Synlett, Inhaltsverzeichnis Synlett 2015; 26(01): 84-86DOI: 10.1055/s-0034-1378920 letter © Georg Thieme Verlag Stuttgart · New YorkDirect Conversion of Aromatic Aldehydes into Benzamides via Oxidation with Potassium Permanganate in Liquid Ammonia Damian Antoniak Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw 42, Poland Fax: +48(22)6326681 eMail: icho-s@icho.edu.pl , Arkadiusz Sakowicz Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw 42, Poland Fax: +48(22)6326681 eMail: icho-s@icho.edu.pl , Rafał Loska Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw 42, Poland Fax: +48(22)6326681 eMail: icho-s@icho.edu.pl , Mieczysław Mąkosza* Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw 42, Poland Fax: +48(22)6326681 eMail: icho-s@icho.edu.pl› InstitutsangabenArtikel empfehlen Abstract Alle Artikel dieser Rubrik Abstract Oxidation of aromatic aldehydes by KMnO4 in liquid ammonia gives amides directly. The reaction proceeds satisfactorily when the aldehydes are activated by electron-withdrawing substituents on the ring. Key words Key wordsaldehydes - amides - aminals - oxidation - liquid ammonia Volltext Referenzen References and Notes 1a Allen CL, Wolliams MJ. Chem. Soc. Rev. 2011; 40: 3405 1b Valeur E, Bradley M. Chem. Soc. Rev. 2009; 38: 606 1c Humpwey JM, Chamberin AR. Chem. Rev. 1997; 97: 2243 2 Shie J.-J, Fang J.-M. J. Org. Chem. 2003; 68: 1158 3 Wang G, Yu Q.-Y, Chen S.-Y, Yu X.-Q. Org. Biomol. Chem. 2014; 12: 414 4 Nie R, Shi J, Xia S, Shen L, Chen P, Hou Z, Xiao F.-S. J. Mater. Chem. 2014; 22: 18115 ; and references cited therein 5a Wang Y, Yamaguchi K, Mizuno N. Angew. Chem. Int. Ed. 2012; 51: 7250 5b Vanjari R, Guntreddi T, Nand Singh K. Org. Lett. 2013; 15: 4908 5c Sharif M, Gong J.-L, Langer P, Beller M, Wu X.-F. Chem. Commun. 2014; 50: 4747 6a Ekone-Kovi K, Wolf C. Org. Synth. 2010; 87: 1 6b Giguère-Bisson M, Yoo W.-J, Li C.-J. Org. Synth. 2011; 88: 14 6c Möhlmann L, Ludwig S, Blechert S. Beilstein J. Org. Chem. 2013; 9: 602 6d Wang W, Zhao X.-M, Wang J.-L, Geng X, Gong J.-F, Hao X.-Q, Song M.-P. Tetrahedron Lett. 2014; 55: 3192 7 Reichardt C. Solvents and Solvent Effects in Organic Chemistry . Wiley-VCH; Weinheim: 2003. 3rd ed 8 Mąkosza M. Tetrahedron 1968; 24: 175 9a Ji P, Atherton J, Page MI. Org. Biomol. Chem. 2012; 10: 5732 9b Ji P, Atherton J, Page MI. J. Org. Chem. 2011; 76: 1425 9c Ji P, Atherton J, Page MI. J. Org. Chem. 2011; 76: 3286 10a van der Plas HC, Woźniak M. Croat. Chem. Acta 1968; 59: 33 10b Szpakiewicz B, Grzegorek M. Russ. J. Org. Chem. 2004; 40: 829 11 Mąkosza M, Staliński K. Chem. Eur. J. 1997; 3: 2025 12 General Procedure for the Oxidation of Aldehydes to Amides in Liquid AmmoniaUnder an argon atmosphere, liquid NH3 (25 mL) was condensed in a two-neck round-bottom flask immersed in a dry ice cooling bath and equipped with a dry ice reflux condenser. Aldehyde (7.34 mmol) was added, and the resulting solution (or suspension) was stirred for 1 h. KMnO4 (7.34 mmol, 1.16 g) was added, the cooling bath was removed, and the reaction mixture was stirred for another hour with gentle reflux of NH3. Na2SO3 (22.0 mmol, 2.78 g) was added, the reflux condenser was removed, and the NH3 was allowed to evaporate spontaneously. The dark-brown residue was treated with 6 M HCl (30 mL), and the resulting precipitate was filtered, washed with H2O (100 mL) and sat. aq NaHCO3 (20 mL). All products were recrystallized from EtOH.3-BromobenzamideColorless crystals; mp 152–156 °C (lit.6d 157–159 °C). IR (KBr): νmax = 3353, 3175, 1659, 1623, 1564, 1427, 1389, 1123, 1066, 901, 794 cm–1. 1H NMR (400 MHz): δ = 7.44 (1 H, t, J = 7.8 Hz), 7.56 (1 H, br s), 7.73 (1 H, ddd, J = 7.8, 2.0, 1.0 Hz), 7.90 (1 H, dm, J = 7.8 Hz), 8.08 (1 H, t, J = 1.8 Hz), 8.15 (1 H, br s). 13C NMR (100 MHz): δ = 122.5, 127.5, 131.1, 131.4, 134.9, 137.4, 167.3. 13 Wiberg KB, Steward R. J. Am. Chem. Soc. 1955; 77: 1786 14 Mąkosza M, Staliński K. Tetrahedron Lett. 1998; 39: 3575 Zusatzmaterial Zusatzmaterial Supporting Information
