LiClO₄-Catalyzed Ring-Opening of Aziridines with Aromatic Amines

Abstract

A variety of N-tosylaziridines undergo smoothly ring opening with aromatic amines using a catalytic amount of lithium perchlorate in acetonitrile at ambient temperature to afford the corresponding 1,2-diamines in excellent yields.

Key words

lithium perchlorate - aziridines - aryl amines - 1,2-diamines

References

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16

General procedure: A mixture of aziridine (5 mmol), aniline (5 mmol) and LiClO₄ (10 mol%) in acetonitrile (10 mL) was stirred at ambient temperature for a specified time (see Table). After complete conversion, as indicated by TLC, the reaction mixture was quenched with water (10 mL) and extracted with ethyl acetate (2 × 15 mL). The combined organic layers were dried over anhydrous Na₂SO_4, concentrated in vacuo and purified by column chromatography on silica gel (Merck, 100-200 mesh, ethyl acetate-hexane, 1:9) to afford pure 1,2-diamine. Spectral data for product 3a: trans-N-(4-methylbenzene sulfonyl)-2 anilinocyclohexamine: ¹H NMR (400 MHz, CDCl₃) δ: 7.70-7.80 (m, 2 H), 7.30-7.35 (m, 2 H), 7.14-7.20 (m, 2 H), 6.71-6.75 (m, 1 H), 6.47-6.50 (m, 2 H), 4.84 (br d, J = 5.1, Hz, 1 H), 3.40 (br s, 1 H), 3.10 (ddd, J = 3.9, 10.0, 10.0, Hz, NCH, 1 H), 2.95 (ddd, J = 4.0, 10.0, 10.0, Hz, NCH, 1 H), 2.46 (s, 3 H), 2.03-2-20 (m, 2 H), 1.65-1.70 (m, 2 H), 1.55-1.58 (m, 1 H), 1.17-1.38 (m, 2 H), 0.94-1.11 (m, 1 H); IR(neat): 3400, 3290, 1600, 1510 1450, 1330, 1300, 1160, 900 cm^-1. Anal. Calcd for C₁₉H₂₄N₂O₂S: C, 66.25; H, 7.02; N, 8.13. Found: C, 66.25; H, 6.85; N, 8.06.