LETTER
Facile C–N Bond Formation
487
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under vacuum and H2O (20 mL) was added into the residue.
It was then extracted by EtOAc. The combined organic
layers were dried over anhyd MgSO4 and evaporated under
vacuum to obtain the crude product. Pure product was
obtained by column chromatography on silica gel.
(33) 2-Chloro-N-(4-methoxyphenyl)-5-methylaniline (8l)
Orange oil. IR (KBr): n = 3402, 3038, 2999, 2952, 2930,
2850, 2834, 1600, 1580, 1513, 1455, 1441, 1398, 1294,
1245, 1180, 1044, 829, 794 cm–1. 1H NMR (300 MHz,
CDCl3): d = 2.20 (s, 3 H, CH3), 3.81 (s, 3H, OCH3), 5.88 (br
s , 1 H, NH), 6.53 (d, J = 8.1 Hz, 1 H, ArH), 6.89 (d, J = 8.7
Hz, 1 H, ArH), 7.12 (d, J = 8.7 Hz, 1 H, ArH), 7.17 (d,
J = 8.1 Hz, 1 H, ArH) ppm. 13C NMR (75 MHz, CDCl3): d =
21.3 (CH3), 55.5 (OCH3), 114.4 (CH), 114.7 (CH), 117.1
(C), 120.0 (CH), 124.6 (CH), 129.1 (CH), 134.2 (C), 137.5
(C), 141.7 (C), 156.3 (C) ppm. ESI-MS: m/z (%) = 248 (6)
[M + 1], 213 (18), 198 (21), 140 (35), 123 (100), 113 (24),
108 (39).
(16) Raposo, M. M. M.; Oliveira-Camposa, A. M. F.; Shannon,
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(34) 2-Chloro-N-(4-methoxyphenyl)acetamide (10)37
White solid; mp 120–122 °C. 1H NMR (300 MHz, CDCl3):
d = 3.81 (s, 3 H, OCH3), 4.19 (s, 2 H, CH2), 6.89 (d, J = 8.8
Hz, 2 H, ArH), 7.44 (d, J = 8.8 Hz, 2 H, ArH), 8.15 (s, 1 H,
NH) ppm. 13C NMR (75 MHz, CDCl3): d = 42.8 (OCH3),
55.5 (CH2), 114.2 (CH), 122.0 (CH), 129.6 (C), 157.1 (C),
163.6 (C) ppm.
(35) 2-(2-Chloro-5-methylphenoxy)-N-(4-
(25) Greiner, A. Tetrahedron Lett. 1989, 30, 931.
(26) Wadia, M. S.; Patil, D. V. Synth. Commun. 2003, 33, 2725.
(27) Acemoglu, M.; Allmendinger, T.; Calienni, J.; Cercus, J.;
Loiseleur, O.; Sedelmeier, G. H.; Xu, D. Tetrahedron 2004,
60, 11571.
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2002, 2412.
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2005, 44, 7961.
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Chandrasekhar, S.; Reddy, C. R.; Shin, D.-S. Tetrahedron
Lett. 2008, 49, 3827.
methoxyphenyl)acetamide (11)
White solid; mp 134–136 °C. 1H NMR (300 MHz, CDCl3):
d = 2.35 (s, 3 H, CH3), 3.81 (s, 3 H, OCH3), 4.64 (s, 2 H,
CH2), 6.78 (s, 1 H, ArH), 6.82 (d, J = 8.1 Hz, 1 H, ArH), 6.90
(d, J = 8.8 Hz, 2 H, ArH), 7.29 (d, J = 14.0 Hz, 1 H, ArH),
7.52 (d, J = 8.8 Hz, 2 H, ArH), 8.75 (s, 1 H, NH) ppm. 13
C
NMR (75 MHz, CDCl3): d = 21.3 (CH3), 55.5 (OCH3), 68.3
(CH2), 114.2 (CH), 115.1 (C), 119.8 (C), 121.6 (CH), 123.8
(C), 130.0 (C), 138.6 (C), 152.5 (C), 161.8 (C), 165.3 (C)
ppm.
(36) 4-Phenethyl-2H-benzo[b][1,4]oxazin-3 (4H)-one (9b)
White solid. IR (KBr): n = 3421, 2930, 1682, 1409, 1058,
743 cm–1. 1H NMR (300 MHz, CDCl3): d = 2.96 (t, J = 9.0
Hz, 2 H, CH2), 4.14 (t, J = 9.0 Hz, 2 H, CH2), 4.58 (s, 2 H,
OCH2CO), 7.00–7.02 (m, 4 H, ArH), 7.25–7.34 (m, 5 H,
ArH) ppm. 13C NMR (75 MHz, CDCl3): d = 33.5 (CH2), 42.7
(CH2), 67.7 (OCH2CO), 114.9 (CH), 117.4 (CH), 123.0
(CH), 124.0 (CH), 126.9 (CH), 128.5 CH), 128.7 (CH),
128.9 (CH), 138.2 (C), 145.5 (C), 164.3 (CO) ppm.
(37) Baraldi, P. G.; Preti, D.; Tabrizi, M. A.; Fruttarolo, F.;
Saponaro, G.; Baraldi, S.; Romagnoli, R.; Moorman, A. R.;
Gessi, S.; Varani, K.; Borea, P. A. Bioorg. Med. Chem. 2007,
15, 2514.
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(b) Warren, L. A.; Smiles, S. J. Chem. Soc. 1930, 1327.
(32) General Procedure of One-Pot Reaction for the C–N
Bond Formation (8)
To a magnetically stirred solution of the appropriate primary
amine 7 (1.0 mmol) and Cs2CO3 (3.2 mmol) in dry DMF
cooled by ice bath were added chloroacetyl chloride (1.2
mmol) and 6 (1.1 mmol). The reaction mixture was then
stirred for 30 min at r.t. and placed into microwave oven
(600 W, 120 °C) and irradiated for 20–60 min or under
conventional heating for 3–6 h. The solvent was removed
Synlett 2010, No. 3, 483–487 © Thieme Stuttgart · New York