(d, J = 8.94 Hz, 2H), 4.26 (s, 2H), 3.72 (s, 3H). 13C NMR
(75 MHz, CDCl3, ppm) d 152.3, 142.4, 139.7, 128.7, 127.6, 127.2,
115.0, 114.2, 55.9, 49.3. ESI-MS m/z 214.2 [M + H]+.
(s, 3H). 13C NMR (150 MHz, DMSO-d6, ppm) d 169.1, 155.0,
136.9, 135.4, 135.3, 129.7, 129.0, 127.6, 112.5, 110.1, 46.2, 21.1.
HR-MS [M + H]+ m/z Calcd for C15H15N2O4: 287.1032. Found:
287.1036.
N-Propylnaphthalen-1-amine (3i¢)25
2-(Dodecylamino)benzoic acid (3n¢)27
Eluent petroleum–ethyl acetate (5 : 1). Yield 154 mg (83%). Pale
1
yellow oil. H NMR (300 MHz, CDCl3, ppm) d 7.76 (d, J =
After completion of the reaction, the resulting solution was
adjusted to pH = 6–7 with HCl (1 M), and the following work-
up was performed according to the general procedure. Eluent
petroleum–ethyl acetate (25 : 1). Yield 265 mg (87%). White
6.54 Hz, 2H), 7.41–7.38 (m, 2H), 7.33 (t, J = 7.91 Hz, 1H), 7.20
(d, J = 7.91 Hz, 1H), 7.58 (d, J = 7.57 Hz, 1H), 4.29 (s, br, 1H),
3.20 (t, J = 7.05 Hz, 2H), 1.79–1.71 (m, 2H), 1.07–1.02 (m, 3H).
13C NMR (75 MHz, CDCl3, ppm) d 143.7, 134.4, 128.8, 126.8,
125.8, 124.7, 123.4, 119.9, 117.2, 104.3, 46.1, 22.7, 12.0. ESI-MS
m/z 186.1 [M + H]+.
◦
◦
1
solid, m.p. 77–78 C (lit.27 80–81 C). H NMR (600 MHz,
DMSO-d6, ppm) d 12.37 (s, br, 1H), 7.77 (d, J = 8.25 Hz, 1H),
7.33 (t, J = 7.91 Hz, 1H), 6.69 (d, J = 8.25 Hz, 1H), 6.53 (t, J =
7.56 Hz, 1H), 3.14 (t, J = 6.88 Hz, 2H), 1.57 (t, J = 7.22 Hz,
2H), 1.35 (s, 2H), 1.23 (s, 16H), 0.85 (t, J = 6.88 Hz, 3H). 13C
NMR (150 MHz, DMSO-d6, ppm) d 170.5, 151.5, 134.9, 132.2,
114.4, 111.5, 110.2, 42.5, 31.8, 29.5, 29.2, 29.1, 27.0, 22.6, 14.4.
ESI-MS m/z 306.4 [M + H]+, m/z 328.4 [M + Na]+.
4-Bromo-N-propylaniline (3j¢)
Eluent petroleum–ethyl acetate (10 : 1). Yield 173 mg (81%).
1
White oil. H NMR (600 MHz, CDCl3, ppm) d 7.22 (d, J =
8.94 Hz, 2H), 6.45 (d, J = 8.94 Hz, 2H), 3.65 (s, br, 1H), 3.01 (t,
J = 6.88 Hz, 2H), 1.63–1.57 (m, 2H), 0.97 (t, J = 7.22 Hz, 3H).
13C NMR (150 MHz, CDCl3, ppm) d 147.5, 131.9, 114.3, 108.5,
45.8, 22.6, 11.7. HR-MS [M + H]+ m/z Calcd for C9H13BrN:
214.0231. Found: 214.0235.
2-(5-Hydroxypentylamino)nicotinic acid (3o¢)
After completion of the reaction, the resulting solution was
adjusted to pH = 6–7 with HCl (1 M), and the following work-
up was performed according to the general procedure. Eluent
petroleum–ethyl acetate (5 : 1). Yield 199 mg (89%). White solid,
N-Cyclohexylnaphthalen-2-amine (3k¢)26
◦
1
m.p. 91–92 C. H NMR (300 MHz, DMSO-d6, ppm) d 12.99
(s, br, 1H), 8.24 (d, J = 3.10 Hz, 1H), 8.11 (s, br, 1H), 8.05 (d,
J = 7.91 Hz, 1H), 6.57 (dd, J = 7.74 Hz, 4.65 Hz, 1H), 4.37
(s, br, 1H), 3.45-3.37 (m, 4H), 1.61–1.54 (m, 2H), 1.48–1.43 (m,
2H), 1.37–1.32 (m, 2H). 13C NMR (150 MHz, DMSO-d6, ppm)
d 169.4, 158.8, 153.8, 140.6, 111.2, 106.2, 61.1, 40.7, 32.8, 29.5,
23.6. HR-MS [M + H]+ m/z Calcd for C11H17N2O3: 225.1239.
Found: 225.1237.
