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DOI: 10.1055/s-0037-1610343
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
Publication History
Received: 26 September 2018
Accepted after revision: 31 October 2018
Publication Date:
07 December 2018 (online)
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 aminesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610343.
- Supporting Information
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References and Notes
- 1 Khunkitti W, Lloyd D, Furr JR, Russell AD. J. Appl. Bacteriol. 1996; 81: 73
- 2 Kuča K, Kivala M, Dohnal V. J. Appl. Biomed. 2004; 2: 195
- 3 Princt DL, Prince HN, Thraenhart O, Muchmore E, Bonder E, Pugh J. J. Clin. Microbiol. 1993; 31: 3296
- 4 Boettler U, Volz N, Pahlke G, Teller N, Kotyczka C, Somoza V, Stiebitz H, Bytof G, Lantz I, Lang R, Hofmann T, Marko D. Mol. Nutr. Food Res. 2011; 55: 798
- 5 Somoza V, Lindenmeier M, Wenzel E, Frank O, Erbersdobler HF, Hofmann T. J. Agric. Food Chem. 2003; 51: 6861
- 6 Liang N, Kitts DD. Molecules 2014; 19: 19180
-
7
Lang R,
Wahl A,
Stark T,
Hofmann T.
Mol. Nutr. Food Res. 2011; 55: 1613
- 8 Breipohl G, Holla W, Jendrala H, Beck G. Patent US 7,084.250 B2, 2, 2006
- 9 Dumur F, Mayer CR, Dumas E, Miomandre F, Frigoli M, Secheresse F. Org. Lett. 2008; 10: 321
- 10 Bhaskar P, Shee S, Chakrabarti K, Kundu K. ChemSusChem 2017; 10: 2370
- 11 Dang TT, Ramalingam B, Seayad AM. ACS Catal. 2015; 5: 4082
- 12 Tsarev VN, Morioka Y, Caner J, Wang Q, Ushimaru R, Kudo A, Naka H, Saito S. Org. Lett. 2015; 17: 2530
- 13a Stíbal D, Sá J, van Bokhoven JA. Catal. Sci. Technol. 2013; 3: 94
- 13b Shiraishi Y, Fujiwara K, Sugano Y, Ichikawa S, Hirai T. ACS Catal. 2013; 3: 312
- 14 Caner J, Liu Z, Takada Y, Kudo A, Naka H, Saito S. Catal. Sci. Technol. 2014; 4: 4093
- 15 Jones JR. Q. Rev., Chem. Soc. 1971; 25: 365
- 16 Boyd RH, Wang C.-H. J. Am. Chem. Soc. 1965; 87: 430
- 17 Neidleinand R, Sui Z. Helv. Chim. Acta 1991; 74: 579
- 18 Judson PN, Richard C, White H. Patent EP 0010396A1, 1980
- 19 Arndt F, Scholz H, Frobel E. Justus Liebigs Ann. Chem. 1936; 521: 95
- 20 McKusick BC, Heckert RE, Cairns TL, Coffman DD, Mower HF. J. Am. Chem. Soc. 1958; 80: 2806
- 21 Cairns TL, McKusick BC. Angew. Chem. 1961; 73: 520
- 22 Chulze W, Willitzer H. J. Prakt. Chem. 1966; 33: 104
- 23a Mirallai SI, Manoli M, Koutentis PA. Tetrahedron 2015; 71: 8766
- 23b Mirallai SI, Manoli M, Koutentis PA. J. Org. Chem. 2013; 78: 8655
- 24 Eremkin AV, Ershov OV, Kayukov YaS, Sheverdov VP, Nasakin OE, Tafeenko VA, Nurieva EV. Tetrahedron Lett. 2006; 47: 1445
- 25 Middleton WJ, Little EL, Coffman DD, Engelhardt VA. J. Am. Chem. Soc. 1958; 80: 2795
- 26 Alekseeva OO, Rodina LL, Ryzhakov AV, Korneev SM. Russ. J. Org. Chem. 1997; 33: 1320
- 27 Middleton WJ, Engelhardt VA. J. Am. Chem. Soc. 1958; 80: 2788
- 28 Ohashi M, Suwa S, Tsujimoto K. J. Chem. Soc., Chem. Commun. 1976; 404
- 29 Middleton WJ, Hekert RE. J. Am. Chem. Soc. 1958; 80: 2783
- 30 Sheverdov VP, Ershov OV, Nasakin OE. Tetrahedron 2001; 57: 5815
- 31a Abbas SA, Haines AH. Carbohydr. Res. 1975; 39: 358
- 31b Havel M, Velek J, Pospisek J, Sousek M. Collect. Czech. Chem. Commun. 1979; 44: 2443
- 32 Sada K, Tani T, Shinkai S. Synlett 2006; 2364
- 33a Problema Raka i Karbonitrile . Sheverdov VP, Nasakin OE, Davydova VV. Cheboksary Ch.G. U. im. I. N. Ulyanova 2017; (in Russian)
- 33b Jesson MI, Johnston JB, Robotham E, Degleiter A. Cancer Res. 1989; 49: 7031
- 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.