Min Shi, Shi-Cong Cui
FULL PAPERS
1.5 g Yb(OPf)3 and 1.5 g LiClO4 were added into this solution.
7.0 g of SiO2 were poured into the resulting solution and the
mixture was stirred at room temperature for 1 h. The obtained
mixture was dried at 1208C for 48 h in an oven.
Nitration of Xylene
A yellow oil, yield: 1.48 g (82%); MS (EI): m/z l51 (M )
[HRMS calcd. for C8H9NO2 (151.1626): 151.0633; found:
151.0630].
1,2-Dimethyl-4-nitrobenzene: 1H NMR (CDC13, TMS,
300 MHz): d 2.38 (6H, s, CH3), 7.25 (1H, d, J 8.0 Hz, Ar),
7.94 8.0 (2H, m, Ar).
General Procedure for the Nitration of Aromatic
Compounds in the Presence of a Mixed Catalyst
l,3-Dimethyl-5-nitrobenzene: 1H NMR (CDCl3, TMS,
300 MHz): d 2.42 (6H, s, CH3), 7.30 (1H, s, Ar), 7.83 (2H, s,
Ar).
To a solution of toluene (2.1 mL, 20 mmol) and 95% nitric acid
(0.5 mg, 12 mmol) were added 15% LiClO4, 15% Yb(OPf)3,
15% MoO3 on SiO2 (50 mg) and reaction mixture was stirred at
608C for 48 h. The reaction mixture was washed with water
(l0 mL) and extracted with ether (Et2O). The solvent was
removed under reduced pressure and the residue was purified
by silica gel column chromatograph (eluent: petroleum ether/
EtOAc, 10/l) to give nitrotoluene as a yellow liquid. Total yield:
l,4-Dimethyl-2-nitrobenzene: 1H NMR (CDCl3, TMS,
300 MHz): d 2,40 (3H, s, CH3), 2.55 (3H, s, CH3), 7.20 7.33
(2H, m, Ar), 7.78 (1H, s, Ar).
1,2-Dimethyl-6-nitrobenzene: 1H NMR (CDCl3, TMS,
300 MHz): d 2.37 (6H, s, CH3), 7.08 7.45 (2H, m, Ar), 7.58
(1H, d, J 7.8 Hz, Ar).
1,3-Dimethyl-6-nitrobenzene: lH NMR (CDCl3, TMS,
300 MHz): d 2.40 (3H, s, CH3), 2.60 (3H, s, CH3), 7.11 7.16
(2H, m, Ar), 7.92 (1H, d, J 7.9 Hz, Ar).
1.32 g (80%); p:m:o 74:2:24; MS (EI): m/z 137 (M )
[HRMS calcd. for C7H7NO2 (137.1360): 137.0477; found:
137.0464].
1,4-Dimethyl-6-nitrobenzene: 1H NMR (CDCl3, TMS,
300 MHz): d 2.30 (6H, s, CH3), 7.11 7.28 (3H, m, Ar).
2-Nitrotoluene: 1H NMR (CDCl3, TMS, 300 MHz): d 2.61
(3H, s, CH3), 7.20 7.45 (2H, m, Ar), 7.48 (1H, d, J 7.5 Hz,
Ar), 7.96 (1H, d, J 7.5 Hz, Ar).
3-Nitrotoluene: lH NMR (CDCl3, TMS, 300 MHz): d 2.48
(3H, s, CH3), 7.40 7.51 (2H, m, Ar), 7.92 8.09 (2H, m, Ar).
4-Nitrotoluene: lH NMR (CDCl3, TMS, 300 MHz): d 2.48
(3H, s, CH3), 7.33 (2H, d, J 8.4Hz, Ar), 8.13 (2H, d, J
8.4Hz, Ar).
Nitration of Ethylbenzene
A yellow oil, yield: 0.86 g (68%), p:m:o 53:0:47; MS (EI):
m/z 151 (M ) [Calcd. for C8H9NO2 (151.1626): 151.0633,
Found: 151.0623 ].
2-Nitroethylbenzene: 1H NMR (CDCl3, TMS, 300 MHz):
d 1.26 (3H, t, J 7.2 Hz, CH3), 2.88 (2H, q, J 7.2 Hz, CH2),
7.10 7.60 (3H, m, Ar), 7.75 (1H, d, J 8.0 Hz, Ar).
