10.1002/cctc.201801858
ChemCatChem
FULL PAPER
rotamers in its 1H and 13C NMR spectra. 1H NMR (300 MHz,
CDCl3) δ 7.32 – 7.20 (m, 8H), 7.18 – 7.13 (m, 2H), 3.62 – 3.54
(m, 2H), 3.52 – 3.46 (m, 2H), 2.94 (s, 3H), 2.86 (s, 3H), 2.90 –
2.79 (m, 4H), 2.05 (s, 3H), 1.84 (s, 3H). 13C NMR (75 MHz,
CDCl3) δ 170.6, 170.4, 139.3, 138.6, 128.9, 128.8, 128.7, 128.5,
126.8, 126.3, 52.6, 49.8, 36.9, 34.8, 33.8, 33.4, 22.0, 21.0.
Methyl 2-(N-methylacetamido)benzoate (3fa): White solid. 12.4
mg, 12% yield. 1H NMR (300 MHz, CDCl3) δ 8.10 (d, J = 7.9 Hz,
1H), 7.70 (t, J = 7.7 Hz, 1H), 7.49 (t, J = 7.6 Hz, 1H), 7.39 (d, J =
7.9 Hz, 1H), 3.92 (s, 3H), 3.32 (s, 3H), 1.92 (s, 3H). 13C NMR (75
MHz, CDCl3) δ 170.3, 167.9, 141.2, 131.6, 129.1, 123.2, 122.5,
122.2, 52.4, 37.2, 22.6.
N-Hexadecyl-N-methylacetamide (3ma): Yellow oil. 74.3 mg,
50% yield. IR (neat) : 2929, 2855, 1699, 1462 cm-1. This
N-Methyl-N-(3-nitrophenyl)acetamide (3ga): Yellow solid. 9.7 mg,
10% yield. H NMR (300 MHz, CDCl3) δ 8.21 – 8.20 (m, 1H),
8.12 – 8.10 (m, 1H), 7.56 – 7.62 (m, 2H), 3.34 (s, 3H), 1.92 (s,
3H). 13C NMR (75 MHz, CDCl3) δ 170.1, 148.1, 142.3, 132.1,
130.2, 118.2, 114.9, 38.2, 21.8.
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1
product was obtained as a mixture of two rotamers in its H and
1
13C NMR spectra. H NMR (300 MHz, CDCl3) δ 3.36 – 3.28 (m,
2H), 3.26 – 3.20 (m, 2H), 2.96 (s, 3H), 2.90 (s, 3H), 2.08 (s, 3H),
2.06 (s, 3H), 1.58 – 1.47 (m, 4H), 1.26 – 1.22 (m, 52H), 0.87 (t, J
= 6.6 Hz, 6H). 13C NMR (75 MHz, CDCl3) δ 170.5, 170.4, 51.0,
47.7, 36.2, 33.4, 32.1, 29.8 x 3, 29.7 x 2, 29.6, 29.5, 28.5, 27.5,
27.0, 26.9, 22.8, 22.1, 21.4, 14.3 ppm. MS m/z 297 (M+, 4), 283
(21), 282 (100), 114 (17), 100 (19), 87 (55), 86 (74), 74 (11), 55
(11); HRMS (EI) calc. for C19H39NO 297.3032, found 297.3036.
Gram scale synthesis of N-methyl-N-phenylacetamide (3aa)
N,N-dimetyhaniline (10 mmol, 1267 L), acetic anhydride (12
mmol, 1134 L) and tert-butyl hydroperoxide (10 equiv.) were
added to a suspension of CuNPs/ZY (400 mg, 1.0 mol% Cu) in
MeCN (40 mL) under air. The reaction mixture was warmed to
70 ºC and monitored by TLC and/or GLC until total conversion of
the starting material. The solvent was removed in vacuo and the
product was purified by flash column chromatography to give N-
methyl-N-phenylacetamide in 93% yield (1.39 g).
1
N,N-Diethylacetamide (3na): Yellow oil. 49.9 mg, 85% yield. H
NMR (300 MHz, CDCl3) δ 3.41 – 3.27 (m, 4H), 2.08 (s, 3H), 1.18
(t, J = 7.0 Hz, 3H), 1.12 (t, J = 7.0 Hz, 3H. 13C NMR (75 MHz,
CDCl3) δ 169.8, 42.9, 40.1, 21.6, 14.3, 13.2.
N-Methyl-N-phenylpropionamide (3ab): Yellow oil. 71.8 mg, 88%
1
yield. H NMR (300 MHz, CDCl3) δ 7.44 – 7.36 (m, 2H), 7.34 –
Acknowledgements
7.27 (m, 2H), 7.20 – 7.30 (m, 1H), 3.25 (s, 3H), 2.15 – 1.98 (m,
2H), 1.03 (t, J = 7.5 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 174.1,
144.3, 129.8, 127.4, 122.5, 37.4, 27.6, 9.8.
