Ethene-1,1,2,2-tetracarbonitrile and Methanol in the Methylating Reaction of Tertiary Amines to the Quaternary Ammonium Compounds of 1,1-Dicyano-2-methoxy-2-oxoethane-1-ide

Abstract

We discovered a new method to methylate tertiary amines such as urotropine, triethylamine, pyridine, 2-methylpyridine, 4-acetylpyridine, and isonicotinamide, up to quaternary ammonium compounds, with 1,1-dicyano-2-methoxy-2-oxoethane-1-ide being the counterion. Methyl-1,3,5,7-tetraazaadamantan-1-ium 1,1-dicyano-2-methoxy-2-oxoethane-1-ide, N,N-diethyl-N-methylethanaminium 1,1-dicyano-2-methoxy-2-oxoethane-1-ide, and substituted-methylpyridinium 1,1-dicyano-2-methoxy-2-oxoethane-1-ides were synthesized. Quaternary ammonium compounds of 1,1-dicyano-2-methoxy-2-oxothane-1-ide were synthesized within a single stage by stirring methanol solutions of tertiary amines with ethene-1,1,2,2-tetracarbonitrile (ETCN) at room temperature. In the reaction of ETCN with tertiary amines in methanol, processes occur that form the 1,1-dicyano-2-methoxy-2-oxoethane-1-ide fragment with simultaneous N-methylation. Crystal structures based on X-ray diffraction analysis of the obtained compounds were studied.

Key words

methylation - ethene-1,1,2,2-tetracarbonitrile - 1,1-dicyano-2-methoxy-2-oxoethane-1-ide - methanol - tertiary amines

• References and Notes

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• 34 1-Methyl-1,3,5,7-tetraazaadamantan-1-ium-1,1-dicyano-2-methoxy-2-oxoethan-1-ide (2); Typical Procedure: To a solution of urotropine 1 (2 mmol, 0.28 g) in methanol (5 mL) was added ethene-1,1,2,2-tetracarbonitrile (2 mmol, 0.256 g) in methanol (5 mL). The reaction was complete in 30–40 seconds (progress monitored by TLC with hydroquinone test). The mixture was kept at room temperature for 5 minutes and then methanol was distilled off under vacuum. The precipitate is filtered off and washed with ethanol–hexane (1:1) to give a light-yellow solid (480 mg, 86% yield); m.p. 167 °C (decomp.); IR: 2184, 2161 (C≡N), 1790, 1656 (С=O) cm^–1. ¹H NMR (400.130 MHz, DMSO-d ₆, TMS): δ = 5.02 (s, 6 H, (СH₂)₃N⁺), 4.61–4.58 (d, J =12.4 Hz, 3 H, (СН₂)₃N), 4.41–4.38 (d, J =12.4 Hz, 3 H, (СН₂)₃N), 3.42 (s, 3 H, OСН₃), 2.45 (s, 3 H, N⁺-СН₃). ¹³C NMR (100.613 MHz, DMSO-d ₆): δ = 169.94, 122.29, 121.88, 79.46, 79.43, 79.39, 69.82, 69.79, 69.76, 49.87, 42.32, 42.31. Anal. calcd (%) for C₁₂H₁₈N₆O₂: C 51.79, H 6.52, N 30.20. Found: С 51.83, H 6.57, N 30.08.