Aminomethyl transfer (Mannich) reactions between an O-triethylsilylated hemiaminal and anilines, RnC6H5-nNH2 leading to new diamines, triamines, imines or 1,3,5-triazines dependent upon substituent R.

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Summary of "Aminomethyl transfer (Mannich) reactions between an O-triethylsilylated hemiaminal and anilines, RnC6H5-nNH2 leading to new diamines, triamines, imines or 1,3,5-triazines dependent upon substituent R."

The reactions of the Mannich reagent Et3SiOCH2NMe2 (1) with a variety of anilines, mono-substituted RC6H4NH2, R = H, 4-CN, 4-NO2, 4-Ph, 4-Me, 4-MeO, 4-Me2N; R2C6H3NH2; di-substituted R2 = 3,5-(CH3)2, 3,5-(CF3)2; R3C6H2NH2; tri-substituted R3 = 3,5-Me2-4-Br; and a "super bulky" aniline (Ar*NH2) [Ar* = 2,6-bis(diphenylmethyl)-4-tert-butylphenyl], led to the immediate formation of a range of products dependent upon the substituent. With electron-withdrawing substituents, previously unknown diamines, RC6H4NH(CH2NMe2) [R = CN (2a), NO2 (2b)] and R2C6H3NH(CH2NMe2) [R2 = 3,5-(CF3)2 (2c)] were formed. Further reaction of 2a, b, c with 1 yielded the corresponding triamines RC6H4N(CH2NMe2)2 (R = CN (3a), NO2 (3b) and R2C6H3N(CH2NMe2)2, R2 = 3,5-(CF3)2 (3c). The new polyamines were characterized by NMR spectroscopy, and for 2a, 2c, and 3c, by single crystal XRD. In the case of electron-donating groups, R = 4-OMe, 4-NMe2, 4-Me, 3,5-Me2, 3,5-Me2-4-Br, and for R = 4-Ph, the reactions with 1 immediately led to the formation of the related 1,3,5-triazines, R = 4-MeO (5a), 4-Me2N (5b), 4-Ph (5c), 3,5-Me2 (5d), 3,5-Me2-4-Br (5e), 4-Ph (5f), 4-Cl (5g). The "super-bulky" aniline rapidly produced a single product, namely the corresponding imine Ar*N=CH2 (4) which was also characterized by single crystal XRD. All reactions are very fast, thus based upon the presence of Si we are tempted to denote the reactions of 1 as examples of Silick Chemistry.


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Name: Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765


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