4-Nitroethylbenzene: 1H NMR (CDCl3, TMS, 300 MHz):
d 1.27 (3H, t, J 7.2 Hz, CH3), 2.74(2H, q, J 7.2 Hz, CH2),
7.30 (2H, d, J 8.0 Hz, Ar), 8.03 (2H, d, J 8.0 Hz, Ar).
Nitration of p-Chlorobenzene
A yellow oil, yield: 194mg (55%); p:m:o 60:0:40; MS (EI):
m/z 158 (M ) [HRMS: calcd. for C6H5ClNO2 (l57.5542):
156.9931; found: 156.9915].
1
4-Nitrochlorobenzene: H NMR (CDCl3, TMS, 300 MHz):
d 7.62 (2H, d, J 8.2 Hz, Ar), 8.06 (2H, d, J 8.2 Hz, Ar).
1
2-Nitrochlorobenzene: H NMR (CDCl3, TMS, 300 MHz):
Nitration of Isopropylbenzene
d 7.30 7.36 (3H, m, Ar), 7.75 (1H, d, J 7.8 Hz, Ar).
A yellow oil, yield: 0.94g (65%); p:m:o 72:0:28; MS (EI):
m/z 165 (M ) [HRMS calcd. for C9H11NO2 (165.1892):
165.0790; found: 165.0786].
1-Isopropyl-2-nitrobenzene: 1H NMR (CDCl3, TMS,
300 MHz): d 1.30 (6H, d, J 7.8 Hz, CH3), 3.32 3.44 (1H,
m, CH), 7.15 7.65 (4H, m, Ar).
Nitration of p-Bromobenzene
A yellow solid, mp 96 1108C, yield: 1.09 g (58%); p:m:o
1-Isopropyl-4-nitrobenzene: 1H NMR (CDCl3, TMS,
300 MHz): d 1.29 (6H, d, J 7.8 Hz, CH3), 2.96 3.08 (1H,
m, CH), 7.37 (2H, d, J 8.2 Hz, Ar), 8.15 (2H, d, J 8.2 Hz,
Ar).
60:0:40; MS (EI): m/z 202 (M ) [HRMS calcd. for
C6H5BrNO2 (202.0055): 200.9425; found: 200.9410].
1
4-Nitrobromobenzene: H NMR (CDCl3, TMS, 300 MHz):
d 7.59 (2H, d, J 8.5 Hz, Ar), 8.01 (2H, d, J 8.5 Hz, Ar).
1
2-Nitrobromobenzene: H NMR (CDCl3, TMS, 300 MHz):
d 7.27 7.33 (3H, m, Ar), 7.70 (1H, d, J 7.8 Hz, Ar).
Nitration of Naphthalene
A yellow solid, mp 96 1108C, yield: 63%.
Nitration of Benzene
A yellow oil, yield: 1.10 g (74%); 1H NMR (CDCl3, TMS,
1-Nitronaphthalene: 1H NMR (CDC13, TMS, 300 MHz):
d 7.56 (1H, t, J 7.8 Hz, CH3), 7.63 (1H, t, J 7.8 Hz, Ar),
7.73 (1H, t, J 7.8 Hz, Ar), 7.97 (1H, d, J 7.8 Hz, Ar), 8.12
(1H, t, J 7.8 Hz, Ar), 8.24(1H, t, J 7.8 Hz, Ar), 8.57 (1H, d,
300 MHz): d 7 31 (2H, t, J 7.7 Hz, Ar), 7.52 7.58 (1H, m,
Ar), 8.24(2H, d, J 7.8 Hz, Ar); MS (EI): m/z 123 (M )
[HRMS calcd. for C6H5NO2 (123.1094): 123.0320; found:
123.0333].
J 7.8 Hz, Ar); MS (EI): m/z 173 (M ); anal. found: C 69.24,
H 4.17, N 7.99%; C10H7NO2 requires: C 69.36, H 4.07, N 8.09%.
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¹ 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Adv. Synth. Catal. 2003, 345, 1329 1333