Synlett, Inhaltsverzeichnis Synlett 2015; 26(13): 1862-1866DOI: 10.1055/s-0034-1380811 letter © Georg Thieme Verlag Stuttgart · New York tert-Butyl Peroxybenzoate Mediated Selective and Mild N-Benzoylation of Ammonia/Amines under Catalyst- and Solvent-Free Conditions Dilip Kumar T. Yadav Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai – 400 019, India eMail: bm.bhanage@gmail.com eMail: bm.bhanage@ictmumbai.edu.in , Bhalchandra M. Bhanage* Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai – 400 019, India eMail: bm.bhanage@gmail.com eMail: bm.bhanage@ictmumbai.edu.in› InstitutsangabenArtikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract A new protocol for the synthesis of amides from tert-butyl peroxybenzoate (TBPB) and ammonia/amines has been developed under catalyst- and solvent-free conditions. The ammonia, primary and secondary amines reacted smoothly with TBPB to furnish the corresponding primary, secondary, and tertiary amides in excellent yields. TBPB proved to be an efficient and highly chemoselective benzoylating reagent for aliphatic amines in the presence of aromatic amines/ hydroxyl groups. Key words Key words tert-butyl peroxybenzoate - N-benzoylation - catalyst-free - solvent-free - amides Volltext Referenzen References and Notes 1a Humphrey JM, Chamberlin AR. Chem. Rev. 1997; 97: 2243 1b Fischbach MA, Walsh CT. Chem. Rev. 2006; 106: 3468 1c Simonovic M, Steitz TA. Biochim. Biophys. Acta 2009; 1789: 612 1d Paul HS, Robert LK, Russell FN. EP 0936864 (A1), 1999 1e Malawska B. Curr. Top. Med. Chem. 2005; 5: 69 1f Funabashi M, Yang Z, Nonaka K, Hosobuchi M, Fujita Y, Shibata T, Chi X, Van Lanen SG. Nat. Chem. Biol. 2010; 6: 581 1g Pelagalli R, Chiarotto I, Feroci M, Vecchio S. Green Chem. 2012; 14: 2251 1h Yadav DK. T, Bhanage BM. 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Lett. 2010; 12: 4876 18 General Experimental Procedure for the Synthesis of Amide from Ammonia/Amine and TBPBA mixture of TBPB (1 mmol) and requisite aq NH3 or amine (1.1 mmol) were charged in a round-bottom flask. The reaction mixture was stirred at r.t. for the indicated time, and progress of the reaction was monitored by TLC/GC. The crude product was directly purified by column chromatography (silica gel, 100–200 mesh, PE–EtOAc) to provide the desired pure product. The identity of the compound was confirmed by 1H NMR and 13C NMR spectroscopic methods. N-(4-Methoxybenzyl)benzamide (3c) 17a 1H NMR (400 MHz, CDCl3): δ = 7.77 (d, J = 7.1 Hz, 2 H), 7.48 (t, J = 7.2 Hz, 1 H), 7.41 (t, J = 7.7 Hz, 2 H), 7.27 (d, J = 8.5 Hz, 2 H), 6.87 (d, J = 8.6 Hz, 2 H), 6.45 (br s, 1 H), 4.56 (d, J = 5.56 Hz, 2 H), 3.79 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.29, 159.11, 134.43, 131.50, 130.25, 129.31, 128.57, 126.95, 114.15, 55.31, 43.63 ppm. N-(4-Fluorobenzyl)benzamide (3e) 17a 1H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 8.0 Hz, 2 H), 7.49 (t, J = 7.3 Hz, 1 H), 7.40 (t, J = 7.7 Hz, 2 H), 7.31–7.25 (m, 2 H), 7.0 (t, J = 8.6 Hz, 2 H), 6.67 (br s, 1 H), 4.58 (d, J = 5.58 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.45, 162.2 (d, J C–F = 244 Hz), 134.21, 134.07, 131.64, 129.53 (d, J C–F = 8 Hz), 128.60, 126.98, 115.56 (d, J C–F = 21 Hz), 43.33 ppm. N-(3-Chlorobenzyl)benzamide (3f) 17b 1H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 7.16 Hz, 2 H), 7.49 (t, J = 8.4 Hz, 1 H), 7.41 (t, J = 7.7 Hz, 2 H), 7.30 (s, 1 H), 7.25–7.18 (m, 3 H), 6.77 (br s, 1 H), 4.58 (d, J = 5.72 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.54, 140.34, 134.52, 134.04, 131.71, 129.99, 128.62, 127.80, 127.68, 127.01, 125.89, 43.42 ppm. N-(4-Cyanobenzyl)benzamide (3g) 17c 1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 7.9 Hz, 2 H), 7.59 (d, J = 6.6 Hz, 2 H), 7.52 (t, J = 7.3 Hz, 1 H), 7.45–7.41 (m, 4 H), 6.89 (br s, 1 H), 4.67 (d, J = 6.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.67, 143.96, 133.76, 132.47, 131.93, 128.70, 128.19, 127.02, 118.73, 111.21, 43.48 ppm. Zusatzmaterial Zusatzmaterial Supporting Information
