The Journal of Organic Chemistry
ARTICLE
5-(4-Nitrophenylamino)pentan-1-ol (7m/5e):20b Following
procedure C, 1-chloro-4-nitrobenzene (790 mg, 5.0 mmol) was allowed
to react with 5-aminopentan-1-ol (775 mg, 7.5 mmol) for 18 h at 110 °C.
The crude brown oil was purified by flash chromatography on silica gel
Sciences (KSCX2-YW-R-215), and the National Major Scientific
and Technological Program for Drug Discovery (2009ZX09103-
101).
1
to provide 67% yield of the desired product as a yellow oil. H NMR
’ REFERENCES
(400 MHz, CDCl3) δ 8.03 (d, J = 9.2 Hz, 2H), 6.49 (d, J = 9.2 Hz, 2H),
3.64 (t, J = 6.2 Hz, 2H), 3.18 (t, J = 6.2 Hz, 2H), 1.69ꢀ1.58 (m, 4H), 1.48
(m, 2H) ppm.
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N1-Benzyl-N4-pentylbenzene-1,4-diamine (9): A flask was
charged with CuBr (14 mg, 0.1 mmol, 1 mol %), L5 (32 mg, 0.2 mmol,
2 mol %), Cs2CO3 (9.75 g, 30.0 mmol), and 1-bromo-4-iodobenzene
(2.82 g, 10.0 mmol). The flask was evacuated and backfilled with argon.
Hexan-1-amine (1.01 g, 10 mmol) and DMSO (10 mL) were added to
the flask under argon atmosphere. Then the mixture was stirred for 48 h
at 65 °C. Then benzylamine (1.07 g, 10.0 mmol) was added subsquently.
The mixture was heated at 120 °C for 60 h. The mixture was allowed to
cool to room temperature and then was diluted with ethyl acetate and
passed through a fritted glass filter to remove the inorganic salts, then the
solvent was removed with the aid of a rotary evaporator. The residue was
purified by flash chromatography on silica gel to provide the product as a
yellow oil (1.41 g, 50% yield). 1H NMR (400 MHz, CDCl3) δ
7.38ꢀ7.31 (m, 4H), 7.26 (m, 1H), 6.57 (m, 4H), 4.26 (s, 2H), 3.04
(t, J = 6.4 Hz, 2H), 1.58 (m, 2H), 1.42ꢀ1.24 (m, 6H), 0.91ꢀ0.84 (m,
3H) ppm; 13C NMR (125 MHz, CDCl3) δ 128.5, 127.6, 127.1, 114.8,
49.6, 45.4, 31.7, 29.7, 26.9, 22.6, 14.0 ppm; MS (EI, m/z) 283 (Mþ þ 1);
HRMS (ESI) C19H27N2 calcd [M þ H]þ 283.2174, found 283.2173.
N-Benzyl-4-(1H-pyrazol-1-yl)benzenamine (10): A flask was
charged with CuBr (14 mg, 0.1 mmol, 1 mol %), L5 (32 mg, 0.2 mmol, 2
mol %), Cs2CO3 (9.75 g, 30.0 mmol), 1-bromo-4-iodobenzene (2.82 g,
10.0 mmol), and 1H-pyrazole (680 mg, 10.0 mmol). The flask was
evacuated and backfilled with argon. DMSO (10 mL) was added to the
flask under argon atmosphere. Then the mixture was stirred for 48 h at
65 °C. Then benzylamine (1.07 g, 10.0 mmol) was added subsquently.
The mixture was heated at 120 °C for 60 h. The mixture was allowed to
cool to room temperature and then was diluted with ethyl acetate and
passed through a fritted glass filter to remove the inorganic salts, then the
solvent was removed with the aid of a rotary evaporator. The residue was
purified by flash chromatography on silica gel to provide the product as a
yellow solid (1.03 g, 41% yield). 1H NMR (400 MHz, CDCl3) δ7.76 (d,
J = 2.4 Hz, 1H), 7.67 (m, 1H), 7.42 (d, J = 8.8 Hz, 2H), 7.36 (m, 4H),
7.28 (m, 1 H), 6.68 (d, J = 8.8 Hz, 2H), 6.40 (dd, J = 8.8 Hz, 1H), 4.37 (s,
2H), 4.17 (brs, 1H) ppm; 13C NMR (125 MHz, CDCl3) δ 147.0, 140.1,
139.1, 131.8, 128.7, 127.4, 127.3, 126.6, 121.2, 113.2, 106.6, 48.5 ppm;
MS (EI, m/z) 250 (Mþ þ 1); HRMS (ESI) C16H16N3 calcd [M þ H]þ
250.1344, found 250.1343.
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’ ASSOCIATED CONTENT
Supporting Information. 1H NMR and 13C NMR spec-
S
b
tra of all compounds. This material is available free of charge via
’ AUTHOR INFORMATION
Corresponding Author
*Phone: 86-20-32015318. Fax: 86-20-32290439. E-mail: jiang_
’ ACKNOWLEDGMENT
This research was supported by a grant from the National
Natural Science Foundation (20802078, 20972160, and
20772035), 973 Program (2009CB940900), the Key Project of
the Knowledge Innovation Program of the Chinese Academy of
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dx.doi.org/10.1021/jo1026035 |J. Org. Chem. 2011, 76, 3151–3159