TiCl₄ induced N-Methyleneamine Equivalents: A New Route to Aminoacetonitriles

References

• Tramontini , M. and Angiolini , L. 1990 . Tetrahedron , 46 : 1791 For a comprehensive review see
   Web of Science ®Google Scholar
• Guillemin , J. C. and Denis , J. M. 1988 . Tetrahedron , 44 : 4431 and references cited therein
   Web of Science ®Google Scholar
• Barluenga , J. , Bayon , A. M. and Asensio , G. 1983 . J. Chem. Soc. Chem. Commun. , : 110
   Google Scholar
• Barluenga , J. , Campos , P. J. and Canal , G. 1989 . Synthesis , : 33
   Google Scholar
• Overman , L. E. and Burk , R. M. 1984 . Tetrahedron Lett. , 25 : 1635
   Web of Science ®Google Scholar
• Hosomi , A. , Iijima , S. and Sakurai , H. 1982 . Tetrahedron Lett. , 23 : 547
   Web of Science ®Google Scholar
• Ikeda , K. , Achiwa , K. and Sekiya , M. 1983 . Tetrahdron Lett. , 24 : 913
   Web of Science ®Google Scholar
• Ha , H.-J. , Nam , G.-S. and Park , K. P. 1990 . Tetrahdron Lett. , 31 : 1567
   Google Scholar
• Ha , H.-J. , Nam , G.-S. and Park , K. P. Bull. Kor. Chem. Soc. , submitted to
   Google Scholar
• Barluenga , J. , Bayon , A. M. , Campos , P. , Asensio , G. , Gonzalez-Nunez , E. and Molina , Y. 1988 . J. Chem. Soc. Perkin Trans. I , : 1631
   Google Scholar
• 1,3,5-Trisubstituted-hexahydro-1,3,5-triazine can be prepared by the conventional method with N-substituted amines and formaldehyde.
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• Unpublished observation
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• When TiCl4 was added into hexahydro-1,3,5-triazine or N-(methoxymethyl)amine solution in CH2Cl2 the color of this reaction mixture became deep wine-red, which indicated the formation of complex with TiCl4. The structure of complex generated from hexahydro-1,3,5-triazine is assumed to be 4, or 5 because N-methyleneamine peaks in 1H and 13C NMR were observed by mixing 1,3,5-tri-n-butylhexahydro-1,3,5-triazine with 5 mol % of TiCl4. However, the 1H and 13C NMR spectra of the mixture of N-(methoxymethyl)-4-nitroaniline with TiCl4 did not show any peak corresponding to N-methyleneamine. This supports tentatively assumed intermediate 6 with the exclusion of the possibility that C-OCH3 bond is cleaved to make N-methyleneamine type of complex before a nucleophile attacks. However, under the reaction condition the intermediate 6 serves as a N-methyleneamine equivalent to a nucleophile with the removal of methoxy group
   Google Scholar
• Ojima , I. , Inaba , S. I. and Nagai , Y. 1975 . Chem Lett. , : 73
   Google Scholar
• Ojima , I. , Inaba , S. I. , Nakatsugawa , K. and Nagai , Y. 1975 . Chem. Lett. , : 331
   Web of Science ®Google Scholar