This work was generously supported by the Argentinian Consejo
Nacional de Investigaciones Científicas y Técnicas (CONICET,
PIP-2011-268) and Agencia Nacional de Promoción Científica y
Tecnológica (ANPCyT, Prest. BID, PICT-2014-2171), the
Spanish Ministerio de Economía y Competitividad (MINECO;
grant no. CTQ2017-88171-P) and the Generalitat Valenciana
(GV; grant no. AICO/2017/007), and the Universidad Nacional
del Sur (UNS, PGI 24/Q072), Argentina. The authors want to
thank Prof. M. A. Volpe for TPR analyses of the catalyst and
helpful discussions.
N-Methyl-N-phenylbutyramide (3ac): Orange oil. 69.1 mg, 78%
yield. H NMR (300 MHz, CDCl3) δ 7.39 – 7.31 (m, 2H), 7.30 –
7.24 (m, 1H), 7.15 – 7.07 (m, 2H), 3.19 (s, 3H), 2.03 – 1.95 (m,
2H), 1.58 – 1.46 (m, 2H), 0.74 (t, J = 7.4 Hz, 3H). 13C NMR (75
MHz, CDCl3) δ 173.5, 144.3, 129.8, 127.8, 127.4, 37.4, 36.1,
19.0, 13.9.
1
N-Methyl-N-phenylpentanamide (3ad): Colorless liquid. 74.7 mg,
1
81% yield. H NMR (300 MHz, CDCl3) δ 7.45 – 7.37 (m, 2H),
7.36 – 7.31 (m, 1H), 7.20 – 7.14 (m, 2H), 3.26 (s, 3H), 2.07 (t, J
= 7.5 Hz, 2H), 1.50 – 1.57 (m, 2H), 1.14 – 1.27 (m, 2H), 0.80 (t,
J = 7.3 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 173.5, 144.4, 129.8,
127.8, 127.4, 37.5, 33.9, 27.8, 22.5, 13.9.
Keywords: Copper Nanoparticles • Direct Oxidative Amidation •
Heterogeneous Catalysis • Tertiary Amines
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M. Breneman, J. F. Liebman), Wiley-VCH, Weinheim, 2000.
N-Methyl-N-phenylhexanamide (3ae): Light yellow liquid. 73.8
mg, 72% yield. 1H NMR (300 MHz, CDCl3) δ 7.45 – 7.37 (m, 2H),
7.36 – 7.28 (m, 1H), 7.20 – 7.12 (m, 2H), 3.25 (s, 3H), 2.05 (t, J
= 7.6 Hz, 2H), 1.51 – 1.60 (m, 2H), 1.23 – 1.09 (m, 4H), 0.81 (t,
J = 6.8 Hz, 3H).13C NMR (75 MHz, CDCl3) δ 173.6, 144.4, 129.8,
127.8, 127.4, 37.5, 34.2, 31.6, 25.4, 22.5, 14.0.
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a) T. Wieland, M. Bodanszky in The World of Peptides: A Brief History
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N-Methyl-N-phenylbenzamide (3af): White solid. 73.9 mg, 70%
1
yield. H NMR (300 MHz, CDCl3) δ 7.32 – 7.11 (m, 8H), 7.06 –
[3]
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a) W.-P. Mai, G. Song, J.-W. Yuan, L.-R. Yang, G.-C. Sun, Y.-M. Xiao,
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7.00 (m, 2H), 3.49 (s, 3H).13C NMR (75 MHz, CDCl3) δ 170.8,
144.9, 135.9, 129.7, 129.2, 128.8, 127.8, 127. 0, 126.6, 38.5.
N,N-Diethylbenzamide (3nf): Light yellow liquid. 60.0 mg, 81%
1
yield. H NMR (300 MHz, CDCl3) δ 7.38 (s, 5H), 3.55 (s, 2H),
a) L. Zhao, H. Ding, B. Zhao, C. Lu, Y. Yao Polyhedron 2014, 83, 50-
59; b) J. C.-H. Yim, J. A. Bexrud, R. O. Ayinla, D. C. Leitch, L. L.
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Shibasaki Angew. Chem. Int. Ed. 2013, 52, 223-234.
3.25 (s, 2H), 1.26 (2, 3H), 1.11 (s, 3H). 13C NMR (75 MHz,
CDCl3) δ 171.6, 137.1, 130.1, 129.3, 128.5, 126.4, 43.4, 39.5,
14.3, 13.0.
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