Eluent petroleum–ethyl acetate (3 : 1). Yield 162 mg (72%).
White solid, m.p. 183-185 ◦C. 1H NMR (300 MHz, CDCl3, ppm)
d 7.65–7.57 (m, 3H), 7.33 (t, J = 7.40 Hz, 1H), 7.15 (t, J =
7.23 Hz, 1H), 6.84-6.79 (m, 2H), 3.74 (s, br, 1H), 3.41–3.38 (m,
1H), 2.11 (d, J = 12.38 Hz, 2H), 1.81–1.64 (m, 3H), 1.47–1.12
(m, 5H). 13C NMR (75 MHz, CDCl3, ppm) d 144.9, 135.3, 129.0,
127.7, 127.3, 126.3, 125.8, 121.8, 118.3, 104.9, 51.8, 33.3, 26.0,
25.1. ESI-MS m/z 226.2 [M + H]+.
2-(5-Hydroxypentylamino)-3-nitrobenzoic acid (3l¢)
Acknowledgements
After completion of the reaction, the resulting solution was
adjusted to pH = 6–7 with HCl (1 M), and the following work-
up was performed according to the general procedure. Eluent
petroleum–ethyl acetate (2 : 1). Yield 244 mg (91%). Yellow solid.
m.p. 138–140 ◦C. 1H NMR (600 MHz, DMSO-d6, ppm) d 13.45
(s, br, 1H), 8.58 (s, br, 1H), 8.08 (d, J = 6.19 Hz, 1H), 7.97
(d, J = 8.25 Hz, 1H), 6.75 (t, J = 7.91 Hz, 1H), 4.36 (s, br,
1H), 3.36 (t, J = 6.53 Hz, 2H), 2.83 (t, J = 6.88 Hz, 2H), 1.59–
1.55 (m, 2H), 1.42–1.37 (m, 2H), 1.34–1.29 (m, 2H). 13C NMR
(150 MHz, DMSO-d6, ppm) d 169.5, 145.7, 137.3, 137.2, 131.7,
117.1, 114.9, 61.0, 46.3, 32.5, 29.8, 23.3. HR-MS [M + H]+ m/z
Calcd for C12H17N2O5: 269.1137. Found: 269.1142.
This work was supported by the National Natural Science
Foundation of China (Grant No. 20672065 and 20972083),
Chinese 863 Project (Grant No. 2007AA02Z160) and the Key
Subject Foundation from Beijing Department of Education
(XK100030514).
References
1 M. Negwer, in Organic-Chemical Drugs and their Synonyms: An
International Survey, 7th edn, Akademie Verlag: Berlin, 1994.
2 N-Arylation of anilines: (a) F. Ullmann, Ber. Dtsch. Chem. Ges., 1903,
36, 2382; (b) S. Gauthier and J. M. J. Fre´chet, Synthesis, 1987, 383;
(c) A. J. Paine, J. Am. Chem. Soc., 1987, 109, 1496; (d) R. Gujadhur,
D. Venkataraman and J. T. Kintigh, Tetrahedron Lett., 2001, 42, 4791.
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F. Tao, J. Am. Chem. Soc., 1998, 120, 12459; (f) J. B. Arterburn,
M. Pannala and A. M. Gonzalez, Tetrahedron Lett., 2001, 42, 1475.
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Volante, Tetrahedron Lett., 2001, 42, 3251.
3 For reviews, see: (a) J. F. Hartwig, Angew. Chem., Int. Ed., 1998,
37, 2046; (b) J. P. Wolfe, S. Wagaw, J.-F. Marcoux and S. L.
Buchwald, Acc. Chem. Res., 1998, 31, 805; (c) A. R. Muci and S. L.
Buchwald, Topics in Current Chemistry, Springer-Verlag: Germany,
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Chem., 1999, 576, 125; (e) J. F. Hartwig, Acc. Chem. Res., 1998, 31,
852.
2-(4-Methylbenzylamino)-5-nitrobenzoic acid (3m¢)
After completion of the reaction, the resulting solution was
adjusted to pH = 6–7 with HCl (1 M), and the following work-
up was performed according to the general procedure. Eluent
petroleum–ethyl acetate (3 : 1). Yield 237 mg (83%). Yellow solid.
m.p. 253–254 ◦C. 1H NMR (300 MHz, DMSO-d6, ppm) d 13.54
(s, br, 1H), 9.15 (t, br, J = 5.68 Hz, 1H), 8.65 (d, J = 2.27 Hz,
1H), 8.13 (dd, J = 9.29 Hz, 2.75 Hz, 1H), 7.25–7.15 (m, 4H),
6.82 (d, J = 9.63 Hz, 1H), 4.57 (d, J = 5.85 Hz, 2H), 2.28
1104 | Green Chem., 2010, 12, 1097–1105
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