudhary, M. I., Khan, K. M., Schumann, W. and Bayer, E. : N-Alkylation of anilines, carboxamides and several nitrogen heterocycles using CsF-Celite/alkyl halides/$CH_3CN$ combination. Tetrahedron 57, 9951 (2001) https://doi.org/10.1016/S0040-4020(01)00989-9
  5. Valot, F, Fache, F, Jacquot, R., Spagnol, M. and Lemaire, M. : Gas-phase selective N-alkylation of amines with alcohols over ${\gamma}$-alumina. Tetrahedron Letters 40, 3689 (1999) https://doi.org/10.1016/S0040-4039(99)00588-2
  6. Sreekumar, K, Jyothi, T. M., Talawar, M. B., Kiran, B. P., Rao, B. S. and Sugunan, S. : Selective N-monomethylation of aniline using $Zn_{1-x}\;Co_xFe_2O_4$ (x=0, 0.2, 0.5, 0.8 and 1.0) type systems. Journal of Molecular Catalysis A: Chemical 152, 225 (2000) https://doi.org/10.1016/S1381-1169(99)00301-5
  7. Narayanan, S. and Deshpande, K. : Aniline alkylation over solid acid catalysts. Applied Catalysis A: General 199, 1 (2000) https://doi.org/10.1016/S0926-860X(99)00540-2
  8. Fujita, K, Li, Z., Ozeki, N. and Yamaguchi, R. : N-Alkylation of amines with alcohols caralyzed by a Cp Ir complex. Tetra-hedron Letters 44, 2687 (2003) https://doi.org/10.1016/S0040-4039(03)00371-X
  9. Anand, R, Khaire, S. S., Maheswari, R., Gore, K. U. and Chumbhale, V. R. : N-Alkylation of aniline with ethanol over HY and dealuminated HY zeolites. Applied Catalysis A: General 242, 171 (2003) https://doi.org/10.1016/S0926-860X(02)00502-1
  10. Romera. J. L., Cid, J. M. and Trabanco, A. A. : Potassium iodide catalysed monoalkylation of anilines under microwave irradiation. Tetrahedron Letters 45, 8797 (2004) https://doi.org/10.1016/j.tetlet.2004.10.002
  11. Selva, M., Bomben, A. and Tundo, P. : Selective mono-N-methylation of primary aromatic amines by dimethyl carbonate over faujasite X- and Y-type zeolites. J. Chem. Soc., Perkin Trans 1, 1041 (1997)
  12. Smith, M. B. and March, J. : March's Advanced Organic Chemistry, Wiley, New York, 5th ed., 499 (2001)
  13. Jonczyk, A., Ochal, Z. and Makosza, M. : Reactions of organic anions; LXXXV. Caralytic two-phase alkylation of cyanamide. Synthesis, 882 (1978)