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DOI: 10.1055/a-1742-3723
Microwave-Assisted Aminoalkylation of Phenols via Mustard Carbonate Analogues
We thank Istituto Nazionale della Previdenza Sociale (INPS) for funding the Ph.D. fellowship of Giacomo Trapasso. Prof. S. Castellano acknowledges Regione Campania (Italy) for funding (Grant B61G18000470007).
Abstract
A microwave-assisted chlorine-free direct phenol substitution is presented, which is indicated as a key green chemistry research area for pharmaceuticals manufacturers. The reaction of β-aminocarbonates (mustard carbonates) with several substituted phenols in the presence of a polar solvent (acetonitrile or butanol) led to the related aminoalkylated products via the anchimeric assistance of the nitrogen incorporated in the organic carbonate backbone. The aminoalkylation required short reaction time (7 min) and the related products were isolated in high yields (>90%) via quick liquid-liquid extraction or column chromatography depending on the solvent employed. Furthermore, microwave irradiation also promoted the one-pot aminoalkylation of phenol in excellent yield. In this approach a β-aminoalcohol was reacted with phenol in the presence of diethyl carbonate, used for the in situ formation β-aminocarbonate, key intermediate in the consequent anchimerically driven alkylation. The resulting product, namely N,N-dimethyl-2-phenoxyethanamine, was isolated as pure in almost quantitative yield.
Key words
alkylation - green chemistry - phenols - neighboring group effects - dialkyl carbonate - microwave chemistrySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1742-3723.
- Supporting Information
Publikationsverlauf
Eingereicht: 05. November 2021
Angenommen nach Revision: 17. Januar 2022
Accepted Manuscript online:
17. Januar 2022
Artikel online veröffentlicht:
01. März 2022
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References
- 1a Wang Q.-Q, Begum RA, Day VW, Bowman-James K. Org. Biomol. Chem. 2012; 10: 8786
- 1b Tang FR, Loke WK. Crit. Rev. Toxicol. 2012; 42: 688
- 1c Ghabili K, Ansarin K, Shoja MM, Agutter PS, Ghanei M. J. Appl. Toxicol. 2010; 7: 627
- 1d Jackson KE. Chem. Rev. 1934; 15: 425
- 1e Malhotra RC, Ganesan K, Sugendran K, Swamy RV. Def. Sci. J. 1999; 49: 9
- 2a Wilen SH, Delguzzo L, Saferstein R. Tetrahedron 1987; 43: 5089
- 2b Francl MM, Hansell G, Patel BP, Swindell CS. J. Am. Chem. Soc. 1990; 11: 3535
- 2c Smith MB, March S. March’s Advanced Organic Chemistry, 6th ed. Wiley; Hoboken: 2007: 446
- 3 Barkhash VA. Top. Curr. Chem. 1984; 116-117: 1
- 4a Wang Q.-Q, Ara Begum R, Day VW, Bowman-James K. Inorg. Chem. 2012; 51: 760
- 4b Choi J.-H, Schloerer NE, Berger J, Prechtl MH. Dalton Trans. 2014; 43: 290
- 4c Sharghi H, Nasseri MA, Niknam K. J. Org. Chem. 2001; 66: 7287
- 5a Bermejo JF, Ortega P, Chonco L, Eritja R, Samaniego R, Müllner M, de Jesus E, de la Mata FJ, Flores JC, Gomez R, MuÇoz-Fernandez A. Chem. Eur. J. 2007; 13: 483
- 5b Liu B, Yu WL, Lai YH, Huang W. Macromolecules 2002; 35: 4975
- 5c Fan QL, Zhou Y, Lu XM, Hou XY, Huang W. Macromolecules 2005; 38: 2927
- 5d Breitenkamp RB, Tew GN. Macromolecules 2007; 34: 1163
- 5e Li J, Meng J, Huang X, Cheng Y, Zhu C. Polymer 2010; 51: 3425
- 6 Chabner B, Roberts T. Nat. Rev. Cancer 2005; 5: 65
- 7 Tundo P, Musolino M, Aricò F. Green Chem. 2018; 20: 28
- 8a Aricò F, Chiurato M, Peltier J, Tundo P. Eur. J. Org. Chem. 2012; 3223
- 8b Trapasso G, Salaris C, Reich M, Logunova E, Salata C, Kümmerer K, Figoli A, Aricò F. Sustainable Chem. Pharm. 2022; 26: 100639
- 9a Aricò F, Evaristo S, Tundo P. ACS Sustainable Chem. Eng. 2013; 1: 1319
- 9b Aricò F, Evaristo S, Tundo P. RSC Adv. 2014; 4: 31071
- 9c Aricò F, Aldoshin AS, Tundo P. ACS Sustainable Chem. Eng. 2016; 4: 2843
- 9d Aricò F, Tundo P. Pure Appl. Chem. 2016; 88: 3
- 9e Aricò F, Udrea I, Crisma M, Tundo P. ChemPlusChem 2015; 80: 471
- 9f Venkataraman S, Ng VW. L, Coady DJ, Horn HW, Jones GO, Fung TS, Sardon H, Waymouth RM, Hedrick JL, Yang YY. J. Am. Chem. Soc. 2015; 137: 13851
- 10 Aricò F, Aldoshin AS, Musolino M, Crisma M, Tundo P. J. Org. Chem. 2018; 83: 236
- 11 Annatelli M, Trapasso G, Salaris C, Salata C, Castellano S, Aricò F. Eur. J. Org. Chem. 2021; 3459
- 12 Bryan MC, Dunn PJ, Entwistle D, Gallou F, Koenig SG, Hayler JD, Hickey MR, Hughes S, Kopach ME, Moine G, Richardson P, Roschangar F, Steven A, Weiberth FJ. Green Chem. 2018; 20: 5082
- 13 Bleicher K, Böhm HJ, Müller K, Alanine AI. Nat. Rev. Drug Discov. 2003; 2: 369
- 14 Kappe C, Dallinger D. Nat. Rev. Drug. Discov. 2006; 5: 51
- 15 Reichardt C, Welton T. Solvents and Solvent Effects in Organic Chemistry, 4th ed. Wiley-VCH; Weinheim: 2011
- 16 Aycock DF. Org. Process Res. Dev. 2007; 11: 156